Interplay of structural chirality, electron spin and topological orbital in chiral molecular spin valves.

Chirality has been a property of central importance in physics, chemistry and biology for more than a century. Recently, electrons were found to become spin polarized after transmitting through chiral molecules, crystals, and their hybrids. This phenomenon, called chirality-induced spin selectivity (CISS), presents broad application potentials and far-reaching fundamental implications involving intricate interplays among structural chirality, topological states, and electronic spin and orbitals. However, the microscopic picture of how chiral geometry influences electronic spin remains elusive, given the negligible spin-orbit coupling (SOC) in organic molecules. In this work, we address this issue via a direct comparison of magnetoconductance (MC) measurements on magnetic semiconductor-based chiral molecular spin valves with normal metal electrodes of contrasting SOC strengths. The experiment reveals that a heavy-metal electrode provides SOC to convert the orbital polarization induced by the chiral molecular structure to spin polarization. Our results illustrate the essential role of SOC in the metal electrode for the CISS spin valve effect. A tunneling model with a magnetochiral modulation of the potential barrier is shown to quantitatively account for the unusual transport behavior.

Efficient Red Light Emitting Diodes Based on a Zero-Dimensional Organic Antimony Halide Hybrid.

Zero-dimensional (0D) organic metal halide hybrids (OMHHs) have recently emerged as a new class of light emitting materials with exceptional color tunability. While near-unity photoluminescence quantum efficiencies (PLQEs) are routinely obtained for a large number of 0D OMHHs, it remains challenging to apply them as emitter for electrically driven light emitting diodes (LEDs), largely due to the low conductivity of wide bandgap organic cations. Here, the development of a new OMHH, triphenyl(9-phenyl-9H-carbazol-3-yl) phosphonium antimony bromide (TPPcarzSbBr4 ), as emitter for efficient LEDs, which consists of semiconducting organic cations (TPPcarz+ ) and light emitting antimony bromide anions (Sb2 Br8 2- ), is reported. By replacing one of the phenyl groups in a well-known tetraphenylphosphonium cation (TPP+ ) with an electroactive phenylcarbazole group, a semiconducting TPPcarz+ cation is developed for the preparation of red emitting 0D TPPcarzSbBr4 single crystals with a high PLQE of 93.8%. With solution processed TPPcarzSbBr4 thin films (PLQE of 86.1%) as light emitting layer, red LEDs are fabricated to exhibit an external quantum efficiency (EQE) of 5.12%, a peak luminance of 5957 cd m-2 , and a current efficiency of 14.2 cd A-1 , which are the best values reported to date for electroluminescence devices based on 0D OMHHs.

Nanoscale Encapsulation of Hybrid Perovskites Using Hybrid Atomic Layer Deposition.

Organic-inorganic hybrid perovskites have shown tremendous potential for optoelectronic applications. Ion migration within the crystal and across heterointerfaces, however, imposed severe problems with material degradation and performance loss in devices. Encapsulating hybrid perovskite with a thin physical barrier can be essential for suppressing the undesirable interfacial reactions without inhibiting the desirable transport of charge carriers. Here, we demonstrated that nanoscale, pinhole-free Al2O3 layer can be coated directly on the perovskite CH3NH3PbI3 using atomic layer deposition (ALD). The success can be attributed to a multitude of strategies including surface molecular modification and hybrid ALD processing combining the thermal and plasma-enhanced modes. The Al2O3 films provided remarkable protection to the underlying perovskite films, surviving by hours in solvents without noticeable decays in either structural or optical properties. The results advanced the understanding of applying ALD directly on hybrid perovskite and provided new opportunities to implement stable and high-performance devices based on the perovskites.

Direct Measurement of the Selective Microwave-Induced Heating of Agglomerates of Dipolar Molecules: The Origin of and Parameters Controlling a Microwave Specific Superheating Effect.

Agglomerates of polar molecules in nonpolar solvents are selectively heated by microwave radiation. The magnitude of the selective heating was directly measured by using the temperature dependence of the intensities of the Stokes and anti-Stokes bands in the Raman spectra of p-nitroanisole (pNA) and mesitylene. Under dynamic heating conditions, a large apparent temperature difference (ΔT) of over 100 °C was observed between the polar pNA solute and the nonpolar mesitylene solvent. This represents the first direct measurement of the selective microwave heating process. The magnitude of the selective microwave heating was affected by the properties of the agglomerated pNA. As the concentration of the pNA increases, the magnitude of the selective heating of the pNA was observed to decrease. This is explained by the tendency of the pNA dipoles to orient in an antiparallel fashion in the aggregates as measured by the Kirkwood g value, which decreased with increasing concentration. This effect reduces the net dipole moment of the agglomerates, which decreases the microwave absorption. After the radiation was terminated, the effective temperature of the dipolar molecules returned slowly to that of the medium. The slow heat transfer was modeled successfully by treating the solutions as a biphasic solvent/solute system. Based on modeling and the fact that the agglomerate can be heated above the boiling temperature of the solvent, an insulating layer of solvent vapor is suggested to form around the heated agglomerate, slowing convective heat transfer out of the agglomerate. This is an effect unique to microwave heating.

Highly Efficient and Stable Perovskite Solar Cells Enabled by Low-Cost Industrial Organic Pigment Coating.

Surface passivation of perovskite solar cells (PSCs) using a low-cost industrial organic pigment quinacridone (QA) is presented. The procedure involves solution processing a soluble derivative of QA, N,N-bis(tert-butyloxycarbonyl)-quinacridone (TBOC-QA), followed by thermal annealing to convert TBOC-QA into insoluble QA. With halide perovskite thin films coated by QA, PSCs based on methylammonium lead iodide (MAPbI3 ) showed significantly improved performance with remarkable stability. A PCE of 21.1 % was achieved, which is much higher than 18.9 % recorded for the unmodified devices. The QA coating with exceptional insolubility and hydrophobicity also led to greatly enhanced contact angle from 35.6° for the pristine MAPbI3 thin films to 77.2° for QA coated MAPbI3 thin films. The stability of QA passivated MAPbI3 perovskite thin films and PSCs were significantly enhanced, retaining about 90 % of the initial efficiencies after more than 1000 hours storage under ambient conditions.

Linear and Nonlinear Two-Terminal Spin-Valve Effect from Chirality-Induced Spin Selectivity.

Various mechanisms of electrical generation of spin polarization in nonmagnetic materials have been a subject of broad interest for their underlying physics and device potential in spintronics. One such scheme is chirality-induced spin selectivity (CISS), with which structural chirality leads to different electric conductivities for electrons of opposite spins. The resulting effect of spin filtering has been reported for a number of chiral molecules assembled on different surfaces. However, the microscopic origin and transport mechanisms remain controversial. In particular, the fundamental Onsager relation was argued to preclude linear-response detection of CISS by a ferromagnet. Here, we report definitive observation of CISS-induced magnetoconductance in vertical heterojunctions of (Ga,Mn)As/AHPA-L molecules/Au, directly verifying spin filtering by the AHPA-L molecules via spin detection by the (Ga,Mn)As. The pronounced and robust magnetoconductance signals resulting from the use of a magnetic semiconductor enable a rigorous examination of its bias dependence, which shows both linear- and nonlinear-response components. The definitive identification of the linear-response CISS-induced two-terminal spin-valve effect places an important constraint for a viable theory of CISS and its device manifestations. The results present a promising route to spin injection and detection in semiconductors without using any magnetic material.

Highly fluorescent hybrid Au/Ag nanoclusters stabilized with poly(ethylene glycol)- and zwitterion-modified thiolate ligands.

We report a simple strategy to grow highly fluorescing, near-infrared-emitting nanoclusters (NCs) made of bimetallic Au/Ag cores, surface capped with a mixture of triphenylphosphine and various monothiol ligands. The ligands include short chain aliphatic monothiols, which yields hydrophobic NCs, and poly(ethylene glycol)- or zwitterion-appended monothiols, which yield NCs that are readily dispersible in buffer media. The reaction uses well-defined triphenylphosphine-protected Au11 clusters (as precursors) that are reacted with Ag(i)-thiolate complexes. The prepared materials are small (diameter <2 nm, as characterized by TEM) with emission peak at 730-760 nm and long lifetime (∼8-12 µs). The quantum yield measured for these materials in both hydrophobic and hydrophilic dispersions is ∼40%. High-magnification dark field STEM and X-ray photoelectron spectroscopy measurements show the presence of both metal atoms in the core, with measured binding energies that agree with reported values for nanocluster materials. The NIR emission combined with high quantum yield, small size, colloidal stability in buffer media and ease of surface functionalization afforded by the coating, make these materials suitable for investigating fundamental questions and potentially useful for biological sensing and imaging applications.

Gold-doped silver nanoclusters with enhanced photophysical properties.

We detail the characterization of atomically precise, luminescent silver and gold bimetallic nanoclusters (Ag and AgAuNCs) grown in the presence of bidentate lipoic acid (LA, the oxidized form) and dihydrolipoic acid (DHLA, the reduced form) ligands. We found that while doping AuNCs with Ag or Cu precursors using up to a 50% molar fraction (during growth) did not lead to any photoluminescence enhancement, doping of AgNCs with Au resulted in a six-fold enhancement of the PL emission compared to undoped AgNCs. The effect of doping is also reflected in the optical absorption and PL excitation spectra of the gold-doped NCs (AgAuNCs), where a clear blue shift in the absorbance features with respect to the pure AgNCs has been measured. Mass spectrometry measurements using ESI-MS showed that the AgNCs and Au-doped AgNCs had the compositions Ag29(DHLA)12 and Ag28Au(DHLA)12, respectively. The bimetallic nature of the AgAuNC cores was further supported by X-ray Photoelectron Spectroscopy (XPS) measurements. Data showed that the binding energies of the Ag and Au atoms measured from the nanoclusters were shifted with respect to those of the Ag and Au metals. Furthermore, the change in the Ag binding energy was affected by the presence of Au atoms. DOSY-NMR measurements performed on both sets of nanoclusters yielded no change in the hydrodynamic radius measured for either set of NCs when capped with the same ligands.

Aqueous Growth of Gold Clusters with Tunable Fluorescence Using Photochemically Modified Lipoic Acid-Based Ligands.

We report a one-phase aqueous growth of fluorescent gold nanoclusters (AuNCs) with tunable emission in the visible spectrum, using a ligand scaffold that is made of poly(ethylene glycol) segment appended with a metal coordinating lipoic acid at one end and a functional group at the other end. This synthetic scheme exploits the ability of the UV-induced photochemical transformation of LA-based ligands to provide DHLA and other thiol byproducts that exhibit great affinity to metal nanoparticles, obviating the need for chemical reduction of the dithiolane ring using classical reducing agents. The influence of various experimental conditions, including the photoirradiation time, gold precursor-to-ligand molar ratios, time of reaction, temperature, and the medium pH, on the growth of AuNCs has been systematically investigated. The photophysical properties, size, and structural characterization were carried out using UV-vis absorption and fluorescence spectroscopy, TEM, DOSY-NMR, and X-ray photoelectron spectroscopy. The hydrodynamic size (RH) obtained by DOSY-NMR indicates that the size of these clusters follows the trend anticipated from the absorption and PL data, with RH(red) > RH(yellow) > RH(blue). The tunable emission and size of these gold nanoclusters combined with their high biocompatibility would make them greatly promising for potential use in imaging and sensing applications.

Crosslinking of extracellular matrix scaffolds derived from pluripotent stem cell aggregates modulates neural differentiation.

At various developmental stages, pluripotent stem cells (PSCs) and their progeny secrete a large amount of extracellular matrices (ECMs) which could interact with regulatory growth factors to modulate stem cell lineage commitment. ECMs derived from PSC can be used as unique scaffolds that provide broad signaling capacities to mediate cellular differentiation. However, the rapid degradation of ECMs can impact their applications as the scaffolds for in vitro cell expansion and in vivo transplantation. To address this issue, this study investigated the effects of crosslinking on the ECMs derived from embryonic stem cells (ESCs) and the regulatory capacity of the crosslinked ECMs on the proliferation and differentiation of reseeded ESC-derived neural progenitor cells (NPCs). To create different biological cues, undifferentiated aggregates, spontaneous embryoid bodies, and ESC-derived NPC aggregates were decellularized. The derived ECMs were crosslinked using genipin or glutaraldehyde to enhance the scaffold stability. ESC-derived NPC aggregates were reseeded on different ECM scaffolds and differential cellular compositions of neural progenitors, neurons, and glial cells were observed. The results indicate that ESC-derived ECM scaffolds affect neural differentiation through intrinsic biological cues and biophysical properties. These scaffolds have potential for in vitro cell culture and in vivo tissue regeneration study. STATEMENT OF SIGNIFICANCE: Dynamic interactions of acellular extracellular matrices and stem cells are critical for lineage-specific commitment and tissue regeneration. Understanding the synergistic effects of biochemical, biological, and biophysical properties of acellular matrices would facilitate scaffold design and the functional regulation of stem cells. The present study assessed the influence of crosslinked embryonic stem cell-derived extracellular matrix on neural differentiation and revealed the synergistic interactions of various matrix properties. While embryonic stem cell-derived matrices have been assessed as tissue engineering scaffolds, the impact of crosslinking on the embryonic stem cell-derived matrices to modulate neural differentiation has not been studied. The results from this study provide novel knowledge on the interface of embryonic stem cell-derived extracellular matrix and neural aggregates. The findings reported in this manuscript are significant for stem cell differentiation toward the applications in stem cell-based drug screening, disease modeling, and cell therapies.

Preparation of Metalloporphyrin-Bound Superparamagnetic Silica Particles via "Click" Reaction.

A facile approach using click chemistry is demonstrated for immobilization of metalloporphyrins onto the surface of silica-coated iron oxide particles. Oleic-acid stabilized iron oxide nanocrystals were prepared by thermal decomposition of iron(III) acetylacetonate. Their crystallinity, morphology, and superparamagnetism were determined using X-ray diffraction, transmission electron microscopy, and a superconducting quantum interference device. Monodisperse core-shell particles were produced in the silica-coating of iron oxide via microemulsion synthesis. Surface modification of these particles was performed in two steps, which included the reaction of silica-coated iron oxide particles with 3-bromopropyltrichlorosilane, followed by azido-functionalization with sodium azide. Monoalkylated porphyrins were prepared using the Williamson ether synthesis of commercially available tetra(4-hydroxyphenyl) porphyrin with propargyl bromide in the presence of a base. (1)H NMR and matrix-assisted laser desorption ionization confirmed the identity of the compounds. The prepared monoalkyne porphyrins were zinc-metalated prior to their introduction to azide-functionalized, silica-coated iron oxide particles in the click reaction. X-ray photoelectron spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy were used to characterize the surface chemistry after each step in the reaction. In addition, particle size was determined using dynamic light scattering and microscopy. The presented methodology is versatile and can be extended to other photoreactive systems, such as phthalocyanines and boron-dipyrromethane, which may lead to new materials for optical, photonic, and biological applications.

Robust Manipulation of Magnetism in Dilute Magnetic Semiconductor (Ga,Mn)As by Organic Molecules.

Surface adsorption of organic molecules provides a new method for the robust manipulation of ferromagnetism in (Ga,Mn)As. Electron acceptor and donor molecules yield significant enhancement and suppression, respectively, of ferromagnetism with modulation of the Curie temperature spanning 36 K. Dip-pen nanolithography is employed to directly pattern monolayers on (Ga,Mn)As, which is presented as a novel pathway toward producing magnetic nanostructures.

Fluoride-induced reduction of Ag(I) cation leading to formation of silver mirrors and luminescent Ag-nanoparticles.

In aprotic solvents, Lewis basic F(-) anion reduces Lewis acidic Ag(I) cation to Ag(0), forming metallic silver mirrors on the inner surfaces of reaction vessels and luminescent Ag-nanoparticles (AgNPs) in supernatant solutions, which emit blue light upon UV irradiation. The F(-)-induced formation of silver mirrors and AgNPs was confirmed through X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), fluorescence spectroscopy, and mass spectrometry, whereas the Ag(I)-induced oxidation of F(-) to F radical, followed by its conversion to HF2(-) via H-abstraction and H-bonding, was evident from (19)F NMR spectroscopy. This redox reaction is deactivated in water, as the reducing power of hydrated F(-) diminishes drastically. Less Lewis basic Cl(-), Br(-), and I(-) ions do not reduce Ag(I) to Ag(0), instead they can only form Ag(I) halide precipitates irrespective of protic or aprotic solvents. The Ag-coated surfaces, luminescent AgNPs, and F radicals produced by this unprecedented redox reaction could be exploited as electrodes, light-emitting materials, and radical initiators, respectively.