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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Sulfur-Donor Solvents Strongly Coordinate Pb 2+ in Hybrid Organic–Inorganic Perovskite Precursor Solutions

Strong coordination between Lewis-basic processing additives and the Lewis-acidic lead halide in hybrid organic–inorganic perovskite (HOIP) precursor solutions is required to solubilize the lead halide, and subsequently access the appropriate crystallization kinetics and attain the desired morphology of perovskite active layers. While oxygen-donor solvents and additives, such as dimethylformamide and dimethyl sulfoxide, are widely used for perovskite processing, we demonstrate here that “soft” sulfur-donor solvents exhibit stronger coordination to the “borderline soft” Lewis acid Pb 2+ center of PbI 2 relative to “hard” O-donor solvents in the precursor solution. The stronger coordination of S-donor solvents compared to O-donor solvents to Pb 2+ implies that such compounds can be useful additives to HOIP precursor solutions. Density-functional calculations of the enthalpy change resulting from the coordination of solvents to Pb 2+ provide direct numerical comparison of the strength of O-donor and S-donor coordination with Pb 2+ and expands the library of candidate S-donor compounds. Our results provide a roadmap for processing additive selection and expand the previously limited choice of perovskite processing additives to include strongly coordinating S-donor compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

La-Based Perovskite Oxide Catalysts for Alkaline Oxygen Reduction: The Importance of Electrochemical Stability

Alkaline fuel cells represent a promising energy conversion technology since they enable the use of precious metal-free electrocatalysts for the oxygen reduction reaction. Among these, La-based perovskite oxides, with great compositional and structural tunability, are especially attractive. However, we believe that the current literature lacks a thorough understanding of their inherent (in)stability issues. Here, in this study, we report on nine La-based perovskite oxide electrocatalysts for the oxygen reduction reaction, including LaMO 3 (M = Mn, Co, Ni) and LaCo x M 1–x O 3 (M = Mn, Ni; x = 0.9, 0.5, 0.1). While some exhibited initial promising activity, they all degraded significantly, even after brief electrochemical testing. Through comprehensive structural characterization of LaCo 0.9 Mn 0.1 O 3 , particularly scanning transmission electron microscopy, we found evidence to support a degradation mechanism in which the B-site cation species irreversibly leach from the perovskite under testing conditions. A sample cycled 10 000 times from +0.4 to +1.2 V vs reversible hydrogen electrode (RHE) showed an amorphous La oxide shell 1–2 nm thick. Bulk analyses showed that B-site leaching also occurs for samples soaked in 1 M KOH or pure EtOH. The mechanistic insights provided here should help inform the future design of La-based perovskite oxide electrocatalysts for alkaline fuel cells and stress the importance of stability metrics validating claims of promising electrocatalytic activity.

Seok, Jeesoo↗
DOE OSTI2023

Kinetic Suppression of Photoinduced Halide Migration in Wide Bandgap Perovskites via Surface Passivation

In this work, we study the kinetics of photoinduced halide migration in FA 0.8 Cs 0.2 Pb(I 0.8 Br 0.2 ) 3 wide (~1.69 eV) bandgap perovskites and show that halide migration slows down following surface passivation with (3-aminopropyl) trimethoxysilane (APTMS). We use scanning Kelvin probe microscopy (SKPM) to probe the contact potential difference (CPD) shift under illumination and the kinetics of surface potential relaxation in the dark. Our results show that APTMS-passivated perovskites exhibit a smaller CPD shift under illumination and a slower surface potential relaxation in the dark. We compare the evolution of the photoluminescence spectra of APTMS-passivated and unpassivated perovskites under illumination. We find that APTMS-passivated perovskites exhibit more than 5 times slower photoluminescence red-shift, consistent with the slower surface potential relaxation as observed by SKPM. In conclusion, these observations provide evidence for kinetic suppression of photoinduced halide migration in APTMS-passivated samples, likely due to reduced halide vacancy densities, opening avenues to more efficient and stable devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ambient Pressure XPS Investigation of Thermally Stable Halide Perovskite Solar Cells via Post-Treatment

Long-term thermal stability is one limiting factor that impedes the commercialization of perovskite solar cell. Inspired by our prior results from machine learning, we discover that coating a thin layer of 4,4’-dibromotriphenylamine (DBTPA) on top of a CH 3 NH 3 PbI 3 (MAPbI 3 ) thin film can improve the stability of the resultant perovskite solar cells. The passivated perovskite solar cells retained more than 96% of their initial power conversion efficiency over 1000 h at 85 °C in N2 atmosphere without encapsulation. Near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) was employed to investigate the evolution of composition and evaluate thermal and moisture stability by in-situ studies. A comparison between pristine MAPbI 3 films and DBTPA-treated films shows the DBTPA treatment suppresses the escape of iodide and methylamine up to 150 °C under 5 mbar humidity. Furthermore, we have used ATR-FTIR and XPS to probe the interactions between DBTPA and MAPbI3 surface. The results prove that DBTPA coordinate with perovskite by Lewis acid-base and cation-π interaction. Compared with the 19.9% efficiency of pristine sample, the champion efficiency of passivated sample reaches 20.6%. Finally, our results reveal DBTPA as a new post-treating molecule that not only leads to the improvement of photovoltaic efficiency but also thermal and moisture stability.

14 SOLAR ENERGY↗
DOE OSTI2022

Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Voltage-induced halide segregation greatly limits the optoelectronic applications of mixed-halide perovskite devices, but a mechanistic explanation behind this phenomenon remains unclear. In this work, we use electron microscopy and elemental mapping to directly measure the halide redistribution in mixed-halide perovskite solar cells with quasi-ion-impermeable contact layers under different bias polarities to find iodide and bromide accumulation at the cathode and anode, respectively. This is consistent with a mechanism based on preferential iodide oxidation at the anode, leading to unbalanced I$^{+}_{i}$, I$^{-}_{X}$, and Br$^{-}_{X}$ fluxes. Importantly, switching the anode from "inert" Au to "active" Ag prevents segregation because Ag oxidation precludes the oxidation of lattice iodide, which suggests employing redox-active additives as a general strategy to suppress halide segregation. Finally, these results show that halide perovskite devices operate as solid-state electrochemical cells when threshold voltages are exceeded, providing fresh insight to understand the impacts of voltage bias on halide perovskite devices.

14 SOLAR ENERGY↗
DOE OSTI2022

Supramolecular Assembly of Halide Perovskite Building Blocks

The structural diversity and tunable optoelectronic properties of halide perovskites originate from the rich chemistry of the metal halide ionic octahedron [MX 6 ] n- (M = Pb 2+ , Sb 3+ , Te 4+ , Sn 4+ , Pt 4+ , etc.; X = Cl - , Br - , and I - ). The properties of the extended perovskite solids are dictated by the assembly, connectivity, and interaction of these octahedra within the lattice environment. Hence, the ability to manipulate and control the assembly of the octahedral building blocks is paramount for constructing new perovskite materials. Here, we propose a systematic supramolecular strategy for the assembly of [MX 6 ] n- octahedra into a solid extended network. Interaction of alkali metal-bound crown ethers with the [M(IV)X 6 ] 2- octahedron resulted in a structurally and optoelectronically tunable "dumbbell" structural unit in solution. Further, single crystals with diverse packing geometries and symmetries will form as the solid assembly of this new supramolecular building block. This supramolecular assembly route introduces a new general strategy for designing halide perovskite structures with potentially new optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Ultrafast Carrier Self-Trapping Driven by Strong Exciton–Phonon Coupling in 2D MA 3 Bi 2 I 6 Cl 3 Perovskite

Two-dimensional (2D) hybrid bismuth halide perovskites have emerged as promising lead-free materials for optoelectronic applications due to their solution processability and tunable structures. Here, in this study, we investigate 2D layered hybrid perovskite MA 3 Bi 2 I 6 Cl 3 using temperature-dependent photoluminescence (PL) and femtosecond transient absorption spectroscopy. Our results reveal strong coupling between excitons and phonons, evidenced by giant Huang–Rhys factors, coherent phonon oscillations, and ultrafast carrier self-trapping into small-polaron and self-trapped exciton (STE) states. These processes appear as time-dependent ground-state bleach and photoinduced absorption features, highlighting the influence of the lattice in carrier dynamics. Wavelength- and time-resolved measurements reveal that PL emission is dominated by STEs, while free exciton emission is weak and short-lived. By comparing 2D MA 3 Bi 2 I 6 Cl 3 with 0D MA 3 Bi 2 I 9 , which contains molecularly isolated [BiI 6 ] 3− octahedra and 2D MA 3 Bi 2 Br 9 perovskites, we demonstrate how halide composition and structural dimensionality influence the balance between free exciton populations and carrier localization. These insights uncover the intrinsic kinetic landscape of photoexcited states in MA 3 Bi 2 I 6 Cl 3 . Overall, our study contributes to a mechanistic understanding of exciton–phonon interactions in lead-free 2D perovskites.

Pradeep, Kodimana Ramakrishnan [Northwestern Univ.↗
DOE OSTI2020

Simple descriptor derived from symbolic regression accelerating the discovery of new perovskite catalysts

Symbolic regression (SR) is an approach of interpretable machine learning for building mathematical formulas that best fit certain datasets. In this work, SR is used to guide the design of new oxide perovskite catalysts with improved oxygen evolution reaction (OER) activities. A simple descriptor, μ/t, where μ and t are the octahedral and tolerance factors, respectively, is identified, which accelerates the discovery of a series of new oxide perovskite catalysts with improved OER activity. We successfully synthesise five new oxide perovskites and characterise their OER activities. Remarkably, four of them, Cs 0.4 La 0.6 Mn 0.25 Co 0.75 O 3 , Cs 0.3 La 0.7 NiO 3 , SrNi 0.75 Co 0.25 O 3 , and Sr 0.25 Ba 0.75 NiO 3 , are among the oxide perovskite catalysts with the highest intrinsic activities. Our results demonstrate the potential of SR for accelerating the data-driven design and discovery of new materials with improved properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO 3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structural descriptor for enhanced spin-splitting in 2D hybrid perovskites

Abstract Two-dimensional (2D) hybrid metal halide perovskites have emerged as outstanding optoelectronic materials and are potential hosts of Rashba/Dresselhaus spin-splitting for spin-selective transport and spin-orbitronics. However, a quantitative microscopic understanding of what controls the spin-splitting magnitude is generally lacking. Through crystallographic and first-principles studies on a broad array of chiral and achiral 2D perovskites, we demonstrate that a specific bond angle disparity connected with asymmetric tilting distortions of the metal halide octahedra breaks local inversion symmetry and strongly correlates with computed spin-splitting. This distortion metric can serve as a crystallographic descriptor for rapid discovery of potential candidate materials with strong spin-splitting. Our work establishes that, rather than the global space group, local inorganic layer distortions induced via appropriate organic cations provide a key design objective to achieve strong spin-splitting in perovskites. New chiral perovskites reported here couple a sizeable spin-splitting with chiral degrees of freedom and offer a unique paradigm of potential interest for spintronics.

42 ENGINEERING↗
DOE OSTI2022

A charge transfer framework that describes supramolecular interactions governing structure and properties of 2D perovskites

The elucidation of structure-to-function relationships for two-dimensional (2D) hybrid perovskites remains a primary challenge for engineering efficient perovskite-based devices. By combining insights from theory and experiment, we describe the introduction of bifunctional ligands that are capable of making strong hydrogen bonds within the organic bilayer. We find that stronger intermolecular interactions draw charge away from the perovskite layers, and we have formulated a simple and intuitive computational descriptor, the charge separation descriptor (CSD), that accurately describes the relationship between the Pb-I-Pb angle, band gap, and in-plane charge transport with the strength of these interactions. A higher CSD value correlates to less distortion of the Pb-I-Pb angle, a reduced band gap, and higher in-plane mobility of the perovskite. These improved material properties result in improved device characteristics of the resulting solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

An embedded interfacial network stabilizes inorganic CsPbI3 perovskite thin films

Abstract The black perovskite phase of CsPbI 3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI 2 -based interfacial microstructure into otherwise-unstable CsPbI 3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and exhibit enhanced long-term stability of the black phase (beyond 2.5 years in a dry environment), due to increasing the phase transition energy barrier and limiting the spread of potential yellow phase formation to structurally isolated domains of the grid. This stabilizing effect is readily achieved at the device level, where unencapsulated CsPbI 3 perovskite photodetectors display ambient-stable operation. These findings provide insights into the nature of phase destabilization in emerging CsPbI 3 perovskite devices and demonstrate an effective stabilization procedure which is entirely orthogonal to existing approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Suppressing phase disproportionation in quasi-2D perovskite light-emitting diodes

Electroluminescence efficiencies and stabilities of quasi-two-dimensional halide perovskites are restricted by the formation of multiple-quantum-well structures with broad and uncontrollable phase distributions. Here, we report a ligand design strategy to substantially suppress diffusion-limited phase disproportionation, thereby enabling better phase control. We demonstrate that extending the π-conjugation length and increasing the cross-sectional area of the ligand enables perovskite thin films with dramatically suppressed ion transport, narrowed phase distributions, reduced defect densities, and enhanced radiative recombination efficiencies. Consequently, we achieved efficient and stable deep-red light-emitting diodes with a peak external quantum efficiency of 26.3% (average 22.9% among 70 devices and cross-checked) and a half-life of ~220 and 2.8 h under a constant current density of 0.1 and 12 mA/cm 2 , respectively. Our devices also exhibit wide wavelength tunability and improved spectral and phase stability compared with existing perovskite light-emitting diodes. These discoveries provide critical insights into the molecular design and crystallization kinetics of low-dimensional perovskite semiconductors for light-emitting devices.

14 SOLAR ENERGY↗
DOE OSTI2023

Uncovering temperature-dependent exciton-polariton relaxation mechanisms in hybrid organic-inorganic perovskites

Hybrid perovskites have emerged as a promising material candidate for exciton-polariton (polariton) optoelectronics. Thermodynamically, low-threshold Bose-Einstein condensation requires efficient scattering to the polariton energy dispersion minimum, and many applications demand precise control of polariton interactions. Thus far, the primary mechanisms by which polaritons relax in perovskites remains unclear. In this work, we perform temperature-dependent measurements of polaritons in low-dimensional perovskite wedged microcavities achieving a Rabi splitting of ℏΩ Rabi = 260 ± 5 meV. We change the Hopfield coefficients by moving the optical excitation along the cavity wedge and thus tune the strength of the primary polariton relaxation mechanisms in this material. We observe the polariton bottleneck regime and show that it can be overcome by harnessing the interplay between the different excitonic species whose corresponding dynamics are modified by strong coupling. This work provides an understanding of polariton relaxation in perovskites benefiting from efficient, material-specific relaxation pathways and intracavity pumping schemes from thermally brightened excitonic species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interfacial alloying between lead halide perovskite crystals and hybrid glasses

The stellar optoelectronic properties of metal halide perovskites provide enormous promise for next-generation optical devices with excellent conversion efficiencies and lower manufacturing costs. However, there is a long-standing ambiguity as to whether the perovskite surface/interface (e.g. structure, charge transfer or source of off-target recombination) or bulk properties are the more determining factor in device performance. Here we fabricate an array of CsPbI 3 crystal and hybrid glass composites by sintering and globally visualise the property-performance landscape. Our findings reveal that the interface is the primary determinant of the crystal phases, optoelectronic quality, and stability of CsPbI 3 . In particular, the presence of a diffusion “alloying” layer is discovered to be critical for passivating surface traps, and beneficially altering the energy landscape of crystal phases. However, high-temperature sintering results in the promotion of a non-stoichiometric perovskite and excess traps at the interface, despite the short-range structure of halide is retained within the alloying layer. By shedding light on functional hetero-interfaces, our research offers the key factors for engineering high-performance perovskite devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite

Abstract In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.

25 ENERGY STORAGE↗
DOE OSTI2026

Single-photon emission from two-dimensional perovskites channeled through low-energy edge states

Two-dimensional perovskites, an emerging family of van der Waals materials with an innate quantum-well structure, exhibit remarkable optical characteristics and compositional tunability. However, their potential as a source for quantum emitters remains unexplored. Here, we investigate low-energy edge states unique to two-dimensional perovskites using comprehensive photoluminescence imaging and spectroscopy, to further leverage them towards uncovering quantum emitters. In contrast to above-bandgap excitation, spatially localized single-photon emitters are realized through sub-bandgap energy excitation at the edges in exfoliated single crystals. Specifically, the sub-bandgap excitation facilitates efficient access to deeply confined states within the bandgap, as charge carriers can channel through low-energy edge states while inhibiting competing processes. Furthermore, we demonstrate single-photon emitters from artificially created edges via strain as well as from two-dimensional perovskites with different quantum-well thicknesses. Our findings provide promising opportunities in the development of two-dimensional quantum emitters, where two-dimensional perovskites may provide added functionalities with versatility in material design, fabrication, and scalability.

Materials for optics↗
DOE OSTI2020

Simplified interconnection structure based on C 60 /SnO 2-x for all-perovskite tandem solar cells

The efficiencies of all-perovskite tandem devices are improving quickly. However, their complex interconnection layer (ICL) structures – with typically four or more layers deposited by different processes – limit their prospects for applications. Here, we report an ICL in all-perovskite tandem cells consisting merely of a fullerene layer and a SnO 2-x (0 60 layer is unintentionally n-doped by iodine ions from the perovskite and thus acts as an effective electron collecting layer. The SnO 2-x layer, formed by the incomplete oxidization of tin (x=1.76), has ambipolar carrier transport property enabled by the presence of a large density of Sn 2+ . The C 60 /SnO 1.76 ICL forms Ohmic contacts with both wide and narrow bandgap perovskite subcells with low contact resistivity. The ICL boosts the efficiencies of small-area tandem cells (5.9 mm 2 ) and large-area tandem cells (1.15 cm 2 ) to 24.4% and 22.2%, respectively. Lastly, the tandem cells remain 94% of its initial efficiency after continues 1-sun illumination for 1,000 hours.

14 SOLAR ENERGY↗