Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 130
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Adv Mater ; : e2002812, 2020 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-32614510

RESUMO

2D hybrid halide perovskites with the formula (A')2 (A)n -1 Pbn I3 n +1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol-gel, oriented 3D, and 2D. Three precursor phases form during the sol-gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.

2.
J Am Chem Soc ; 2020 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-32698577

RESUMO

Emerging non-fullerene acceptors (NFAs) with crystalline domains enable high-performance bulk heterojunction (BHJ) solar cells. Thermal annealing is known to enhance BHJ photoactive layer morphology and performance. However, the microscopic mechanism of annealing-induced performance enhancement is poorly understood in emerging NFAs, espe-cially regarding competing factors. Here, optimized thermal annealing of the model system PBDB-TF:Y6 (Y6 = 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2",3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]-thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) decreases open circuit voltage (VOC) but increases the short circuit current (JSC) and fill factor (FF) such that the resulting power conversion efficiency (PCE) increases from 14% to 15% in ambient. Here we systematically investigate these thermal annealing effects through in-depth characteri-zations of carrier mobility, film morphology, charge photogeneration and recombination, using SCLC, GIXRD, AFM, XPS, NEXAFS, R-SoXS, TEM, STEM, fs/ns TA spectroscopy, 2DES, and impedance spectroscopy. Surprisingly, thermal annealing does not alter film crystallinity, nor R-SoXS characteristic size scale, relative average phase purity, nor TEM-imaged phase separation, but rather facilitates Y6 migration to the BHJ film top surface, changes the PBDB-TF/Y6 vertical phase separa-tion and intermixing, and reduces bottom surface roughness. While these morphology changes increase bimolecular re-combination (BR) and lower the free charge (FC) yield, they also increase the average of electron and hole mobility by at least two-fold. Importantly, the increased µh dominates and underlies the increased FF and PCE. Single-crystal X-ray diffraction reveals that Y6 molecules co-facially pack via their end-groups/cores, with the shortest π-π distance as close as 3.34 Å, clarifying out-of-plane π-face-on molecular orientation in the nano-crystalline BHJ domains. DFT analysis of Y6 crystals reveals hole/electron re-organization energies as low as 160/150 meV, large intermolecular electronic coupling integrals of 12.1 - 37.9 meV, ra-tionalizing the 3D electron transport and relatively high µe of 10-4 cm2 V-1 s-1. Taken all together, this work clarifies the richness of thermal annealing effects in high-efficiency NFA solar cells and tasks for future materials design.

3.
Proc Natl Acad Sci U S A ; 117(28): 16187-16192, 2020 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-32636264

RESUMO

Earth-abundant oxygen evolution catalysts (OECs) with extended stability in acid can be constructed by embedding active sites within an acid-stable metal-oxide framework. Here, we report stable NiPbOx films that are able to perform oxygen evolution reaction (OER) catalysis for extended periods of operation (>20 h) in acidic solutions of pH 2.5; conversely, native NiOx catalyst films dissolve immediately. In situ X-ray absorption spectroscopy and ex situ X-ray photoelectron spectroscopy reveal that PbO2 is unperturbed after addition of Ni and/or Fe into the lattice, which serves as an acid-stable, conductive framework for embedded OER active centers. The ability to perform OER in acid allows the mechanism of Fe doping on Ni catalysts to be further probed. Catalyst activity with Fe doping of oxidic Ni OEC under acid conditions, as compared to neutral or basic conditions, supports the contention that role of Fe3+ in enhancing catalytic activity in Ni oxide catalysts arises from its Lewis acid properties.

4.
J Am Chem Soc ; 2020 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-32657123

RESUMO

Large singlet exciton diffusion lengths are a hallmark of high performance in organic based devices such as photovoltaics, chemical sensors, and photodetectors. In this study, exciton dynamics of a two-dimensional covalent organic framework, COF-5, is investigated using ultrafast spectroscopic techniques. Following photoexcitation, the COF-5 exciton decays via three pathways: 1) excimer formation (4 ± 2 ps), 2) excimer relaxation (160 ± 40 ps), and 3) excimer decay (>3 ns). Excita-tion fluence-dependent transient absorption studies suggest that COF-5 has a relatively large diffusion coefficient (0.08 cm2/s). Furthermore, exciton-exciton annihilation processes are characterized as a function of COF-5 crystallite domain size in four different samples, which reveal domain-size dependent exciton diffusion kinetics. These results reveal that exciton diffusion in COF-5 is constrained by its crystalline domain size. These insights indicate the outstanding promise of delocalized excitonic processes available in 2D COFs, which motivate their continued design and implementation into optoelectronic devices.

5.
J Chem Phys ; 152(20): 204115, 2020 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-32486681

RESUMO

In the past few decades, prediction of macromolecular structures beyond the native conformation has been aided by the development of molecular dynamics (MD) protocols aimed at exploration of the energetic landscape of proteins. Yet, the computed structures do not always agree with experimental observables, calling for further development of the MD strategies to bring the computations and experiments closer together. Here, we report a scalable, efficient MD simulation approach that incorporates an x-ray solution scattering signal as a driving force for the conformational search of stable structural configurations outside of the native basin. We further demonstrate the importance of inclusion of the hydration layer effect for a precise description of the processes involving large changes in the solvent exposed area, such as unfolding. Utilization of the graphics processing unit allows for an efficient all-atom calculation of scattering patterns on-the-fly, even for large biomolecules, resulting in a speed-up of the calculation of the associated driving force. The utility of the methodology is demonstrated on two model protein systems, the structural transition of lysine-, arginine-, ornithine-binding protein and the folding of deca-alanine. We discuss how the present approach will aid in the interpretation of dynamical scattering experiments on protein folding and association.

7.
Opt Lett ; 45(10): 2942-2945, 2020 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-32412506

RESUMO

A passively phase-stable, broadband (∼7fs, >2000cm-1) two-dimensional (2D) electronic spectroscopy apparatus that achieves rapid acquisition rates by continuously-rather than step-wise-scanning the Fourier-transform dimension is demonstrated for the first time, to the best of our knowledge. This is made possible through use of a partially common path interferometer design in which the coherence time τ is sampled in a "rotating frame." Rapid, continuous scanning of τ increases the duty cycle of signal collection, rejects the majority of excitation pulse scatter, and enables the measurement of a complete 2D spectrum in 92 ms, which minimizes the influence of pulse intensity and delay fluctuations on the 2D spectrum. In practice, these improvements make possible the acquisition of hundreds of 2D spectra in tens of minutes, which opens the door to dense sampling of ultrafast relaxation dynamics and to generating extremely broadband 3D Fourier-transform spectra.

8.
Molecules ; 25(10)2020 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-32456192

RESUMO

Recent studies have shown that molecular aggregation structures in precursor solutions of organic photovoltaic (OPV) polymers have substantial influence on polymer film morphology, exciton and charge carrier transport dynamics, and hence, the resultant device performance. To distinguish photophysical impacts due to increasing π-conjugation from chain lengthening and π-π stacking from single/multi chain aggregation in solution and film, we used oligomers of a well-studied charge transfer polymer PTB7 with different lengths as models to reveal intrinsic photophysical properties of a conjugated segment in the absence of inter-segment aggregation. In comparison with previously studied photophysical properties in polymeric PTB7, we found that oligomer dynamics are dominated by a process of planarization of the conjugated backbone into a quinoidal structure that resembles the self-folded polymer and that, when its emission is isolated, this quinoidal excited state resembling the planar polymer chain exhibits substantial charge transfer character via solvent-dependent emission shifts. Furthermore, the oligomers distinctly lack the long-lived charge separated species characteristic of PTB7, suggesting that the progression from charge transfer character in isolated chains to exciton splitting in neat polymer solution is modulated by the interchain interactions enabled by self-folding.

9.
11.
Artigo em Inglês | MEDLINE | ID: mdl-31872540

RESUMO

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge-storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large-scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two-dimensional imine-linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 µm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.

12.
J Chem Phys ; 151(11): 114303, 2019 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-31542032

RESUMO

Bimetallic platinum complexes have interesting luminescent properties and feature long-lasting vibrational coherence and ultrafast intersystem crossing (ISC) after photoexcitation. Ultrafast triplet formation is driven by very strong spin-orbit coupling in these platinum (II) systems, where relativistic theoretical approaches beyond first-order perturbation theory are desirable. Using a fully variational relativistic theoretical method recently developed by the authors, we investigate the origins of ultrafast ISC in the [Pt(ppy) (µ-tBu2pz)]2 complex (ppy = phenylpyridine, pz = pyrazolate). Spin-orbit coupling values, evaluated along a Born-Oppenheimer molecular dynamics trajectory, are used to propagate electronic populations in time. Using this technique, we estimate ultrafast ISC rates of 15-134 fs in this species for the possible ISC pathways into the three low-lying triplet states.

13.
Inorg Chem ; 58(12): 7730-7745, 2019 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-31140791

RESUMO

Three new copper(I) complexes [Cu(LX)2]+(PF6-) (where LX stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysical properties of these new complexes (hereafter named Cu-X) were characterized in both their ground and excited states. Femtosecond ultrafast spectroscopy revealed that early photoinduced processes are faster for Cu-I than for Cu-Cl or Cu-Br, both showing similar behaviors. Their electronic absorption and electrochemical properties are comparable to benchmark [Cu(dmp)2]+ (where dmp stands for 2,9-dimethyl-1,10-phenanthroline); furthermore, their optical features were fully reproduced by time-dependent density functional theory and ab initio molecular dynamics calculations. All three complexes are luminescent at room temperature, showing that halogen atoms bound to positions 2 and 9 of phenanthroline are sufficiently bulky to prevent strong interactions between the excited Cu complexes and solvent molecules in the coordination sphere. Their behavior in the excited state, more specifically the extent of the photoluminescence efficiency and its dependence on the temperature, is, however, strongly dependent on the nature of the halogen. A combination of ultrafast transient absorption spectroscopy, temperature-dependent steady-state fluorescence spectroscopy, and computational chemistry allows one to gain a deeper understanding of the behavior of all three complexes in their excited state.

14.
Chem Sci ; 10(13): 3796-3801, 2019 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-30996969

RESUMO

Covalent organic frameworks (COFs) consist of monomers arranged in predictable structures with emergent properties. However, improved crystallinity, porosity, and solution processability remain major challenges. To this end, colloidal COF nanoparticles are useful for mechanistic studies of nucleation and growth and enable advanced spectroscopy and solution processing of thin films. Here we present a general approach to synthesize imine-linked 2D COF nanoparticles and control their size by favoring imine polymerization while preventing the nucleation of new particles. The method yields uniform, crystalline, and high-surface-area particles and is applicable to several imine-linked COFs. In situ X-ray scattering experiments reveal the nucleation of amorphous polymers, which crystallize via imine exchange processes during and after particle growth, consistent with previous mechanistic studies of imine-linked COF powders. The separation of particle formation and growth processes offers control of particle size and may enable further improvements in crystallinity in the future.

15.
Nat Commun ; 10(1): 504, 2019 01 30.
Artigo em Inglês | MEDLINE | ID: mdl-30700706

RESUMO

Significant interest exists in lead trihalides that present the perovskite structure owing to their demonstrated potential in photovoltaic, lasing, and display applications. These materials are also notable for their unusual phase behavior often displaying easily accessible phase transitions. In this work, time-resolved X-ray diffraction, performed on perovskite cesium lead bromide nanocrystals, maps the lattice response to controlled excitation fluence. These nanocrystals undergo a reversible, photoinduced orthorhombic-to-cubic phase transition which is discernible at fluences greater than 0.34 mJ cm-2 through the loss of orthorhombic features and shifting of high-symmetry peaks. This transition recovers on the timescale of 510 ± 100 ps. A reversible crystalline-to-amorphous transition, observable through loss of Bragg diffraction intensity, occurs at higher fluences (greater than 2.5 mJ cm-2). These results demonstrate that light-driven phase transitions occur in perovskite materials, which will impact optoelectronic applications and enable the manipulation of non-equilibrium phase characteristics of the broad perovskite material class.

16.
J Phys Chem B ; 123(9): 2016-2021, 2019 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-30763085

RESUMO

Many biomaterials can adapt to changes in the local biological environment (such as pH, temperature, or ionic composition) in order to regulate function or deliver a payload. Such adaptation to environmental perturbation is typically a hierarchical process that begins with a response at a local structural level and then propagates to supramolecular and macromolecular scales. Understanding fast structural dynamics that occur upon perturbation is important for rational design of functional biomaterials. However, few nanosecond time-resolved methods can probe both intra- and intermolecular scales simultaneously with a high structural resolution. Here, we utilize time-resolved X-ray scattering to probe nanosecond to microsecond structural dynamics of poly-l-glutamic acid undergoing protonation via a pH jump initiated by photoexcitation of a photoacid. Our results provide insights into the protonation-induced hierarchical changes in packing of peptide chains, formation of a helical structure, and the associated collapse of the peptide chain.

17.
ACS Nano ; 12(10): 10008-10015, 2018 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-30226751

RESUMO

The optoelectronic properties of semiconductor nanocrystals (NCs) have led to efforts to integrate them as the active material in light-emitting diodes, solid-state lighting, and lasers. Understanding related high carrier injection conditions is therefore critical as resultant thermal effects can impact optical properties. The physical integrity of NCs is indeed questionable as recent transient X-ray diffraction studies have suggested that nanoscopic particles reversibly lose crystalline order, or melt, under high fluence photoexcitation. Informed by such studies, here, we examine CdSe NCs under elevated fluences to determine the impact of lattice disordering on optical properties. To this end, we implement intensity-dependent transient absorption using both one- and two-pump methods where the latter effectively subtracts out the NC optical signatures associated with lower fluence photoexcitation, especially band-edge features. At elevated fluences, we observe a long-lived induced absorption at a lower energy than the crystalline-NC bandgap across a wide range of sizes that follows power-dependent trends and kinetics consistent with the prior transient X-ray measurements. NC photoluminescence studies provide further evidence that melting influences optical properties. These methods of characterizing bandgap narrowing caused by lattice disordering could facilitate routes to improved optical amplification and band-edge emission at high excitation density.

18.
Science ; 361(6397): 52-57, 2018 07 06.
Artigo em Inglês | MEDLINE | ID: mdl-29930093

RESUMO

Polymerization of monomers into periodic two-dimensional networks provides structurally precise, layered macromolecular sheets that exhibit desirable mechanical, optoelectronic, and molecular transport properties. Two-dimensional covalent organic frameworks (2D COFs) offer broad monomer scope but are generally isolated as powders comprising aggregated nanometer-scale crystallites. We found that 2D COF formation could be controlled using a two-step procedure in which monomers are added slowly to preformed nanoparticle seeds. The resulting 2D COFs are isolated as single-crystalline, micrometer-sized particles. Transient absorption spectroscopy of the dispersed COF nanoparticles revealed improvement in signal quality by two to three orders of magnitude relative to polycrystalline powder samples, and suggests exciton diffusion over longer length scales than those obtained through previous approaches. These findings should enable a broad exploration of synthetic 2D polymer structures and properties.

19.
ChemSusChem ; 11(14): 2421-2428, 2018 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-29851241

RESUMO

The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBu8 ) with a 500 ps lifetime was investigated by X-ray transient absorption (XTA) spectroscopy. Previous optical, vibrational, and computational studies have suggested that this photoexcited state has a ligand-to-metal charge transfer (LMCT) nature. By using XTA, which provides unambiguous information on the local electronic and nuclear configuration around the Ni center, the nature of the excited state of NiPcOBu8 was reassessed. Using X-ray probe pulses from a synchrotron source, the ground- and excited-state X-ray absorption spectra of NiPcOBu8 were measured. Based on the results, we identified that the excited state exhibits spectral features that are characteristic of a Ni1, 3 (3dz2 ,3dx2-y2 ) state rather than a LMCT state with a transiently reduced Ni center. This state resembles the (d,d) state of nickel(II) tetramesitylphorphyrin. The XTA features are rationalized based on the inherent cavity sizes of the macrocycles. These results may provide useful guidance for the design of photocatalysts in the future.

20.
Photochem Photobiol Sci ; 17(7): 874-882, 2018 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-29855030

RESUMO

The structural dynamics of insulin hexamer dissociation were studied by the photoinduced temperature jump technique and monitored by time-resolved X-ray scattering. The process of hexamer dissociation was found to involve several transient intermediates, including an expanded hexamer and an unstable tetramer. Our findings provide insights into the mechanisms of protien-protein association.


Assuntos
Insulina/química , Multimerização Proteica , Animais , Bovinos , Cinética , Modelos Moleculares , Espalhamento a Baixo Ângulo , Difração de Raios X
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA