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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Superior photo-carrier diffusion dynamics in organic-inorganic hybrid perovskites revealed by spatiotemporal conductivity imaging

Abstract The outstanding performance of organic-inorganic metal trihalide solar cells benefits from the exceptional photo-physical properties of both electrons and holes in the material. Here, we directly probe the free-carrier dynamics in Cs-doped FAPbI 3 thin films by spatiotemporal photoconductivity imaging. Using charge transport layers to selectively quench one type of carriers, we show that the two relaxation times on the order of 1 μs and 10 μs correspond to the lifetimes of electrons and holes in FACsPbI 3 , respectively. Strikingly, the diffusion mapping indicates that the difference in electron/hole lifetimes is largely compensated by their disparate mobility. Consequently, the long diffusion lengths (3~5 μm) of both carriers are comparable to each other, a feature closely related to the unique charge trapping and de-trapping processes in hybrid trihalide perovskites. Our results unveil the origin of superior diffusion dynamics in this material, crucially important for solar-cell applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Observation of [VCu1–Ini2+VCu1–] Defect Triplets in Cu-Deficient CuInS2

Copper indium disulfide (CuInS2) is a semiconductor with a direct energy band gap of 1.53 eV, an optimal value for highly efficient thin-film solar cells. But it has reached only ~ 11 % power conversion efficiency, far less than the theoretically achievable value of ~ 30 %. The cause of this low performance is not understood. A single crystal grown from 1 mol% Cu-deficient melt was studied, using atomic resolution high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) and electron dispersive spectroscopy (EDS). While the bulk crystal is exactly stoichiometric CuInS2, it contains nanometer-thick, structurally coherent, Cu-deficient interphases that form along rotational twin boundaries in the {112} plane. Transition zones from bulk crystal to interphase are observed, where In is seen to move from its normal site InIn in the chalcopyrite structure to a tetrahedral interstitial site Ini, while Cu remains in its normal CuCu position. Two InIn rows of the bulk crystal merge into one row of Ini, causing excess Ini in the interphase. The concentrations of CuCu and Ini reflect a ratio of Cu vacancies, VCu, to excess Ini of ~ 2. Their relative lattice positions, and the high electrical resistivity of the crystal, suggests that VCu and excess Ini ‘precipitate’ as self-compensating, electrically neutral, [VCu1- Ini2+ VCu1-] defect triplets. This is the first atomic-level observation of the ordered defect that has been invoked as the basic structural modifier in chalcopyrite compound homologs. The interphases introduce an optical gap of 1.47 eV. Electron trapping in band tail states, evident from a photoconductivity exponent of 0.54, is the likely cause of an unusually low electron mobility of 0.1 cm2V-1s-1. The overall result is that making CuInS2 slightly copper-poor inserts nanometer-thick layers of the interphase into the bulk crystal. This study shows that apparently conflicting results of the effect of Cu deficiency on CuInS2 thin-film solar cells may be resolved by analyzing structure and composition at nanometer spatial resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Why Perovskite Thermal Stress is Unaffected by Thin Contact Layers

Metal halide perovskite photovoltaics have emerged as a high efficiency, low-cost alternative that can potentially rival or enhance conventional silicon technology. Despite exceptional initial power conversion efficiencies, achieving compliance with international standards and widespread adoption requires further enhancements to their operational stability. Notably, addressing mechanical strain and stress in brittle perovskites has emerged as a pivotal approach to mitigate chemical degradation and improve reliability during thermal cycling. Here, in this study, a popularized strain engineering strategy is investigated in which a high coefficient of thermal expansion (CTE) hole transport layer (i.e., PDCBT) is cast onto inorganic perovskite (CsPbI 2 Br) at 100 °C. Contrary to previously published results, the X-ray diffraction (XRD):Sin 2 ψ and substrate curvature measurement techniques show that the hole transport layer has no discernible impact on perovskite strain. The accuracy of the XRD:Sin 2 ψ method for measuring strain is highlighted in contrast to an analysis based on shifts of single XRD peaks which can be influenced by multiple artifacts. The findings in this study are in accordance with mechanics theory: thin layers are unable to induce significant strain changes in perovskite thin films as the force they apply is negligible compared to that applied by a thick and stiff substrate.

14 SOLAR ENERGY↗
DOE OSTI2025

Nacre-like MXene/Polyacrylic Acid Layer-by-Layer Multilayers as Hydrogen Gas Barriers

MXenes are a promising class of 2D nanomaterials and are of particular interest for gas barrier applications due to their high aspect ratio. However, MXene nanosheets naturally bear a negative charge, which prevents assembly with negatively charged polymers, such as polyacrylic acid (PAA), into gas barrier coatings. Here, we present MXene- and PAA-based layer-by-layer (MXene/ PAA LbL) multilayers formed by leveraging hydrogen bonding interactions. When assembled in acidic conditions, MXene/PAA LbL multilayers exhibit conformal, pinhole-free, nacre-like structures. The MXene/PAA LbL multilayers yield high blocking capability and low permeability (0.14 ± 0.01 cc·mm·m −2 ·day −1 · MPa −1 ) for hydrogen gas which is over 9000 times lower than uncoated niobium (Nb) substrate. These nacre-like structures are also electronically conductive (σ DC , up to 370 ± 30 S cm −1 ). Because these multilayers utilize hydrogen bonding, their properties are highly sensitive to the pH of the assembly and its external environment. Specifically, the reversible deconstruction of these multilayers under basic conditions is experimentally verified. This study shows that hydrogen bonding interactions can be leveraged to form MXene LbL multilayers as gas barriers, electronically conductive coatings, and deconstructable thin films via pH control.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Critical Practices in Rigorously Assessing the Inherent Activity of Nanoparticle Electrocatalysts

Accurate activity measurements for electrocatalytic materials are the backbone of impactful electrocatalyst research. Inherent to accurate measurements is the correct accounting of the active catalyst sites and the design of experiments to ensure that these sites are participating in the measured reaction. Improvements in electrocatalyst activity for fuel cell reactions (hydrogen oxidation and oxygen reduction) are essential for the widespread adoption of this carbon-neutral energy source. Activities for these half-reactions can be reported in a variety of ways including specific activities, mass activities, volumetric activities, and half-wave potentials. These values are traditionally measured with a rotating disk electrode (RDE) in which the electrocatalyst is supported on a porous active layer film attached to the RDE. To accurately measure electrocatalyst activity with an RDE, two major sources of errors must be addressed: (i) accurate electrochemical surface area (ECSA) quantification and (ii) fast diffusion of reactants through the active layer film. In this contribution, we first aim to detail through RDE experiments and mass transport modeling the potential errors that can be observed when these factors are not properly addressed. We then present recommendations and discuss techniques for properly constructing electrocatalyst thin films and characterizing the ECSA on monometallic and novel alloy electrocatalysts. These practices, when adopted, ensure greater confidence and reliability in reports of electrocatalyst activity.

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

All-vacuum-deposited inorganic cesium lead halide perovskite light-emitting diodes

Polycrystalline CsPbBr 3 thin films are deposited by vacuum co-evaporation of cesium halide and lead halide precursors, leading to uniform pinhole-free morphology and precise control over the film thickness and precursor stoichiometry. By utilizing the organic hole and electron transport layers, all-vacuum-deposited perovskite LEDs are fabricated. The resulting devices exhibit a maximum luminance of 1800 cd/m 2 , a 531 nm emission wavelength peak with a spectral linewidth of 21 nm, and an external quantum efficiency of 1.1%.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Variable Laser Ignition Pathways in Al/Pt Reactive Multilayers across 10 Decades of Pulse Duration

Pulsed laser irradiation is used to investigate the local initiation of rapid, self-propagating formation reactions in Al/Pt multilayers. The single pulse direct laser ignition of these 1.6 μm thick freestanding foils was characterized over 10 decades of pulse duration (10 ms to 150 fs). Finite element, reactive heat transport modeling of the near-threshold conditions has identified three distinct ignition pathways. For milli- to microsecond pulses, ignition occurs following sufficient absorption of laser energy to enable diffusion of Al and Pt between layers such that the heat released from the corresponding exothermic reaction overcomes conductive losses outside the laser-irradiated zone. When pulse duration is decreased into the nanosecond regime, heat is concentrated near the surface such that the Al locally melts, and a portion of the top-most bilayers react initially. The favorable kinetics and additional heat enable ignition. Further reducing pulse duration to hundreds of femtoseconds leads to a third ignition pathway. In this work, while much of the energy from these pulses is lost to ablation, the remaining heat beneath the crater can be sufficiently concentrated to drive a transverse self-propagating reaction, wherein the heat released from mixing at each interface occurs under kinetic conditions capable of igniting the subsequent layer.

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

Organic Cation Influence on Organic–Inorganic Thermal Equilibration within 2D Metal Halide Perovskites

Two-dimensional inorganic–organic lead halide perovskites exhibit tunable optoelectronic properties that are dictated by alternating layers of metal halide octahedra and organic cations. In such hybrid materials, vibrational coupling and thermalization between the low mass, insulating, organic cation spacers, and high mass inorganic octahedra remains poorly understood. Here, in this study, using femtosecond infrared-pump electronic-probe (IPEP) spectroscopy, we investigate the role of organic cation identity regarding the kinetics of vibrational energy exchange and sublattice mechanical coupling. Linear aliphatic cation-containing 2D perovskites with 4, 6, or 8 carbons (butylammonium = BA, hexylammonium = HA, and octylammonium = OA) were produced as thin films and mid-infrared pump pulses and then selectively excited organic cation stretch vibrations. Thermal energy introduction was evaluated via visible-wavelength optical probing that conveys inorganic octahedra response, owing to changes in electronic absorption. Multiple distinct spectral shifts appear upon excitation of the organic cations. Following an initial optical Stark shift caused by pump–probe temporal overlap, a redshift occurs within the first 10 ps that we attribute to compression of the octahedra by the expanded organic layers. Subsequently, a blueshift of the bandgap occurs commensurate with equilibration of both sublattices at an elevated temperature with a time constant of 21.8 to 31.6 ps depending on the spacer identity, with thermal energy transfer slowing by nearly 50% for the longest linker. By examining the effect that altered cation identity has on vibrational energy exchange, this work begins to offer routes to tune nonequilibrium response as well as provides insight into the fundamental impacts of organic spacers on thermal energy exchange in perovskite materials.

Peifer, Shoshanna E. [Northwestern Univ., Evanston↗
DOE OSTI2025

Topochemical Synthesis and Electronic Structure of High-Crystallinity Infinite-Layer Nickelates on an Orthorhombic Substrate

Superconductivity in infinite-layer nickelates has stirred much research interest, to which questions regarding the nature of superconductivity remain elusive. A critical leap forward to address these intricate questions is through the growth of high-crystallinity infinite-layer nickelates, including the “parent” phase. Here, we report the synthesis of a high-quality thin-film nickelate, NdNiO 2 . This is achieved through the growth of a perovskite precursor phase (NdNiO 3 ) of superior crystallinity on the NdGaO 3 substrate by off-axis RF magnetron sputtering and a low-temperature topochemical reduction using NaH. We observe a nonlinear Hall effect at low temperatures in this “non-doped” phase. We further study the electronic properties using advanced X-ray scattering and first-principles calculations. We observe spectroscopic indications of the enhanced two-dimensionality and a reduced hybridization of Nd 5d and Ni 3d orbitals. These findings unlock new pathways for preparing high-quality infinite-layer nickelates and provide new insights into the intrinsic features of these compounds.

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

Direct Optical Lithography of Colloidal Metal Oxide Nanomaterials for Diffractive Optical Elements with 2π Phase Control

Spatially patterned dielectric materials are ubiquitous in electronic, photonic, and optoelectronic devices. These patterns are typically made by subtractive or additive approaches utilizing vapor-phase reagents. On the other hand, recent advances in solution-phase synthesis of oxide nanomaterials have unlocked a materials library with greater compositional, microstructural, and interfacial tunability. However, methods to pattern and integrate these nanomaterials in real-world devices are less established. In this work, we directly optically pattern oxide nanoparticles (NPs) by mixing them with photosensitive diazo-2-naphthol-4-sulfonic acid and irradiating with widely available 405 nm light. We demonstrate the direct optical lithography of ZrO 2 , TiO 2 , HfO 2 , and ITO NPs and investigate the chemical and physical changes responsible for this photoinduced decrease in solubility. Micron-thick layers of amorphous ZrO 2 NPs were patterned with micron resolution and shown to allow 2 pi phase control of visible light. We also show multilayer patterning and use it to fabricate features with different thicknesses and distinct structural colors. Upon annealing at 400 degrees C, the deposited ZrO 2 structures have excellent optical transparency across a wide wavelength range (0.3-10 mu m), a high refractive index (n = 1.84 at 633 nm), and are optically smooth. We then fabricate diffractive optical elements, such as binary phase diffraction gratings, that show efficient diffractive behavior and good thermal stability. Different oxide NPs can also be mixed prior to patterning, providing a high level of material tunability. This work demonstrates a general patterning approach that harnesses the processability and diversity of colloidal oxide nanomaterials for use in photonic applications.

2𝜋 phase shift↗
DOE OSTI2022

Cesium Lead Halide Perovskite Nanocrystals Assembled in Metal–Organic Frameworks for Stable Blue Light Emitting Diodes

All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here we demonstrate CsPb(BrCl) 1.5 nanocrystals in metal-organic frameworks (MOF) thin films to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10~20 nm nanocrystals. This is revealed by X-ray scattering and transmission electron microscopy. Employing the CsPbX 3 - MOF thin films as emission layers, bright deep blue and sky-blue LEDs are demonstrated that emit at 452 nm and 476 nm respectively. The maximum external quantum efficiencies of these devices are 0.72% for deep blue LEDs and 5.6% for sky blue LEDs. More importantly, the device can maintain 50% of its original electroluminescence (T 50 ) for 2.23 hours when driving at 4.2V. Detailed optical spectroscopy and time-of-flight secondary ion mass spectroscopy suggest that the ion migration can be suppressed that maintains the emission brightness and spectra. Our study provides a new route for fabricating stable blue light emitting diodes with all-inorganic perovskite nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Resistive Switching Memory Performance of Two-Dimensional Polyimide Covalent Organic Framework Films

Two-dimensional polyimide covalent organic framework (2D PI-NT COF) films were constructed on indium tin oxide-coated glass substrates to fabricate two-terminal sandwiched resistive memory devices. The 2D PI-NT COF films condensated from the reaction between 4,4',4"-triaminotriphenylamine and naphthalene-1,4,5,8-tetracarboxylic dianhydride under solvothermal conditions demonstrated high crystallinity, good orientation preference, tunable thickness, and low surface roughness. The well-aligned electron-donor (triphenylamine unit) and -acceptor (naphthalene diimide unit) arrays rendered the 2D PI-NT COF films a promising candidate for electronic applications. The memory devices based on 2D PI-NT COF films exhibited a typical write-once-read-many-time resistive switching behavior under an operating voltage of +2.30 V on the positive scan and -2.64 V on the negative scan. A high ON/OFF current ratio (>10 6 for the positive scan and 10 4 -10 6 for the negative scan) and long-term retention time indicated the high fidelity, low error, and high stability of the resistive memory devices. The memory behavior was attributed to an electric field-induced intramolecular charge transfer in an ordered donor-acceptor system, which provided the effective charge-transfer channels for injected charge carriers. Furthermore, this work represents the first example that explores the resistive memory properties of 2D PI-COF films, shedding light on the potential application of 2D COFs as information storage media.

2D covalent organic framework film↗
DOE OSTI2023

Understanding the unique optical and vibrational signatures of sequential infiltration synthesis derived indium oxyhydroxide clusters for CO 2 absorption

Sequential infiltration synthesis (SIS) is a vapor phase synthesis technique with potential to exert precise control over metal oxyhydroxide incorporation into polymer scaffolds. Here, we observe strong size-dependent properties of InO x (OH) y few-atom clusters deposited with variable SIS cycle numbers within a polymethylmethacrylate (PMMA) matrix. Infrared spectroscopy and ultraviolet-visible absorption spectroscopy reveal that the metal atom coordination and optical properties of the clusters depend on the number of SIS cycles performed as well as the choice of processing parameters. The incorporation of indium oxyhydroxide in PMMA via SIS presents an opportunity to improve the CO 2 absorption capacity and gas selectivity of inexpensive polymers.

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

Characterizing and Improving the Thermal Stability of Organic Photovoltaics Based on Halogen-Rich Non-Fullerene Acceptors

In this work, the thermal stability of inverted, halogen-rich non-fullerene acceptor (NFA)-based organic photovoltaics (OPVs) with MoO x as the hole transporting layer is studied at temperatures up to 80°C. Over time, the power conversion efficiency shows a “check-mark” shaped thermal aging pattern, featuring an early decrease, followed by a long-term recovery. A high Cl concentration at the BHJ/MoO x interface in the thermally aged device is found using energy dispersive X-ray spectroscopy. X-Ray photoelectron spectroscopy shows that the MoO x is chlorinated after thermal aging. With bulk quantum efficiency analysis, we propose an explanation to the check-mark shaped pattern. Inserting a thin C 70 layer between the BHJ and MoO x suppresses the thermal degradation mechanisms, resulting in 3 orders of magnitude increase in device lifetime at 80°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nonpyrophoric alternative to trimethylaluminum for the atomic layer deposition of Al 2 O 3

We have examined the atomic layer deposition (ALD) of Al 2 O 3 using a nonpyrophoric precursor, which possesses only Al–N bonds and no Al–C bonds: Al(N(CH 3 ) 2 ) 2 (–N(C 2 H 5 )–C 2 H 4 –N(C 2 H 5 ) 2 ), which we refer to as bis-dimethylamino-diamino-aluminum (BDMADA-Al). We employed a quartz crystal microbalance (QCM) to monitor ALD in situ and in real time, and the deposited thin films have been characterized using x-ray photoelectron spectroscopy, spectroscopic ellipsometry, x-ray reflectivity, and atomic force microscopy. Films deposited with BDMADA-Al result in near-stoichiometric Al2O3 at temperatures ranging from T = 120 to 285 °C using H 2 O as the coreactant and at T = 285 °C using t-BuOH as the coreactant. The properties of the films (density, C incorporation, stoichiometry, growth rates) are comparable using either BDMADA-Al or trimethylaluminum (TMA) as the precursor under similar reaction conditions. The N content in the films deposited with BDMADA-Al as the precursor is <1% at both T = 120 and 285 °C. Additionally, both BDMADA-Al|t-BuOH and TMA|t-BuOH processes deposit near-stoichiometric Al 2 O 3 at T = 285 °C, while neither process chemistry produces a constant growth rate per cycle at T = 120 °C. Close examination of single cycle QCM data from BDMADA-Al ALD indicates unique ligand exchange reaction mechanisms during each of the half-reactions. Experimentally, we have evidence supporting the mechanism in which upon the chemisorption of BDMADA-Al, the species on the surface retains the –N(CH 3 ) 2 ligands, while the diamine ligand is mostly lost on dissociative adsorption, except possibly at the higher temperature (285 °C). As a result, our work demonstrates that BDMADA-Al can be used as an effective alternative precursor to TMA for the ALD of Al 2 O 3 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lead-Free Organic–Perovskite Hybrid Quantum Wells for Highly Stable Light-Emitting Diodes

Two-dimensional perovskites that could be regarded as natural organic-inorganic hybrid quantum wells (HQWs) are promising for light-emitting diode (LED) applications. High photoluminescence quantum efficiencies (approaching 80%) and extremely narrow emission bandwidth (less than 20 nm) have been demonstrated in their single crystals; however, a reliable electrically driven LED device has not been realized owing to inefficient charge injection and extremely poor stability. Furthermore, the use of toxic lead raises concerns. Here, we report Sn(II)-based organic-perovskite HQWs employing molecularly tailored organic semiconducting barrier layers for efficient and stable LEDs. Utilizing femtosecond transient absorption spectroscopy, we demonstrate the energy transfer from organic barrier to inorganic perovskite emitter occurs faster than the intramolecular charge transfer in the organic layer. Consequently, this process allows efficient conversion of lower-energy emission associated with the organic layer into higher-energy emission from the perovskite layer. Thus, this greatly broadened the candidate pool for the organic layer. Incorporating a bulky small bandgap organic barrier in the HQW, charge transport is enhanced and ion migration is greatly suppressed. We demonstrate a HQW-LED device with pure red emission, a maximum luminance of 3466 cd m -2 , a peak external quantum efficiency up to 3.33%, and an operational stability of over 150 h, which are significantly better than previously reported lead-free perovskite LEDs.

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

Impact of Hydration on Supported V 2 O 5 /TiO 2 Catalysts as Explored by Magnetic Resonance Spectroscopy

Supported vanadium oxide catalysts are important industrial materials for a wide array of chemical transformations. The condition of surface hydration is of particular interest as a reflection of the state of a freshly manufactured catalysts prior to its activation in catalytic reactors or under conditions of photocatalysis where surface vandia are exposed to moisture. Under such conditions, the surface vanadia species undergo structural changes as evidenced by 51 V MAS NMR in this study. For low surface vanadia densities on titania, a modest trend towards the formation of dimeric and oligomeric vanadia species was observed under hydrated conditions when compared to the corresponding dehydrated catalyst, which contains a large abundance of monomeric vanadia species. The incorporation of tungsten oxide to the V 2 O 5 /TiO 2 catalyst with low surface vanadia density, however, is found to better stabilize the surface vanadia species on the titania support upon hydration than its tungsta-free counterpart. This stabilization is not an intrinsic property of more extensively oligomerized surface vanadia species in the presence of tungsten oxide, evidenced by conditions of high concentrations of surface vanadia oligomers on titania that exhibit dramatic structural changes upon hydration. At high surface vanadia coverage under hydrated environments, the simultaneous observation of crystalline V 2 O 5 nanoparticles and a mobile phase of surface vanadia species is apparent, where vanadia species are dissolved in the thin hydration layer on the titania support. These new findings have broad implications on the behavior of other metal oxide species on high surface oxide supports under hydrated conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗