Nanoscale Chemistry Research Articles

Design a Friendly Nanoscale Chemical Sensor Based on Gold Nanoclusters for Detecting Thiocyanate Ions in Food Industry Applications.

The surfactant cetyltrimethylammonium bromide (CTAB) induces the aggregation of gold nanoclusters (GNCs), leading to the development of a proposed fluorometric technique for detecting thiocyanate (SCN-) ions based on an anti-aggregation mechanism. This approach is straightforward to execute, highly sensitive, and selective. A significant quenching effect occurs in fluorescence upon using the aggregation agent CTAB in GNCs synthesis, resulting in a transition from intense red fluorescence to dim red. The decrease in fluorescence intensity of GNCs in the presence of CTAB is caused by the mechanism of fluorescence quenching mediated by aggregation. As the levels of SCN- rise, the fluorescence of CTAB-GNCs increases; this may be detected using spectrofluorometry or by visually inspecting under UV irradiation. The recovery of red fluorescence of CTAB-GNCs in the presence of SCN- enables the precise and discerning identification of SCN- within the concentration range of 2.86-140 nM. The minimum detectable concentration of the SCN- ions was 1 nM. The selectivity of CTAB-GNCs towards SCN- ions was investigated compared to other ions, and it was demonstrated that CTAB-GNCs exhibit exceptional selectivity. Furthermore, we believe that CTAB-GNCs have novel possibilities as favorable sensor candidates for various industrial applications. Our detection technique was validated by analyzing SCN- ions in milk samples, which yielded promising results.

Formation of pure zirconium islands inside c-component loops in high-burnup fuel cladding

High-burnup Zr-based nuclear fuel claddings exhibit accelerated irradiation growth, corrosion and hydrogen pick-up, all correlated with the emergence of c-component dislocation loops. We made use of sub-nm-resolution atom probe tomography to characterize the nanoscale chemistry of c-loops in fuel cladding from boiling water reactor operation. We found segregation of Fe, Ni and Sn to dislocation lines and depletion of Sn and O inside the loops, resulting in nearly pure Zr islands. We also observed nucleation of suboxide inside one c-loop, pointing to a possible mechanism of accelerated in-reactor corrosion. The Zr islands might also promote hydride precipitation and associated degradation.

Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy.

Metal-supported ultrathin ferrous oxide (FeO) has attracted immense interest in academia and industry due to its widespread applications in heterogeneous catalysis. However, chemical insight into the local structural characteristics of FeO, despite its critical importance in elucidating structure-property relationships, remains elusive. In this work, we report the nanoscale chemical probing of gold (Au)-supported ultrathin FeO via ultrahigh-vacuum tip-enhanced Raman spectroscopy (UHV-TERS) and scanning tunneling microscopy (STM). For comparative analysis, single-crystal Au(111) and Au(100) substrates are used to tune the interfacial properties of FeO. Although STM images show distinctly different moiré superstructures on FeO nanoislands on Au(111) and Au(100), TERS demonstrates the same chemical nature of FeO by comparable vibrational features. In addition, combined TERS and STM measurements identify a unique wrinkled FeO structure on Au(100), which is correlated to the reassembly of the intrinsic Au(100) surface reconstruction due to FeO deposition. Beyond revealing the morphologies of ultrathin FeO on Au substrates, our study provides a thorough understanding of the local interfacial properties and interactions of FeO on Au, which could shed light on the rational design of metal-supported FeO catalysts. Furthermore, this work demonstrates the promising utility of combined TERS and STM in chemically probing the structural properties of metal-supported ultrathin oxides on the nanoscale.

Facilitating excited-state plasmonics and photochemical reaction dynamics

Continuously advancing technologies is crucial to tackling modern challenges such as efficient energy transfer, directing catalytic behavior, and better understanding of microscopic phenomena. At the heart of many of these problems is nanoscale chemistry. In previous decades, the scientific community has made significant progress in nanoscale structures and technologies, especially relating to their interactions with light. Plasmonic nanostructures have been extensively studied over the past decades because of their fascinating properties and vast technological applications. They can confine light into intense local electromagnetic fields, which has been exploited in the fields of spectroscopy, energy harvesting, optoelectronics, chemical sensing, and biomedicine. Recently, however, plasmonic nanostructures have shown great potential to trigger chemical transformations of proximal molecular species via hot carrier and thermally driven processes. In this review, we discuss the basic concepts governing nanoscale light–matter interactions, the immediate phenomena induced by them, and how we can use nanoscale light–matter interactions to our advantage with surface-enhanced spectroscopy techniques and chemical reactions in confined plasmonic environments.

Nanoscale Chemical Diversity of Coke Deposits on Nanoprinted Metal Catalysts Visualized by Tip-Enhanced Raman Spectroscopy.

Coke formation is the prime cause of catalyst deactivation, where undesired carbon wastes block the catalyst surface and hinder further reaction in a broad gamut of industrial chemical processes. Yet, the origins of coke formation and their distribution across the catalyst remain elusive, obstructing the design of coke-resistant catalysts. Here, the first-time application of tip-enhanced Raman spectroscopy (TERS) is demonstrated as a nanoscale chemical probe to localize and identify coke deposits on a post-mortem metal nanocatalyst. Monitoring coke at the nanoscale circumvents bulk averaging and reveals the local nature of coke with unmatched detail. The nature of coke is chemically diverse and ranges from nanocrystalline graphite to disordered and polymeric coke, even on a single nanoscale location of a top-down nanoprinted SiO2 -supported Pt catalyst. Surprisingly, not all Pt is an equal producer of coke, where clear isolated coke "hotspots" are present non-homogeneously on Pt which generate large amounts of disordered coke. After their formation, coke shifts to the support and undergoes long-range transport on the surrounding SiO2 surface, where it becomes more graphitic. The presented results provide novel guidelines to selectively free-up the coked metal surface at more mild rejuvenation conditions, thus securing the long-term catalyst stability.

Liquid-Templating Aerogels.

Modern materials science has witnessed the era of advanced fabrication methods to engineer functionality from the nano- to macroscales. Versatile fabrication and additive manufacturing methods are developed, but the ability to design a material for a given application is still limited. Here,a novel strategy that enables target-oriented manufacturing of ultra-lightweight aerogels with on-demand characteristics is introduced. The process relies on controllable liquid templating through interfacial complexation to generate tunable, stimuli-responsive 3D-structured (multiphase) filamentous liquid templates. The methodology involves nanoscale chemistry and microscale assembly of nanoparticles (NPs) at liquid-liquid interfaces to produce hierarchical macroscopic aerogels featuring multiscale porosity, ultralow density (3.05-3.41mg cm-3 ), and high compressibility (90%) combined with elastic resilience and instant shape recovery. The challenges are overcome facing ultra-lightweight aerogels, including poor mechanical integrity and the inability to form predefined 3D constructs with on-demand functionality, for a multitude of applications. The controllable nature of the coined methodology enables tunable electromagnetic interference shielding with high specific shielding effectiveness (39 893dB cm2 g-1 ), and one of the highest-ever reported oil-absorption capacities (487 times the initial weight of aerogel for chloroform), to be obtained. These properties originate from the engineerable nature of liquid templating, pushing the boundaries of lightweight materials to systematic function design and applications.

Defect and Interface Engineered Tungsten Bronze Superstructure Anode toward Advanced Sodium Storage

AbstractDefect and interface engineering, which can facilitate exceptional electrochemical stability and activity, are some of the most important strategies in devising electrode materials. However, the complex nanoscale chemistry and structure characteristics make the origin of electrochemical mechanism extremely difficult to understand. To eliminate this issue, the delicately designed 1D tungsten bronze superstructure anode, guided by defect and interface engineering, is successfully prepared for sodium storage to gain insight into the endogenous structure‐property relationships. It can realize the intensely enhanced Na+‐storage performance with a safe operating potential of ≈0.5 V, a high specific capacity of 228 mAh g−1 at 0.1 C and superior rate performance, which is attributed to the rapid electron and ion transfer process induced by abundant heterointerfaces. More importantly, it can convey an ultra‐stable long‐term cycling performance, with the capacity retention close to 90% after 4500 cycles at 5 C and 10000 cycles at 10 C, which can be explained by the inherently zero‐strain characteristic of a novel vacancy‐ordered superstructure in tungsten bronze Ba3.4Nb10O28.4 (BNO). This study reveals the structural origins of defect and interface engineering responsible for electrochemical mechanism, providing critical insight into the design of superior electrode materials.

Understanding the nanoscale chemistry of as-received and fast neutron irradiated Nb3Sn RRP® wires using atom probe tomography

Atom probe tomography (APT) has been used to study the effect of fast neutron irradiation on the local chemistry of Nb3Sn samples. Two RRP® wires doped with 2 at% Ti were analysed, one in the as-received condition and the other irradiated to a neutron fluence (E > 0.1 MeV) of 2.82 × 1022m−2 in the TRIGA-II reactor. The irradiated sample had a reduced T c, an increase in F p, a shift in the peak of the F p curve suggesting the introduction of secondary point pinning, and an increase in the estimated scaling field B*. APT analysis has shown that polycrystalline Nb3Sn has three distinct regions of composition, near stoichiometry Nb3Sn (low Nb), regions with a higher Nb content than expected in equilibrium Nb3Sn (high Nb) and grain boundaries. The summed composition of these three regions lies within the Nb3Sn phase for both the as-received and irradiated samples. The distinct regions of high Nb Nb3Sn demonstrate incomplete diffusion in the as-received sample, and the reduction in volume of these high Nb regions after irradiation implies significant radiation induced diffusion has occurred. The presence of other features in the atomic-scale chemistry, such as the extent of Cu segregation at grain boundaries, three types of dislocation array, and unreacted Nb nanoparticles, are compared between samples.

AFM-IR for Nanoscale Chemical Characterization in Life Sciences: Recent Developments and Future Directions.

Despite the ubiquitous absorption of mid-infrared (IR) radiation by virtually all molecules that belong to the major biomolecules groups (proteins, lipids, carbohydrates, nucleic acids), the application of conventional IR microscopy to the life sciences remained somewhat limited, due to the restrictions on spatial resolution imposed by the diffraction limit (in the order of several micrometers). This issue is addressed by AFM-IR, a scanning probe-based technique that allows for chemical analysis at the nanoscale with resolutions down to 10 nm and thus has the potential to contribute to the investigation of nano and microscale biological processes. In this perspective, in addition to a concise description of the working principles and operating modes of AFM-IR, we present and evaluate the latest key applications of AFM-IR to the life sciences, summarizing what the technique has to offer to this field. Furthermore, we discuss the most relevant current limitations and point out potential future developments and areas for further application for fruitful interdisciplinary collaboration.

Correlating local chemical and structural order using Geographic Information Systems-based spatial statistics

Analysis of nanoscale short-range chemical and/or structural order via (scanning) transmission electron microscopy (S/TEM) imaging is fundamentally limited by projection of the three dimensional sample, which averages informational along the beam direction. Extracting statistically significant spatial correlations between the structure and chemistry determined from these two-dimensional datasets thus remains challenging. Here, we apply methods commonly used in Geographic Information Systems (GIS) to determine the spatial correlation between measures of local chemistry and structure from atomic-resolution STEM imaging of a compositionally complex relaxor, Pb(Mg1/3Nb2/3)O3 (PMN). The approach is used to determine the type of ordering present and to quantify the spatial variation of chemical order, oxygen octahedral distortions, and oxygen octahedral tilts. The extent of autocorrelation and inter-feature correlation among these short-range ordered regions are then evaluated through a spatial covariance analysis, showing correlation as a function of distance. The results demonstrate that integrating GIS tools for analyzing microscopy datasets can serve to unravel subtle relationships among chemical and structural features in complex materials that can be hidden when ignoring their spatial distributions.

Influence of Aliphatic Chain Length on Structural, Thermal and Electrochemical Properties of n-alkylene Benzyl Alcohols: A Study of the Odd-Even Effect.

The century-old, well-known odd–even effect phenomenon is still a very attractive and intriguing topic in supramolecular and nano-scale organic chemistry. As a part of our continuous efforts in the study of supramolecular chemistry, we have prepared three novel aromatic alcohols (1,2-bis[2-(hydroxymethyl)phenoxy]butylene (Do4OH), 1,2-bis[2-(hydroxymethyl)phenoxy]pentylene (Do5OH) and 1,2-bis[2-(hydroxymethyl)phenoxy]hexylene (Do6OH)) and determined their crystal and molecular structures by single-crystal X-ray diffraction. In all compounds, two benzyl alcohol groups are linked by an aliphatic chain of different lengths (CH2)n; n = 4, 5 and 6. The major differences in the molecular structures were found in the overall planarity of the molecules and the conformation of the aliphatic chain. Molecules with an even number of CH2 groups tend to be planar with an all-trans conformation of the aliphatic chain, while the odd-numbered molecule is non-planar, with partial gauche conformation. A direct consequence of these structural differences is visible in the melting points—odd-numbered compounds of a particular series display systematically lower melting points. Crystal and molecular structures were additionally studied by the theoretical calculations and the melting points were correlated with packing density and the number of CH2 groups. The results have shown that the generally accepted rule, higher density = higher stability = higher melting point, could not be applied to these compounds. It was found that the denser packaging causes an increase in the percentage of repulsive H‧‧‧H interactions, thereby reducing the stability of the crystal, and consequently, the melting points. Another interesting consequence of different molecular structures is their electrochemical and antioxidative properties—a non-planar structure displays the highest oxidation peak of hydroxyl groups and moderate antioxidant activity.

Rational Vaccinology: Harnessing Nanoscale Chemical Design for Cancer Immunotherapy.

Cancer immunotherapy is a powerful treatment strategy that mobilizes the immune system to fight disease. Cancer vaccination is one form of cancer immunotherapy, where spatiotemporal control of the delivery of tumor-specific antigens, adjuvants, and/or cytokines has been key to successfully activating the immune system. Nanoscale materials that take advantage of chemistry to control the nanoscale structural arrangement, composition, and release of immunostimulatory components have shown significant promise in this regard. In this Outlook, we examine how the nanoscale structure, chemistry, and composition of immunostimulatory compounds can be modulated to maximize immune response and mitigate off-target effects, focusing on spherical nucleic acids as a model system. Furthermore, we emphasize how chemistry and materials science are driving the rational design and development of next-generation cancer vaccines. Finally, we identify gaps in the field that should be addressed moving forward and outline future directions to galvanize researchers from multiple disciplines to help realize the full potential of this form of cancer immunotherapy through chemistry and rational vaccinology.

Correlation between thickness dependent nanoscale structural chemistry and superconducting properties of ultrathin epitaxial NbN films

NbN-based superconductors have attracted interest for superconducting circuits, quantum computation and high frequency devices. The superconducting properties of NbN films are predominately reliant on the microstructure, therefore, an atomic-level understanding of the structure-chemistry is required to achieve high quality epitaxial NbN films. Here, the thickness-dependent superconducting properties of NbN films (5, 10, and 50 nm) within NbN/AlN/Al2O3 heterostructures are investigated. NbN and AlN were epitaxially grown by an industrial scale physical vapor deposition technique. The role of nanoscale chemistry on the ultrathin NbN superconducting film is investigated at the atomic level for the first time via atom probe tomography, providing three-dimensional atomic distribution, chemical homogeneity, effect of impurities, specially, in secondary phase formations and interfacial abruptness. The NbN film with 5 nm of thickness demonstrates a superconducting transition temperature of 11.2 K as compared to 50 nm NbN films with a transition temperature of 15.3 K. These thickness dependent variation of superconducting properties are associated with the chemical inhomogeneity in terms of in-plane N:Nb distribution, secondary phase formations and NbN/AlN interfacial abruptness as a function of the NbN films thicknesses. The analysis depicts the interplay between the surface/interface and the superconducting properties of ultrathin NbN films. These results provide insights on material design and growth that will enable the development of optimized superconducting NbN films for quantum devices.

Nanoscale chemistry and ion segregation in zirconia-based ceramic at grain boundaries by atom probe tomography

In this work nanoscale features that are of importance in the stability of yttria-stabilized tetragonal zirconia (Y-TZP) are quantified through atom probe tomography. In-depth analysis of grain boundary chemistry revealed preferential segregation of lighter and smaller ions towards specific grain boundaries. The relationship between elemental segregation and the local atomistic structure is investigated at the sub-nanometer level to gain insights on nanoscale features associated with the tetragonal-monoclinic phase transformation in Y-TZP through grain boundary characterization. Principal component analysis was implemented to reveal any potential biases from varied field evaporation across stabilizer-rich grain boundaries. The observed variations in ion density across different grains suggested a variation in field which was attributed to potential variations in grain crystal orientation. In order to reveal the subtle depletion of oxygen atoms within grain boundaries a new methodology to map oxygen vacancies is proposed, utilizing the relative neighborhood chemistry of individual yttrium atoms.

Nanoscale chemistry of Zircaloy-2 exposed to three and nine annual cycles of boiling water reactor operation — an atom probe tomography study

Atom probe tomography was used in this work to study the metal close to the metal/oxide interface in the zirconium alloy Zircaloy-2 exposed to three and nine annual cycles of operation in a commercial boiling water reactor. The two exposure times correspond to before and after the onset of acceleration in corrosion, hydrogen pickup, and growth.The alloying elements Sn, Fe, Cr, and Ni were observed to be redistributed after exposure. After both three and nine cycles, clusters containing Fe and Cr and typically of a spheroidal shape with an approximate diameter of 5 nm were observed to be located in layers presumed to be layers of <a>-loops. On average, the cluster number density was slightly higher after nine cycles, with larger and more Cr-rich clusters. However, there were large grain-to-grain variations, which were larger than the differences between the two exposure times. Ni was only occasionally observed in the clusters. Sn was observed to be slightly enriched in the Fe–Cr clusters, but the Sn concentration was higher between than inside the layers of clusters. After nine cycles, clusters of Sn were detected in regions that were depleted of Fe and Cr. Enrichment of Sn, Fe, and Ni at features that appeared to be <c>-component loops was observed after nine cycles, whereas no such features were observed after three cycles. Enrichment of Sn and Fe, and small amounts of Cr and Ni, was observed at grain boundaries after both exposure times. After three cycles, a partially dissolved second phase particle of Zr(Fe,Cr)2 type that contained about ten times more Cr than Fe was observed.

Nanoscale Chemical Imaging of Coadsorbed Thiolate Self-Assembled Monolayers on Au(111) by Tip-Enhanced Raman Spectroscopy.

Self-assembled monolayers (SAMs) of thiolates on metal surfaces are of key importance for engineering surfaces with tunable properties. However, it remains challenging to understand binary thiolate SAMs on metals at the nanoscale under ambient conditions. Here, we employ tip-enhanced Raman spectroscopy (TERS) and density functional theory (DFT) calculations to investigate the local information of binary SAMs on Au(111) coadsorbed from an equimolar mixture of p-cyanobenzenethiol (pCTP) and p-aminothiophenol (pATP), including chemical composition, coadsorption behavior, phase segregation, plasmon-induced photocatalysis, and solvation effects. We found that upon competitive adsorption of pCTP and pATP on Au(111) from a methanolic solution, the coadsorption initially occurs randomly and homogeneously; eventually, pATP is replaced by pCTP through the gradual growth of pCTP nanodomains. TERS imaging also allows for visualization of the plasmon-induced coupling of pATP to p,p'-dimercaptoazobenzene (DMAB) and the solvation-induced phase segregation of the binary SAMs into nanodomains, with a spatial resolution of ∼9 nm under ambient conditions. According to DFT calculations, these aromatic thiolates differing only in their functional groups, -CN versus -NH2, show different adsorption energies on Au(111) in vacuum and methanol, and thus, the solvation effect on the adsorption energy of these thiolates in methanol can determine the dispersion state and replacement order of the binary thiolates on Au(111).

Tellurium biogeochemical transformation and cycling in a metalliferous semi-arid environment

Tellurium (Te) is a Critical Mineral and its biogeochemical behaviour has mostly been interpreted from laboratory-based studies rather than direct field observations, due to the scarcity of Te in the environment. The historic mining district of Moctezuma, Sonora, Mexico, hosts the only Au mine worldwide where native tellurium is the main ore mineral (Bambolla mine). In contrast to Bambolla, the nearby San Miguel mine features a typical epithermal-style assemblage of silver sulfides, selenides, and tellurides; this dichotomy provides comparative sites to study environmental Te mobility during weathering as a function of source composition (same host rock and climate). This study characterised the regolith geochemistry, mineralogy and microbial diversity around these two Te-enriched sites. Scanning electron microscopy of fresh mineral surfaces from the weathering zone suggests that Te was released to the environment through oxidative dissolution of primary Te minerals, especially native tellurium at Bambolla. Micron-scale gold grains (<100 μm) in regolith samples have morphologies consistent with the dealloying of the gold telluride calaverite (AuTe2). Secondary Te minerals observed in situ include abundant tellurite (TeO2) and highly Te-enriched Fe (hydr)oxides, which may contain up to 20mole% Te substitution for Fe. The presence of residual organic material in association with embedded secondary nano-minerals suggests that Te (bio)transformation processes were likely associated with weathering. In particular, carbon-rich globules on the surface of millimetre-sized grains of native tellurium contain abundant Te nanoparticles, suggestive of bioreduction. DNA extraction and sequencing of the bacterial 16S rRNA gene revealed that the Te-enriched (up to 1750 ppm) regolith proximal to the Te-rich veins hosted microbial communities with varying composition but similar overall diversity compared to regolith collected from distal locations (more than 50 m from the mineralised veins). Of the detected bacterial Amplicon Sequence Variants (ASVs) from Te-rich regolith which could play an active role in Te (bio)transformation processes, representatives from the phyla Proteobacteria, Actinobacteria and Acidobacteria were the most abundant, followed by Firmicutes, candidate phylum WPS-2, Chloroflexi, Planctomycetes and Patescibacteria. This study provides the first evidence that Te undergoes dynamic cycling in the environment, with nanoscale chemical and structural changes governing the biogeochemical behaviour of Te on the macroscale. In doing so, this work provides important information on the underlying controls for Te mobility in both environmental settings, such as Te-rich rock outcrops and anthropogenic settings, such as Te-containing solar panel stockpiles.

Development of a Nanoscale Chemical Exchange Saturation Transfer Magnetic Resonance Imaging Contrast Agent That Measures pH.

AcidoCEST MRI can measure the extracellular pH (pHe) of the tumor microenvironment in mouse models of human cancers and in patients who have cancer. However, chemical exchange saturation transfer (CEST) is an insensitive magnetic resonance imaging (MRI) contrast mechanism, requiring a high concentration of small-molecule agent to be delivered to the tumor. Herein, we developed a nanoscale CEST agent that can measure pH using acidoCEST MRI, which may decrease the requirement for high delivery concentrations of agent. We also developed a monomer agent for comparison to the polymer. After optimizing CEST experimental conditions, we determined that the polymer agent could be used during acidoCEST MRI studies at 125-fold and 488-fold lower concentration than the monomer agent and iopamidol, respectively. We also determined that both agents can measure pH with negligible dependence on temperature. However, pH measurements with both agents were dependent on concentration, which may be due to concentration-dependent changes in hydrogen bonding and/or steric hindrance. We performed in vivo acidoCEST MRI studies using the three agents to study a xenograft MDA-MB-231 model of mammary carcinoma. The tumor pHe measurements were 6.33 ± 0.12, 6.70 ± 0.15, and 6.85 ± 0.15 units with iopamidol, the monomer agent, and polymer agent, respectively. The higher pHe measurements with the monomer and polymer agents were attributed to the concentration dependence of these agents. This study demonstrated that nanoscale agents have merit for CEST MRI studies, but consideration should be given to the dependence of CEST contrast on the concentration of these agents.

Highly sensitive label-free detection of analytes at different scales using uniform graphene-nanopyramids hybrid SERS system

Surface-enhanced Raman spectroscopy (SERS) has attracted enormous interests as a biological sensing technique. However, the wide application of SERS technique suffers from the limitation of sensitivity, uniformity and universality for the analytes. Herein, a graphene-nanopyramids hybrid SERS system with high uniformity and sensitivity was used to label-freely detect analytes at different scales. Colloidal lithography and modern semiconductor nanofabrication process were employed for the fabrication of wafer-scale highly-ordered array of Au nanopyramids, which ensures the uniformity of the system. The graphene layer not only plays a role of biology-compatible supporting layer for analytes but also further enhances the Raman signals and facilitates the quantitative analysis capability of the hybrid system as an intensity gauge. For nanoscale chemical and protein molecules including Rhodamine 6G (R6G), methylene blue (MB), catalase and lysozyme with concentrations lower than 10−10 M, clear SERS signals can be obtained with analytical enhancement factors (EFs) of ~109 for R6G and MB. For micron-scale analytes, Raman fingerprints of cells, i.e. erythrocyte and leukocyte have been obtained. Moreover, using statistical principal component analysis method, one can easily distinguish different analytes based on their Raman fingerprints. The experiment results of EF are in good agreement with the theoretical values predicted by finite-difference time-domain simulation. Such a wafer-scale, highly uniform and universal system will certainly enable the wider application of SERS in multiscale label-free detection of chemicals, proteins and cells, etc. with high sensitivity and specificity.

Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells.

Halide perovskites perform remarkably in optoelectronic devices. However, this exceptional performance is striking given that perovskites exhibit deep charge-carrier traps and spatial compositional and structural heterogeneity, all of which should be detrimental to performance. Here, we resolve this long-standing paradox by providing a global visualization of the nanoscale chemical, structural and optoelectronic landscape in halide perovskite devices, made possible through the development of a new suite of correlative, multimodal microscopy measurements combining quantitative optical spectroscopic techniques and synchrotron nanoprobe measurements. We show that compositional disorder dominates the optoelectronic response over a weaker influence of nanoscale strain variations even of large magnitude. Nanoscale compositional gradients drive carrier funnelling onto local regions associated with low electronic disorder, drawing carrier recombination away from trap clusters associated with electronic disorder and leading to high local photoluminescence quantum efficiency. These measurements reveal a global picture of the competitive nanoscale landscape, which endows enhanced defect tolerance in devices through spatial chemical disorder that outcompetes both electronic and structural disorder.