Additive-Assisted Hydrothermal Growth Enabling Defect Passivation and Void Remedy in Antimony Selenosulfide Solar Cells.

Antimony selenosulfide (Sb2(S,Se)3) has recently emerged as a promising light-absorbing material, attributed to its tunable photovoltaic properties, low toxicity, and robust environmental stability. However, despite these advantages, the current record efficiency for Sb2(S,Se)3 solar cells significantly lags behind their Shockley-Queisser limit, especially when compared to other well-established chalcogenide-based thin-film solar cells, such as CdTe and Cu(In,Ga)Se2. This underperformance primarily arises from the formation of unfavorable defects, predominately located at deep energy levels, which act as recombination centers, thereby limiting the potential for performance enhancement in Sb2(S,Se)3 solar cells. Specifically, deep-level defects, such as sulfur vacancy (VS), have a lower formation energy, leading to severe non-radiative recombination and compromising device performance. To address this challenge, thioacetamide (TA), a sulfur-containing additive is introduced, into the precursor solution for the hydrothermal deposition of Sb2(S,Se)3. This results indicate that the incorporation of TA helps in passivating deep-level defects such as sulfur vacancies and in suppressing the formation of large voids within the Sb2(S,Se)3 absorber. Consequently, Sb2(S,Se)3 solar cells, with reduced carrier recombination and improved film quality, achieved a power conversion efficiency of 9.04%, with notable improvements in open-circuit voltage and fill factor. This work provides deeper insights into the passivation of deep-level donor-like VS defects through the incorporation of a sulfur-containing additive, highlighting pathways to enhance the photovoltaic performance of Sb2(S,Se)3 solar cells.

Submolecular Ligand Size and Spacing for Cell Adhesion.

Cell adhesion occurs when integrin recognizes and binds to Arg-Gly-Asp (RGD) ligands present in fibronectin. In this work, submolecular ligand size and spacing are tuned via template-mediated in situ growth of nanoparticles for dynamic macrophage modulation. To tune liganded gold nanoparticle (GNP) size and spacing from 3 to 20 nm, in situ localized assemblies of GNP arrays on nanomagnetite templates are engineered. 3 nm-spaced ligands stimulate the binding of integrin, which mediates macrophage-adhesion-assisted pro-regenerative polarization as compared to 20 nm-spaced ligands, which can be dynamically anchored to the substrate for stabilizing integrin binding and facilitating dynamic macrophage adhesion. Increasing the ligand size from 7 to 20 nm only slightly promotes macrophage adhesion, not observed with 13 nm-sized ligands. Increasing the ligand spacing from 3 to 17 nm significantly hinders macrophage adhesion that induces inflammatory polarization. Submolecular tuning of ligand spacing can dominantly modulate host macrophages.

Manipulating Nanoparticle Aggregates Regulates Receptor-Ligand Binding in Macrophages.

The receptor-ligand interactions in cells are dynamically regulated by modulation of the ligand accessibility. In this study, we utilize size-tunable magnetic nanoparticle aggregates ordered at both nanometer and atomic scales. We flexibly anchor magnetic nanoparticle aggregates of tunable sizes over the cell-adhesive RGD ligand (Arg-Gly-Asp)-active material surface while maintaining the density of dispersed ligands accessible to macrophages at constant. Lowering the accessible ligand dispersity by increasing the aggregate size at constant accessible ligand density facilitates the binding of integrin receptors to the accessible ligands, which promotes the adhesion of macrophages. In high ligand dispersity, distant magnetic manipulation to lift the aggregates (which increases ligand accessibility) stimulates the binding of integrin receptors to the accessible ligands available under the aggregates to augment macrophage adhesion-mediated pro-healing polarization both in vitro and in vivo. In low ligand dispersity, distant control to drop the aggregates (which decreases ligand accessibility) repels integrin receptors away from the aggregates, thereby suppressing integrin receptor-ligand binding and macrophage adhesion, which promotes inflammatory polarization. Here, we present "accessible ligand dispersity" as a novel fundamental parameter that regulates receptor-ligand binding, which can be reversibly manipulated by increasing and decreasing the ligand accessibility. Limitless tuning of nanoparticle aggregate dimensions and morphology can offer further insight into the regulation of receptor-ligand binding in host cells.

Dynamic Ligand Screening by Magnetic Nanoassembly Modulates Stem Cell Differentiation.

In native microenvironment, diverse physical barriers exist to dynamically modulate stem cell recruitment and differentiation for tissue repair. In this study, nanoassembly-based magnetic screens of various sizes are utilized, and they are elastically tethered over an RGD ligand (cell-adhesive motif)-presenting material surface to generate various nanogaps between the screens and the RGDs without modulating the RGD density. Large screens exhibiting low RGD distribution stimulate integrin clustering to facilitate focal adhesion, mechanotransduction, and differentiation of stem cells, which are not observed with small screens. Magnetic downward pulling of the large screens decreases the nanogaps, which dynamically suppress the focal adhesion, mechanotransduction, and differentiation of stem cells. Conversely, magnetic upward pulling of the small screens increases the nanogaps, which dynamically activates focal adhesion, mechanotransduction, and differentiation of stem cells. This regulation mechanism is also shown to be effective in the microenvironment in vivo. Further diversifying the geometries of the physical screens can further enable diverse modalities of multifaceted and safe unscreening of the distributed RGDs to unravel and modulate stem cell differentiation for tissue repair.

Elucidating and Mitigating High-Voltage Degradation Cascades in Cobalt-Free LiNiO2 Lithium-Ion Battery Cathodes.

LiNiO2 (LNO) is a promising cathode material for next-generation Li-ion batteries due to its exceptionally high capacity and cobalt-free composition that enables more sustainable and ethical large-scale manufacturing. However, its poor cycle life at high operating voltages over 4.1 V impedes its practical use, thus motivating efforts to elucidate and mitigate LiNiO2 degradation mechanisms at high states of charge. Here, a multiscale exploration of high-voltage degradation cascades associated with oxygen stacking chemistry in cobalt-free LiNiO2 , is presented. Lattice oxygen loss is found to play a critical role in the local O3-O1 stacking transition at high states of charge, which subsequently leads to Ni-ion migration and irreversible stacking faults during cycling. This undesirable atomic-scale structural evolution accelerates microscale electrochemical creep, cracking, and even bending of layers, ultimately resulting in macroscopic mechanical degradation of LNO particles. By employing a graphene-based hermetic surface coating, oxygen loss is attenuated in LNO at high states of charge, which suppresses the initiation of the degradation cascade and thus substantially improves the high-voltage capacity retention of LNO. Overall, this study provides mechanistic insight into the high-voltage degradation of LNO, which will inform ongoing efforts to employ cobalt-free cathodes in Li-ion battery technology.

Controllable Nonclassical Conductance Switching in Nanoscale Phase-Separated (PbI2 )1- x (BiI3 )x Layered Crystals.

Layered 2D (PbI2 )1- x (BiI3 )x materials exhibit a nonlinear dependence in structural and charge transport properties unanticipated from the combination of PbI2 and BiI3 . Within (PbI2 )1- x (BiI3 )x crystals, phase integration yields deceptive structural features, while phase boundary separation leads to new conductance switching behavior observed as large peaks in current during current-voltage (I-V) measurements (±100 V). Temperature- and time-dependent electrical measurements demonstrate that the behavior is attributed to ionic transport perpendicular to the layers. High-resolution transmission electron microscopy reveals that the structure of (PbI2 )1- x (BiI3 )x is a "brick wall" consisting of two phases, Pb-rich and Bi-rich. These brick-like features are 10s nm a side and it is posited that iodide ion transport at the interfaces of these regions is responsible for the conductance switching action.

Magnetic Control and Real-Time Monitoring of Stem Cell Differentiation by the Ligand Nanoassembly.

Native extracellular matrix (ECM) exhibits dynamic change in the ligand position. Herein, the ECM-emulating control and real-time monitoring of stem cell differentiation are demonstrated by ligand nanoassembly. The density of gold nanoassembly presenting cell-adhesive Arg-Gly-Asp (RGD) ligand on Fe3 O4 (magnetite) nanoparticle in nanostructures flexibly grafted to material is changed while keeping macroscale ligand density invariant. The ligand nanoassembly on the Fe3 O4 can be magnetically attracted to mediate rising and falling ligand movements via linker stretching and compression, respectively. High ligand nanoassembly density stimulates integrin ligation to activate the mechanosensing-assisted stem cell differentiation, which is monitored via in situ real-time electrochemical sensing. Magnetic control of rising and falling ligand movements hinders and promotes the adhesion-mediated mechanotransduction and differentiation of stem cells, respectively. These rising and falling ligand states yield the difference in the farthest distance (≈34.6 nm) of the RGD from material surface, thereby dynamically mimicking static long and short flexible linkers, which hinder and promote cell adhesion, respectively. Design of cytocompatible ligand nanoassemblies can be made with combinations of dimensions, shapes, and biomimetic ligands for remotely regulating stem cells for offering novel methodologies to advance regenerative therapies.

Remote Control of Time-Regulated Stretching of Ligand-Presenting Nanocoils In Situ Regulates the Cyclic Adhesion and Differentiation of Stem Cells.

Native extracellular matrix (ECM) can exhibit cyclic nanoscale stretching and shrinking of ligands to regulate complex cell-material interactions. Designing materials that allow cyclic control of changes in intrinsic ligand-presenting nanostructures in situ can emulate ECM dynamicity to regulate cellular adhesion. Unprecedented remote control of rapid, cyclic, and mechanical stretching ("ON") and shrinking ("OFF") of cell-adhesive RGD ligand-presenting magnetic nanocoils on a material surface in five repeated cycles are reported, thereby independently increasing and decreasing ligand pitch in nanocoils, respectively, without modulating ligand-presenting surface area per nanocoil. It is demonstrated that cyclic switching "ON" (ligand nanostretching) facilitates time-regulated integrin ligation, focal adhesion, spreading, YAP/TAZ mechanosensing, and differentiation of viable stem cells, both in vitro and in vivo. Fluorescence resonance energy transfer (FRET) imaging reveals magnetic switching "ON" (stretching) and "OFF" (shrinking) of the nanocoils inside animals. Versatile tuning of physical dimensions and elements of nanocoils by regulating electrodeposition conditions is also demonstrated. The study sheds novel insight into designing materials with connected ligand nanostructures that exhibit nanocoil-specific nano-spaced declustering, which is ineffective in nanowires, to facilitate cell adhesion. This unprecedented, independent, remote, and cytocompatible control of ligand nanopitch is promising for regulating the mechanosensing-mediated differentiation of stem cells in vivo.

Realization of Wafer-Scale 1T-MoS2 Film for Efficient Hydrogen Evolution Reaction.

The octahedral structure of 2D molybdenum disulfide (1T-MoS2 ) has attracted attention as a high-efficiency and low-cost electrocatalyst for hydrogen production. However, the large-scale synthesis of 1T-MoS2 films has not been realized because of higher formation energy compared to that of the trigonal prismatic phase (2H)-MoS2 . In this study, a uniform wafer-scale synthesis of the metastable 1T-MoS2 film is performed by sulfidation of the Mo metal layer using a plasma-enhanced chemical vapor deposition (PE-CVD) system. Thus, plasma-containing highly reactive ions and radicals of the sulfurization precursor enable the synthesis of 1T-MoS2 at 150 °C. Electrochemical analysis of 1T-MoS2 shows enhanced catalytic activity for the hydrogen evolution reaction (HER) compared to that of previously reported MoS2 electrocatalysts 1T-MoS2 does not transform into stable 2H-MoS2 even after 1000 cycles of HER. The proposed low-temperature synthesis approach may offer a promising solution for the facile production of various metastable-phase 2D materials.

Large and Externally Positioned Ligand-Coated Nanopatches Facilitate the Adhesion-Dependent Regenerative Polarization of Host Macrophages.

Macrophages can associate with extracellular matrix (ECM) demonstrating nanosequenced cell-adhesive RGD ligand. In this study, we devised barcoded materials composed of RGD-coated gold and RGD-absent iron nanopatches to show various frequencies and position of RGD-coated nanopatches with similar areas of iron and RGD-gold nanopatches that maintain macroscale and nanoscale RGD density invariant. Iron patches were used for substrate coupling. Both large (low frequency) and externally positioned RGD-coated nanopatches stimulated robust attachment in macrophages, compared with small (high frequency) and internally positioned RGD-coated nanopatches, respectively, which mediate their regenerative/anti-inflammatory M2 polarization. The nanobarcodes exhibited stability in vivo. We shed light into designing ligand-engineered nanostructures in an external position to facilitate host cell attachment, thereby eliciting regenerative host responses.

Independent Tuning of Nano-Ligand Frequency and Sequences Regulates the Adhesion and Differentiation of Stem Cells.

The native extracellular matrix (ECM) can exhibit heterogeneous nano-sequences periodically displaying ligands to regulate complex cell-material interactions in vivo. Herein, an ECM-emulating heterogeneous barcoding system, including ligand-bearing Au and ligand-free Fe nano-segments, is developed to independently present tunable frequency and sequences in nano-segments of cell-adhesive RGD ligand. Specifically, similar exposed surface areas of total Fe and Au nano-segments are designed. Fe segments are used for substrate coupling of nanobarcodes and as ligand-free nano-segments and Au segments for ligand coating while maintaining both nanoscale (local) and macroscale (total) ligand density constant in all groups. Low nano-ligand frequency in the same sequences and terminally sequenced nano-ligands at the same frequency independently facilitate focal adhesion and mechanosensing of stem cells, which are collectively effective both in vitro and in vivo, thereby inducing stem cell differentiation. The Fe/RGD-Au nanobarcode implants exhibit high stability and no local and systemic toxicity in various tissues and organs in vivo. This work sheds novel insight into designing biomaterials with heterogeneous nano-ligand sequences at terminal sides and/or low frequency to facilitate cellular adhesion. Tuning the electrodeposition conditions can allow synthesis of unlimited combinations of ligand nano-sequences and frequencies, magnetic elements, and bioactive ligands to remotely regulate numerous host cells in vivo.

In Situ Magnetic Control of Macroscale Nanoligand Density Regulates the Adhesion and Differentiation of Stem Cells.

Developing materials with remote controllability of macroscale ligand presentation can mimic extracellular matrix (ECM) remodeling to regulate cellular adhesion in vivo. Herein, we designed charged mobile nanoligands with superparamagnetic nanomaterials amine-functionalized and conjugated with polyethylene glycol linker and negatively charged RGD ligand. We coupled negatively a charged nanoligand to a positively charged substrate by optimizing electrostatic interactions to allow reversible planar movement. We demonstrate the imaging of both macroscale and in situ nanoscale nanoligand movement by magnetically attracting charged nanoligand to manipulate macroscale ligand density. We show that in situ magnetic control of attracting charged nanoligand facilitates stem cell adhesion, both in vitro and in vivo, with reversible control. Furthermore, we unravel that in situ magnetic attraction of charged nanoligand stimulates mechanosensing-mediated differentiation of stem cells. This remote controllability of ECM-mimicking reversible ligand variations is promising for regulating diverse reparative cellular processes in vivo.

Efficient, stable silicon tandem cells enabled by anion-engineered wide-bandgap perovskites.

Maximizing the power conversion efficiency (PCE) of perovskite/silicon tandem solar cells that can exceed the Shockley-Queisser single-cell limit requires a high-performing, stable perovskite top cell with a wide bandgap. We developed a stable perovskite solar cell with a bandgap of ~1.7 electron volts that retained more than 80% of its initial PCE of 20.7% after 1000 hours of continuous illumination. Anion engineering of phenethylammonium-based two-dimensional (2D) additives was critical for controlling the structural and electrical properties of the 2D passivation layers based on a lead iodide framework. The high PCE of 26.7% of a monolithic two-terminal wide-bandgap perovskite/silicon tandem solar cell was made possible by the ideal combination of spectral responses of the top and bottom cells.

Unconventional Defects in a Quasi-One-Dimensional KMn6Bi5.

Quasi-one-dimensional (Q1D) structures comprising a compact array of indefinitely long 1D nanowires (NWs) are scarce, especially in a bulk device-scale showing metallic and semiconducting behaviors along different axes. Unlike plentiful observations of nature of defects in three-/two-dimensional materials, there is a notable paucity of such reports in Q1D. Herein we present unconventional motific defects and their properties in a bulk Q1D KMn6Bi5 crystal, in which an individual NW motif acts as one body. We discovered motific inter- and intra-NW defects, such that a linear set of 1D motifs are displaced. Stress generates two domains with altered inter-NW spacings and a Bi-Mn solid solution grain, leading to a local bulk plasmon shift due to NW array reconfiguration as well as atomic rearrangement. The observation of such exotic defects and associated phenomena in this Q1D may provide guidance on overall defect mechanism in other Q1D systems and their collective anisotropic properties.

Self-Passivation of 2D Ruddlesden-Popper Perovskite by Polytypic Surface PbI2 Encapsulation.

Two-dimensional Ruddlesden-Popper (2D RP) halide perovskites, C2MAn-1PbnI3n+1 (C = bulky ammonium cation; MA = methylammonium) with low n-members (n < 5), have been garnering sensational attention for photovoltaic and optoelectronic applications because of the long carrier diffusion lengths, long-term stability, and tunable bandgap. Yet, the surface modification of 2D RP under kinetic particle irradiation, such as light or electron irradiation, is ambiguous, even though it is imperative to elucidate long-stabilized conversion efficiency. Herein, we present molecular-scale observations of dynamic surface reconstruction of BA2MA2Pb3I10 (n = 3) 2D RP induced by the electron beam. The surface dynamics reveal lateral growth of polytypic PbI2 with 3R, 4H, and 2H structures at the edge and surface of the 2D perovskite, accompanied by simultaneous annihilation at the other edges. Local radiolysis occurs dominantly by the internal energy increase of electron momentum transfer, which triggers a sequential layer-by-layer degradation into PbI2. In situ observation of the polytypic PbI2 growth at the whole surface and edges of 2D RP under electron irradiation elucidates how the outer PbI2 self-passivation can protect inner 2D RP, causing longer operando stability.

An In Situ Reversible Heterodimeric Nanoswitch Controlled by Metal-Ion-Ligand Coordination Regulates the Mechanosensing and Differentiation of Stem Cells.

In situ and cytocompatible nanoswitching by external stimuli is highly appealing for reversibly regulating cellular adhesion and functions in vivo. Here, a heterodimeric nanoswitch is designed to facilitate in situ switchable and combinatorial presentation of integrin-binding cell-adhesive moieties, such as Mg2+ and Arg-Gly-Asp (RGD) ligand in nanostructures. In situ reversible nanoswitching is controlled by convertible coordination between bioactive Mg2+ and bisphosphonate (BP) ligand. A BP-coated gold-nanoparticle monomer (BP-AuNP) on a substrate is prepared to allow in situ assembly of cell-adhesive Mg2+ -active Mg-BP nanoparticles (NPs) on a BP-AuNP surface via Mg2+ -BP coordination, yielding heterodimeric nanostructures (switching "ON"). Ethylenediaminetetraacetic acid (EDTA)-based Mg2+ chelation allows in situ disassembly of Mg2+ -BP NP, reverting to Mg2+ -free monomer (switching "OFF"). This in situ reversible nanoswitching on and off of cell-adhesive Mg2+ presentation allows reversible cell adhesion and release in vivo, respectively, and spatiotemporally controls cyclic cell adhesion. In situ heterodimeric assembly of dual RGD ligand- and Mg2+ -active RGD-BP-Mg2+ NP (switching "Dual ON") further tunes and promotes focal adhesion, spreading, and differentiation of stem cells. The modular nature of this in situ nanoswitch can accommodate various bioactive nanostructures via metal-ion-ligand coordination to regulate diverse cellular functions in vivo in reversible and compatible manner.

Stability of Halide Perovskite Solar Cell Devices: In Situ Observation of Oxygen Diffusion under Biasing.

Using in situ electrical biasing transmission electron microscopy, structural and chemical modification to n-i-p-type MAPbI3 solar cells are examined with a TiO2 electron-transporting layer caused by bias in the absence of other stimuli known to affect the physical integrity of MAPbI3 such as moisture, oxygen, light, and thermal stress. Electron energy loss spectroscopy (EELS) measurements reveal that oxygen ions are released from the TiO2 and migrate into the MAPbI3 under a forward bias. The injection of oxygen is accompanied by significant structural transformation; a single-crystalline MAPbI3 grain becomes amorphous with the appearance of PbI2 . Withdrawal of oxygen back to the TiO2 , and some restoration of the crystallinity of the MAPbI3 , is observed after the storage in dark under no bias. A subsequent application of a reverse bias further removes more oxygen ions from the MAPbI3 . Light current-voltage measurements of perovskite solar cells exhibit poorer performance after elongated forward biasing; recovery of the performance, though not complete, is achieved by subsequently applying a negative bias. The results indicate negative impacts on the device performance caused by the oxygen migration to the MAPbI3 under a forward bias. This study identifies a new degradation mechanism intrinsic to n-i-p MAPbI3 devices with TiO2 .

In Situ Observation of Resistive Switching in an Asymmetric Graphene Oxide Bilayer Structure.

Graphene oxide decorated with oxygen functional groups is a promising candidate as an active layer in resistive switching devices due to its controllable physical-chemical properties, high flexibility, and transparency. However, the origin of conductive channels and their growth dynamics remain a major challenge. We use in situ transmission electron microscopy techniques to demonstrate that nanoscale graphene oxide sheets bonded with oxygen dynamically change their physical and chemical structures upon an applied electric field. Artificially engineered bilayer reduced graphene oxide films with asymmetric oxygen content exhibit nonvolatile write-once-read-many memory behaviors without experiencing the bubble destruction due to the efficient migration of oxygen ions. We clearly observe that a conductive graphitic channel with a conical shape evolves from the upper oxygen-rich region to the lower oxygen-poor region. These findings provide fundamental guidance for understanding the oxygen motions of oxygen-containing carbon materials for future carbon-based nanoelectronics.

Magnetic Manipulation of Reversible Nanocaging Controls In Vivo Adhesion and Polarization of Macrophages.

Macrophages are key immune cells that perform various physiological functions, such as the maintenance of homeostasis, host defense, disease progression, and tissue regeneration. Macrophages adopt distinctly polarized phenotypes, such as pro-inflammatory M1 phenotype or anti-inflammatory (pro-healing) M2 phenotype, to execute disparate functions. The remotely controlled reversible uncaging of bioactive ligands, such as Arg-Gly-Asp (RGD) peptide, is an appealing approach for temporally regulating the adhesion and resultant polarization of macrophages on implants in vivo. Here, we utilize physical and reversible uncaging of RGD by a magnetic field that allows facile tissue penetration. We first conjugated a RGD-bearing gold nanoparticle (GNP) to the substrate and then a magnetic nanocage (MNC) to the GNP via a flexible linker to form the heterodimeric nanostructure. We magnetically manipulated nanoscale displacement of MNC and thus its proximity to the GNP to reversibly uncage and cage RGD. The uncaging of RGD temporally promoted the adhesion and subsequent M2 polarization of macrophages while inhibiting their M1 polarization both in vitro and in vivo. The RGD uncaging-mediated adhesion and M2 polarization of macrophages involved rho-associated protein kinase signaling. This study demonstrates physical and reversible uncaging of RGD to regulate the adhesion and polarization of host macrophages in vivo. This approach of magnetically regulating the heterodimer conformation for physical and reversible uncaging of RGD offers the promising potential to manipulate inflammatory or tissue-regenerative immune responses to the implants in vivo.

High spectral resolution of gamma-rays at room temperature by perovskite CsPbBr3 single crystals.

Gamma-ray detection and spectroscopy is the quantitative determination of their energy spectra, and is of critical value and critically important in diverse technological and scientific fields. Here we report an improved melt growth method for cesium lead bromide and a special detector design with asymmetrical metal electrode configuration that leads to a high performance at room temperature. As-grown centimeter-sized crystals possess extremely low impurity levels (below 10 p.p.m. for total 69 elements) and detectors achieve 3.9% energy resolution for 122 keV 57Co gamma-ray and 3.8% for 662 keV 137Cs gamma-ray. Cesium lead bromide is unique among all gamma-ray detection materials in that its hole transport properties are responsible for the high performance. The superior mobility-lifetime product for holes (1.34 × 10-3 cm2 V-1) derives mainly from the record long hole carrier lifetime (over 25 µs). The easily scalable crystal growth and high-energy resolution, highlight cesium lead bromide as an exceptional next generation material for room temperature radiation detection.