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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH 3 CH 2 NH 3 ) 4 Pb 3 Br 10– x Cl x

Two-dimensional (2D) hybrid halide perovskites come as a family (B) 2 (A) n-1 PbnX 3n+1 (B and A= cations; X= halide). These perovskites are promising semiconductors for solar cells and optoelectronic applications. Among the fascinating properties of these materials is white-light emission, which has been mostly observed in single-layered 2D lead bromide or chloride systems (n = 1), where the broad emission comes from the transient photoexcited states generated by self-trapped excitons (STEs) from structural distortion. Here we report a multilayered 2D perovskite (n = 3) exhibiting a tunable white-light emission. Ethylammonium (EA+) can stabilize the 2D perovskite structure in EA 4 Pb 3 Br 10–x Cl x (x = 0, 2, 4, 6, 8, 9.5, and 10) with EA + being both the A and B cations in this system. Because of the larger size of EA, these materials show a high distortion level in their inorganic structures, with EA4Pb3Cl10 having a much larger distortion than that of EA 4 Pb 3 Br 10 , which results in broadband white-light emission of EA 4 Pb 3 Cl 10 in contrast to narrow blue emission of EA4Pb3Br10. The average lifetime of the series decreases gradually from the Cl end to the Br end, indicating that the larger distortion also prolongs the lifetime (more STE states). The band gap of EA 4 Pb 3 Br 10–x Cl x ranges from 3.45 eV (x = 10) to 2.75 eV (x = 0), following Vegard’s law. First-principles density functional theory calculations (DFT) show that both EA 4 Pb 3 Cl 10 and EA 4 Pb 3 Br 10 are direct band gap semiconductors. The color rendering index (CRI) of the series improves from 66 (EA 4 Pb 3 Cl 10 ) to 83 (EA 4 Pb 3 Br 0.5 Cl 9.5 ), displaying high tunability and versatility of the title compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Highly Efficient Photocatalytic Water Splitting over Edge-Modified Phosphorene Nanoribbons

Two-dimensional phosphorene with desirable optoelectronic properties (ideal band gap, high carrier mobility, and strong visible light absorption) is a promising metal-free photocatalyst for water splitting. However, the band edge positions of the valence band maximum (VBM) and conduction band maximum (CBM) of phosphorene are higher than the redox potentials in photocatalytic water splitting reactions. Here, phosphorene can only be used as the photocathode for hydrogen evolution reaction as a low-efficiency visible-light-driven photocatalyst for hydrogen production in solar water splitting cells. Here, we propose a new mechanism to improve the photocatalytic efficiency of phosphorene nanoribbons (PNRs) by modifying their edges for full reactions in photocatalytic water splitting. By employing first-principles density functional theory calculations, we find that pseudohalogen (CN and OCN) passivated PNRs not only show desired VBM and CBM band edge positions induced by edge electric dipole layer, but also possess intrinsic optoelectronic properties of phosphorene, for both water oxidation and hydrogen reduction in photocatalytic water splitting without using extra energy. Furthermore, our calculations also predict that the maximum energy conversion efficiency of heterojunction solar cells consisting of different edge-modified PNRs can be as high as 20% for photocatalytic water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Quantitative Evaluation of Optical Free Carrier Generation in Semiconducting Single-Walled Carbon Nanotubes

Gauging free carrier generation (FCG) in optically excited, charge-neutral single-walled carbon nanotubes (SWNTs) has important implications for SWNT-based optoelectronics that rely upon conversion of photons to electrical current. Earlier investigations have largely provided only qualitative insights into optically triggered SWNT FCG, due to the heterogeneous nature of commonly interrogated SWNT samples and the lack of direct, unambiguous spectroscopic signatures that could be used to quantify charges. Here, employing ultrafast pump–probe spectroscopy in conjunction with chirality-enriched, length-sorted, ionic-polymer-wrapped SWNTs, we develop a straightforward approach for quantitatively evaluating the extent of optically driven FCG in SWNTs. Owing to the previously identified trion transient absorptive hallmark (Tr + 11 → Tr + nm ) and the rapid nature of trion formation dynamics (<1 ps) relative to established free-carrier decay time scales (>ns), we correlate FCG with trion formation dynamics. Experimental determination of the trion absorptive cross section further enables evaluation of the quantum yields for optically driven FCG [Φ(E nn → h + + e – )] as a function of optical excitation energy and medium dielectric strength. We show that (i) E 33 excitons give rise to dramatically enhanced Φ(E nn → h + + e – ) relative to those derived from E 22 and E 11 excitons and (ii) Φ(E 33 → h + + e – ) monotonically increases from ~5% to 18% as the solvent dielectric constant increases from ~32 to 80. Furthermore, this work highlights the extent to which the nature of the medium and excitation conditions control FCG quantum yields in SWNTs: such studies have the potential to provide new design insights for SWNT-based compositions for optoelectronic applications that include photodetectors and photovoltaics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Two-Dimensional Hybrid Halide Perovskites: Principles and Promises

Hybrid halide perovskites have become the “next big thing” in emerging semiconductor materials as the past decade witnessed their successful application in high-performance photovoltaics. This resurgence has seen enormous and widespread development of the three-dimensional (3D) perovskites, spearheaded by CH 3 NH 3 PbI 3 . The next generation of halide perovskites, however, is characterized by reduced dimensionality perovskites, emphasizing on the two-dimensional (2D) perovskite derivatives which expand as a more diverse subgroup of semiconducting hybrids that possesses even higher tunability and excellent photophysical properties. In this perspective, we start with a histori-cal flashback that traces back to early reports before the “perovskite fever” and we follow this original work to its fruition in the present day, where 2D halide perov-skites are on the spotlight of current research, thriving on several aspects of high-performance optoelectronics. We approach the evolution of 2D halide perovskites from a structural perspective, providing a classification for the diverse structure-types of the materials, which largely dictate the unusual physical properties ob-served. We sort out the 2D hybrid halide perovskite based on two key components: the inorganic layers and their modification and the organic cation diversity. As these two heterogeneous components blend, either by synthetic manipulation (shuffling the organic cations or inorganic elements) or by external stimuli (temperature and pressure), the modular perovskite structure evolves to construct crystallographically defined quantum wells (QW). The complex electronic structure that arises is sensitive to the structural features that could be in turn used as a knob to control the dielectric and optical properties the QWs. We end this perspective with the most notable optoelectronic device achievements that have been demonstrated to date with an eye to-wards future material discovery and potential techno-logical developments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Dye Aggregation and Complex Formation Effects in 7-(Diethylamino)-coumarin-3-carboxylic Acid

7-(Diethylamino)-coumarin-3-carboxylic acid (1) has been used as a laser dye, fluorescent label, and biomedical inhibitor in many different applications. Although this dye is typically used in the solution phase, it is prone to molecular aggregation, resulting in many inconsistent optoelectronic properties being reported in the literature. In this paper, the UV—vis absorption and fluorescence spectra of 1 are investigated in three representative solvents: cyclohexane [nonpolar and non-hydrogen bonding (NHB)], ethanol (moderately polar and hydrogen-bond accepting/donating), and DMSO (strongly polar and hydrogen-bond accepting). These experimental results, in conjunction with (time-dependent) density functional theory (DFT/TDDFT) based quantum calculations, have led to the identification of the J-aggregates of 1, and rationalized its different aggregation characteristic in cyclohexane in contrast to that of another similar compound, coumarin 343. We show here that these aggregates are largely responsible for the anomalous optoelectronic properties of this compound. In addition, DFT calculations and 1H NMR spectroscopy measurements suggest that the intramolecular hydrogen bond in 1 could be "opened up" in hydrogen-bond accepting solvents, affording significant molecular conformational changes and complex formation effects. The comprehensive understanding of the molecular aggregation and complex formation mechanisms of 1 acquired through this work forms a foundation for the knowledge-based molecular design of organic dyes with tailored aggregation tendencies or anti-aggregation characteristics to cater for different opapplications.

Liu, Xiaogang↗
DOE OSTI2014

Doping against the native propensity of MoS₂: Degenerate hole doping by cation substitution

Layered transition metal dichalcogenides (TMDs) draw much attention as the key semiconducting material for two-dimensional electrical, optoelectronic, and spintronic devices. For most of these applications, both n- and p-type materials are needed to form junctions and support bipolar carrier conduction. However, typically only one type of doping is stable for a particular TMD. For example, molybdenum disulfide (MoS₂) is natively an n-type presumably due to omnipresent electron-donating sulfur vacancies, and stable/controllable p-type doping has not been achieved. The lack of p-type doping hampers the development of charge-splitting p–n junctions of MoS₂, as well as limits carrier conduction to spin-degenerate conduction bands instead of the more interesting, spin-polarized valence bands. Traditionally, extrinsic p-type doping in TMDs has been approached with surface adsorption or intercalation of electron-accepting molecules. However, practically stable doping requires substitution of host atoms with dopants where the doping is secured by covalent bonding. In this work, we demonstrate stable p-type conduction in MoS₂ by substitutional niobium (Nb) doping, leading to a degenerate hole density of ~3 × 10¹⁹ cm⁻³. Structural and X-ray techniques reveal that the Nb atoms are indeed substitutionally incorporated into MoS₂ by replacing the Mo cations in the host lattice. van der Waals p–n homojunctions based on vertically stacked MoS₂ layers are fabricated, which enable gate-tunable current rectification. A wide range of microelectronic, optoelectronic, and spintronic devices can be envisioned from the demonstrated substitutional bipolar doping of MoS₂. From the miscibility of dopants with the host, it is also expected that the synthesis technique demonstrated here can be generally extended to other TMDs for doping against their native unipolar propensity.

molybdenum disulfide↗
DOE OSTI2016

Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Lastly, our findings offer significant fundamental insight on the temperature-and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Photo-induced halide redistribution in organic–inorganic perovskite films

Organic-inorganic perovskites such as CH 3 NH 3 PbI 3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH 3 NH 3 PbI 3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. In conclusion, our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Patterned arrays of lateral heterojunctions within monolayer two-dimensional semiconductors

The formation of semiconductor heterojunctions and their high density integration are foundations of modern electronics and optoelectronics. To enable two-dimensional (2D) crystalline semiconductors as building blocks in next generation electronics, developing methods to deterministically form lateral heterojunctions is crucial. Here we demonstrate a process strategy for the formation of lithographically-patterned lateral semiconducting heterojunctions within a single 2D crystal. E-beam lithography is used to pattern MoSe 2 monolayer crystals with SiO 2 , and the exposed locations are selectively and totally converted to MoS 2 using pulsed laser deposition (PLD) of sulfur in order to form MoSe 2 /MoS 2 heterojunctions in predefined patterns. The junctions and conversion process are characterized by atomically resolved scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy. This demonstration of lateral semiconductor heterojunction arrays within a single 2D crystal is an essential step for the lateral integration of 2D semiconductor building blocks with different electronic and optoelectronic properties for high-density, ultrathin circuitry.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electrically tunable excitonic light-emitting diodes based on monolayer WSe2 p–n junctions

The development of light-emitting diodes with improved efficiency, spectral properties, compactness and integrability is important for lighting, display, optical interconnect, logic and sensor applications1, 2, 3, 4, 5, 6, 7, 8. Monolayer transition-metal dichalcogenides have recently emerged as interesting candidates for optoelectronic applications due to their unique optical properties9, 10, 11, 12, 13, 14, 15, 16. Electroluminescence has already been observed from monolayer MoS2 devices17, 18. However, the electroluminescence efficiency was low and the linewidth broad due both to the poor optical quality of the MoS2 and to ineffective contacts. Here, we report electroluminescence from lateral p–n junctions in monolayer WSe2 induced electrostatically using a thin boron nitride support as a dielectric layer with multiple metal gates beneath. This structure allows effective injection of electrons and holes, and, combined with the high optical quality of WSe2, yields bright electroluminescence with 1,000 times smaller injection current and 10 times smaller linewidth than in MoS2 (refs 17,18). Furthermore, by increasing the injection bias we can tune the electroluminescence between regimes of impurity-bound, charged and neutral excitons. This system has the required ingredients for new types of optoelectronic device, such as spin- and valley-polarized light-emitting diodes, on-chip lasers and two-dimensional electro-optic modulators.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Dynamically controlled Purcell enhancement of visible spontaneous emission in a gated plasmonic heterostructure

Emission control of colloidal quantum dots (QDs) is a cornerstone of modern high-quality lighting and display technologies. Dynamic emission control of colloidal QDs in an optoelectronic device is usually achieved by changing the optical pump intensity or injection current density. Here we propose and demonstrate a distinctly different mechanism for the temporal modulation of QD emission intensity at constant optical pumping rate. Our mechanism is based on the electrically controlled modulation of the local density of optical states (LDOS) at the position of the QDs, resulting in the modulation of the QD spontaneous emission rate, far-field emission intensity, and quantum yield. We manipulate the LDOS via field effect-induced optical permittivity modulation of an ultrathin titanium nitride (TiN) film, which is incorporated in a gated TiN/SiO 2 /Ag plasmonic heterostructure. In conclusion, the demonstrated electrical control of the colloidal QD emission provides a new approach for modulating intensity of light in displays and other optoelectronics.

42 ENGINEERING↗
DOE OSTI2018

Scaling law for excitons in 2D perovskite quantum wells

Ruddlesden–Popper halide perovskites are 2D solution-processed quantum wells with a general formula A 2 A’ n-1 M n X 3n+1 , where optoelectronic properties can be tuned by varying the perovskite layer thickness (n-value), and have recently emerged as efficient semiconductors with technologically relevant stability. However, fundamental questions concerning the nature of optical resonances (excitons or free carriers) and the exciton reduced mass, and their scaling with quantum well thickness, which are critical for designing efficient optoelectronic devices, remain unresolved. Here, using optical spectroscopy and 60-Tesla magneto-absorption supported by modeling, we unambiguously demonstrate that the optical resonances arise from tightly bound excitons with both exciton reduced masses and binding energies decreasing, respectively, from 0.221 m 0 to 0.186 m 0 and from 470 meV to 125 meV with increasing thickness from n equals 1 to 5. Based on this study we propose a general scaling law to determine the binding energy of excitons in perovskite quantum wells of any layer thickness.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Revealing the biexciton and trion-exciton complexes in BN encapsulated WSe 2

Strong Coulomb interactions in single-layer transition metal dichalcogenides (TMDs) result in the emergence of strongly bound excitons, trions, and biexcitons. These excitonic complexes possess the valley degree of freedom, which can be exploited for quantum optoelectronics. However, in contrast to the good understanding of the exciton and trion properties, the binding energy of the biexciton remains elusive, with theoretical calculations and experimental studies reporting discrepant results. In this work, we resolve the conflict by employing low-temperature photoluminescence spectroscopy to identify the biexciton state in BN-encapsulated single-layer WSe 2 . The biexciton state only exists in charge-neutral WSe 2 , which is realized through the control of efficient electrostatic gating. In the lightly electron-doped WSe 2 , one free electron binds to a biexciton and forms the trion–exciton complex. Improved understanding of the biexciton and trion–exciton complexes paves the way for exploiting the many-body physics in TMDs for novel optoelectronics applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3

Abstract Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI 3 ) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl 2 + 3MAI) (MA = CH 3 NH 3 ). The as-spun film consists of crystalline MA 2 PbI 3 Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. This enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH 3 NH 3 PbI 3 ) are game-changing semiconductors for solar cells and light-emitting devices owing to their defect tolerance and exceptionally long carrier lifetimes and diffusion lengths. Determining whether the dynamically disordered organic cations with large dipole moment benefit the optoelectronic properties of CH 3 NH 3 PbI 3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the inorganic sublattice. The resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that the induced atomic motions of the organic cations do not alter the absorption or the photoluminescence response of CH 3 NH 3 PbI 3 , beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH 3 NH 3 PbI 3 mainly derive from the inorganic lead-halide framework.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Long-range exciton transport and slow annihilation in two-dimensional hybrid perovskites

Two-dimensional hybrid organic-inorganic perovskites with strongly bound excitons and tunable structures are desirable for optoelectronic applications. Exciton transport and annihilation are two key processes in determining device efficiencies; however, a thorough understanding of these processes is hindered by that annihilation rates are often convoluted with exciton diffusion constants. Here we employ transient absorption microscopy to disentangle quantum-well-thickness-dependent exciton diffusion and annihilation in twodimensional perovskites, unraveling the key role of electron-hole interactions and dielectric screening. The exciton diffusion constant is found to increase with quantum-well thickness, ranging from 0.06 ± 0.03 to 0.34 ± 0.03 cm 2 s –1 , which leads to long-range exciton diffusion over hundreds of nanometers. The exciton annihilation rates are more than one order of magnitude lower than those found in the monolayers of transition metal dichalcogenides. The combination of long-range exciton transport and slow annihilation highlights the unique attributes of two-dimensional perovskites as an exciting class of optoelectronic materials.

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

Reversible multicolor chromism in layered formamidinium metal halide perovskites

Abstract Metal halide perovskites feature crystalline-like electronic band structures and liquid-like physical properties. The crystal–liquid duality enables optoelectronic devices with unprecedented performance and a unique opportunity to chemically manipulate the structure with low energy input. In this work, we leverage the low formation energy of metal halide perovskites to demonstrate multicolor reversible chromism. We synthesized layered Ruddlesden-Popper FA n+1 Pb n X 3n+1 (FA = formamidinium, X = I, Br; n = number of layers = 1, 2, 3 … ∞) and reversibly tune the dimensionality ( n ) by modulating the strength and number of H-bonds in the system. H-bonding was controlled by exposure to solvent vapor (solvatochromism) or temperature change (thermochromism), which shuttles FAX salt pairs between the FA n+1 Pb n X 3n+1 domains and adjacent FAX “reservoir” domains. Unlike traditional chromic materials that only offer a single-color transition, FA n+1 Pb n X 3n+1 films reversibly switch between multiple colors including yellow, orange, red, brown, and white/colorless. Each colored phase exhibits distinct optoelectronic properties characteristic of 2D superlattice materials with tunable quantum well thickness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗