Self-limiting Reactions Research Articles

WP4.6 - Reducing Unnecessary Transfusion of Blood Products – A Quality Improvement Project in a General Surgical Department in a District General Hospital

Abstract Aims To audit adherence of transfusion of blood products against NICE guideline thresholds. To reduce unnecessary blood transfusions following departmental teaching sessions and installation of posters on surgical wards. Methods We retrospectively audited all patients receiving packed red cells transfusions consecutively across two consecutive four-month periods in a general surgery department. Departmental teaching sessions were held after the first audit cycle, supplemented by installation of posters including NICE guideline thresholds on surgical wards. The medical notes for each patient were assessed for pre-transfusion haemoglobin, indication for transfusion, and whether each transfusion was prescribed according to NICE guidelines. Results A total of 112 units of packed red blood cells in 42 patients and 133 units in 43 patients were transfused, respectively, before and after intervention. 45 units (40.2%) were prescribed according to NICE guidelines on first audit, improving to 67 units (50.4%) following intervention. 23 units of blood (20.5% of total) were transfused back-to-back inappropriately on first audit, reducing to 6 units (4.51% of total) after intervention. There were 2 self-limiting transfusion-related reactions (1.79%) on first audit, both in patients transfused above guidance thresholds, and no reactions following intervention. At a raw cost of approximately £135 per unit of donated blood, savings of £1830 were made over a four-month period (£5493pa), not including nursing and administration costs Conclusions Through simple local interventions and stricter adherence to transfusion thresholds, we reduced inappropriate above-threshold blood product transfusions in our hospital. This corresponded to a reduction in unnecessary blood-transfusion reactions and significant hospital savings.

The Impact of ALD Precursor Choice on Nucleation and Growth of Dielectrics on 2D Materials

Recently, atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDs) have received significant attention due to their unique optical and electrical properties, lending themselves to exciting applications such as microelectronics, sensing, catalysis, photonics, and more. The properties of TMDs can be acutely impacted by their environment due to their atomic thinness. For instance, in a TMD-based transistor with a high-k dielectric surrounding the TMD semiconductor, the dielectric could dope the channel via charge transfer; it can improve charge carrier mobility by screening the impact of charged impurities on scattering; or it can worsen charge carrier mobility by introducing defect states or interfacial roughness. As such, the quality and nature of the dielectric is critical, and ultimately those properties are determined by the means of dielectric deposition. Atomic layer deposition (ALD) is a common thin film deposition technique used for depositing high-k dielectrics for transistor devices. ALD relies on sequential self-limiting reactions between a precursor or co-reactant and a surface in order to deposit a material in a layer-by-layer manner with a high degree of control over thickness, composition, and uniformity. However, the ideal basal planes of 2D materials possess no dangling bonds or reactive functional groups, making their surfaces largely inert to ALD chemistry. Hence, when conventional ALD is performed on TMDs, nucleation and growth proceeds only at defect sites, grain boundaries, and the more reactive edge sites. This sparse nucleation leads to poor quality films of low density, high surface roughness, and pinholes.In this work, we employ physisorption-assisted ALD processes and study the nucleation and quality of the deposited dielectrics. We deposit AlOx on atomically thin monolayer MoS2 (itself on SiO2/Si) using a series of ALD precursors in order to investigate the impact of the ALD precursor on nucleation. Using scanning electron microscopy (SEM), we study film nucleation and continuity as a function of ALD precursor, cycle number, and temperature. After optimizing each process for each precursor in terms of temperature and purge time for maximized nucleation, we fabricate transistor devices in which the deposited AlOx serves as a seed layer for high-k HfO2 deposition to create the gate stack. Au contacts and a Pd top gate were used to complete the devices. Using x-ray photoelectron spectroscopy (XPS) and electrical testing, we investigate the character of the dielectric/MoS2 interface. We observe that the precursor used in the ALD process can lead to a wide range of coverages, with more conventional precursors resulting in sparse coverage, and novel precursors introduced in this study leading to nearly full coverage after just 3 nm of AlOx is deposited. We hypothesize that the improved coverage for the novel precursor is the result of enhanced interactions between the precursor and the 2D material due to its particular chemical structure. The reduced nucleation delay leads to a denser, smoother film with fewer defects at the 2D/3D material interface. The devices fabricated using the novel precursor and improved dielectric show excellent performance such as good on/off ratios (106), small device-to-device variation (ΔV T < 1 V), and low effective oxide thickness (~1 nm). This work provides useful insights into how ALD precursors could be designed to improve the quality of dielectrics on 2D materials, potentially improving the viability of 2D materials for wide ranging applications.

Synthesis of low-k SiONC thin films by plasma-assisted molecular layer deposition with tetraisocyanatesilane and phloroglucinol

Low-k SiONC thin films with excellent thermal stabilities were deposited using plasma-assisted molecular layer deposition (PA-MLD) with a tetraisocyanatesilane (Si(NCO)4) precursor, N2 plasma, and phloroglucinol (C6H3(OH)3). By adjusting the order of the N2 plasma exposure steps within the PA-MLD process, we successfully developed a deposition technique that allows accurate control of thickness at the Ångström level via self-limiting reactions. The thicknesses of the thin films were measured through spectroscopic ellipsometry (SE). By tuning the N2 plasma power, we facilitated the formation of –NH2 sites for phloroglucinol adsorption, achieving a growth per cycle of 0.18 Å cycle−1 with 300 W of N2 plasma power. Consequently, the thickness of the films increased linearly with each additional cycle. Moreover, the organic linkers within the film formed stable bonds through surface reactions, resulting in a negligible decrease in thickness of approximately −11% even upon exposure to a high annealing temperature of 600 °C. This observation was confirmed by SE, distinguishing the as-prepared film from previously reported low-k films that fail to maintain their thickness under similar conditions. X-ray photoelectron spectroscopy (XPS) and current–voltage (I–V) and capacitance–voltage (C–V) measurement were conducted to evaluate the composition, insulating properties, and dielectric constant according to the deposition and annealing conditions. XPS results revealed that as the plasma power increased from 200 to 300 W, the C/Si ratio increased from 0.37 to 0.67, decreasing the dielectric constant from 3.46 to 3.12. Furthermore, there was no significant difference in the composition before and after annealing, and the hysteresis decreased from 0.58 to 0.19 V owing to defect healing, while maintaining the leakage current density, breakdown field, and dielectric constant. The low dielectric constant, accurate thickness control, and excellent thermal stability of this MLD SiONC thin film enable its application as an interlayer dielectric in back-end-of-line process.

Versatile fitting approach for operando spectroscopic imaging ellipsometry of HfS2 oxidation

Facile mapping of 2D heterostructures and resolving anisotropic formation kinetics down to the monolayer level are critical to developing scalable interfacing solutions and unlocking their application potential in emerging nano-optoelectronics. We adapt a Kramers–Kronig constrained variational fitting algorithm for spectroscopic imaging ellipsometry (SIE) to facilitate multi-scale heterostructure analysis comprising films with unknown complex dielectric functions and demonstrate how this enables non-destructive, scalable mapping and operando capability for the model system of HfS2 oxidation. This methodology proves highly accurate for assessing the thickness of buried HfS2 layers, oxide quality, and lateral and vertical uniformity. We capture dynamic stack evolution during thermal oxidation up to 400 ∘C, providing insights into the temperature and time-dependent nature of self-limiting oxide growth and reaction kinetics that involve the localised trapping and release of sulphur reaction products. Our methodology is versatile in material and device horizons, and advantageously agnostic to the underlying substrate. Combined with the various modes of SIE operation, it unlocks fast, high-throughput, large-area capability to accelerate process development at the atomic scale.

Safe Penicillin Allergy Delabeling in Primary Care: A Systematic Review and Meta-Analysis

BackgroundTen % of the population is labeled as allergic to penicillin(s), when in fact 90% of these labels are inappropriate. Recent studies have shown that inpatient de-labelling by a direct drug challenge (dDC) is safe in low-risk patients. However, there is a need for outpatient and non-allergist de-labelling. ObjectiveTo assess the safety of de-labelling low-risk adults by means of dDC in primary care. MethodsWe searched MEDLINE, EMBASE and the Conchrane Library databases, from inception to March 15, 2022 (updated June 5, 2023) for studies performing dDC in adults in primary care or other outpatient settings. Two researchers independently screened studies for eligibility. The data extraction and critical appraisal was performed by one reviewer and we pooled the results in a meta-analysis. ResultsOut of 2,138 results, 12 studies (1070 participants) were eligible for inclusion. Three studies evaluated de-labelling in primary care and 9 studies in an outpatient hospital setting. There were no critical adverse events during dDC. No reaction occurred in 97.13% of the 1070 patients, who previously labeled as penicillin-allergic, and were safely de-labelled. Ten patients (<1%) developed an immediate reaction: three had self-limiting reactions, and seven needed antihistaminics, steroids, epinephrine and/or salbutamol. ConclusionNo serious allergic reactions are observed during direct amoxicillin challenge in adults in an outpatient setting. However, with the exception of one recent report, these studies are of low to moderate quality. Non-specialist de-labelling is promising but further research is required on correct risk stratification and safety assessment in large cohort studies evaluating dDC in primary care.

Systemic inflammatory cytokine profiles in patients with gout during flare, intercritical and treat-to-target phases: TNFSF14 as new biomarker

IntroductionUntreated gout is characterised by monosodium urate (MSU) crystal accumulation responsible for recurrent flares that are commonly separated by asymptomatic phases. Both phases are inflammatory conditions of variable intensity. Gout...

Controlled NiOx Defect Engineering to Harnessing Redox Reactions in Perovskite Photovoltaic Cells via Atomic Layer Deposition.

Albeit the undesirable attributes of NiOx, such as low conductivity, unmanageable defects, and redox reactions occurring at the perovskite/NiOx interface, which impede the progress in inverted perovskite solar cells (i-PSCs), it is the most favorable choice of technology for industrialization of PSCs. In this study, we propose a novel Ni vacancy defect modulate approach to leverage the conformal growth and surface self-limiting reaction characteristics of the atomic layer deposition (ALD)-fabricated NiOx by varying the O2 plasma injection time (tOE) to induce self-doping. Consequently, NiOx thin films with enhanced conductivity, an appropriate Ni3+/Ni2+ ratio, stable surface states, and ultrathinness are realized as hole-transporting layers (HTLs) in p-i-n PSCs. As a result of these improvements, ALD-NiOx-based devices exhibit the highest power conversion efficiency (PCE) of 19.86% and a fill factor (FF) of 81.86%. Notably, the optimal interfacial defects effectively suppressed the severe reaction between the perovskite and NiOx. This suppression is evidenced by the lowest decay rate observed in a harsh environment, lasting for 500 consecutive hours. The proposed approach introduces the possibility of a hierarchical distribution of defects and offers feasibility for the fabrication of large-area, uniform, and high-quality films.

Attaining quantitatively fewer defects in close-packed InGaZnO synthesized using atomic layer deposition

Owing to their uniformity across large areas, low-temperature processability, and low off-current characteristics, oxide semiconductors demonstrate significant potential for integration into displays, memories, and logic devices. In the hyper scaling era, atomic layer deposition (ALD) is well suited for downsizing device fabrication, leveraging self-limiting chemical reactions to provide nanoscale control, and conformal coating on substrates with high aspect ratios. Hence, in this study, we fabricated highly oriented c-axis-aligned crystalline (CAAC) indium-gallium-zinc oxide (IGZO) thin films using plasma-enhanced ALD (PEALD), introducing an additional thermodynamic driving force for crystallization. A comparative study was conducted on the properties of CAAC-IGZO in correspondence to conventional sputter-based IGZO. In particular, photo-induced current transient spectroscopy (PICTS) is employed to map the electronic structure (density of states (DOS)) of the films, which quantitatively confirmed fewer defects in CAAC-IGZO. Fewer defects result in highly stable CAAC-IGZO transistors with positive bias stress threshold (PBTS) at 0.03 V and negative bias stress threshold (NBTS) at - 0.06 V. Thus, this research on thermally and electrically stable CAAC-IGZO synthesized at low temperatures through PEALD offers insights into the processing and material perspectives for the application of oxide semiconductors in 3D integration.

Low temperature (002)-oriented zinc oxide films prepared using ozone-based spatial atomic layer deposition

In this study, ZnO films are prepared at a low temperature of 150 °C by using spatial atomic layer deposition (sALD) with diethylzinc and ozone as precursor and oxidant. The ozone flow rate is varied to systematically investigate its effect on optical, structural and electrical properties. The experimental results show that the self-limiting surface reactions can occur at the low ozone flow rate of 200 sccm, confirming ALD growth mode. All the ozone flow rates lead to ZnO (002) crystalline orientation, which is difficult to be obtained for conventional water-based ALD ZnO films at the low temperature. The increased ozone flow rate results in an increased amount of oxygen vacancies, enhanced carrier concentration and a reduced stress. The resistivity and carrier concentration can be tuned in the range of 4.75–0.08 Ω-cm and (1.1–5.5) × 1018 cm−3. Finally, the sALD ZnO film on polyethylene terephthalate reveals a high stability in the film property against bending. This study is beneficial for the utilization of ZnO films in optoelectronic devices that demand the (002) preferred orientation, especially under low-temperature conditions.

Cutaneous adverse events following COVID-19 vaccination: A case series of 30 Japanese patients and a review of 93 Japanese studies.

In Japan, cutaneous adverse events (AEs) following the coronavirus disease 2019 (COVID-19) vaccination have been frequently described; however, a larger case series and literature review are lacking. There is an urgent need for an extensive investigation of new cases and previous reports to provide a thorough body of information about post-COVID-19 immunization cutaneous AEs. We aimed to analyze patients with cutaneous AEs after COVID-19 vaccination in our hospital and review previous studies of cutaneous AEs. We analyzed post-COVID-19 vaccination cutaneous AEs in our department, the Japanese Registry, and previous literature. We enrolled 30 patients with cutaneous post-vaccination AEs in our department over 2 years (April 1, 2021, to March 31, 2023). We also confirmed cases registered in the Ministry of Health, Labor, and Welfare COVID-19 vaccine side effect reporting system (February 17, 2021-March 12, 2023). A total of 587 records were retrieved and 93 articles were included for data extraction. A total of 28 non-injection-site cutaneous AEs and two injection-site AEs were identified. Six (20.0%) patients developed new-onset erythematous eruptions, and five (16.7%) patients developed urticaria. Pruritic eruption, eczema, shingles, and sweating symptoms have also been reported. In previous studies on non-injection-site cutaneous AEs, individuals who received the BNT162b2 vaccine were older than those who received mRNA-1273 (P < 0.01). Cutaneous AEs were mostly nonsignificant and self-limiting reactions; however, rare, severe, or life-threatening AEs were also reported. Physicians should be aware of the various possible cutaneous AEs associated with the COVID-19 vaccination.

Area-selective atomic layer deposition (AS-ALD) of low temperature (300 °C) cobalt thin film using octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs)

As the semiconductor industry advances, manufacturing technologies encounter challenges in achieving precise alignment and thickness control with smaller and more intricate 3D structures. Addressing this, Area-selective atomic layer deposition (AS-ALD) emerges as a promising “bottom-up” approach, offering an alternative to current nano-patterning techniques. To achieve AS-ALD, self-assembled monolayers (SAMs) are employed as inhibitor agents. In this study, we employed plasma-enhanced atomic layer deposition (PEALD) to promote self-limiting surface reactions and enable low-temperature processing, thereby facilitating the implementation of high purity cobalt (Co) film through AS-ALD using octadecyltrichlorosilane (ODTS) SAM as an inhibitor. The selective deposition is achieved by employing SAMs as an inhibitor, belonging to the deactivation process, a common method for realizing a bottom-up approach. SAMs can form a thin organic film on a solid surface, allowing for surface modifications to become hydrophobic or hydrophilic. Through the selective deposition of Co in the PEALD low-temperature process (300 °C), we successfully addressed the degradation issue of ODTS SAM and verified the successful achievement of a high-purity selectively deposited 13.4 nm Co film. Our findings highlight the potential of selective Co deposition for realizing complex 3D structures and narrow interconnection layers.

Safety and immunogenicity of the H56:IC31 tuberculosis vaccine candidate in adults successfully treated for drug-susceptible pulmonary TB: a phase 1 randomized trial.

H56:IC31 is a candidate vaccine against tuberculosis (TB) with the potential to reduce TB recurrence rate. It is thus important for future clinical trials to demonstrate safety and immunogenicity of H56:IC31 in individuals treated for TB. 22 adults confirmed to be Mtb negative (by 2 GeneXpert tests or 2 sputum cultures) after four-five months of TB treatment, and not more than 28 days after completion of TB treatment, were randomized to receive two doses of H56:IC31 (5 mg H56:500 nmol IC31; N=16) or placebo (N=6) 56 days apart. Participants were followed for 420 days for safety and immunogenicity. H56:IC31 vaccination was associated with an acceptable safety profile, consisting mostly of mild self-limited injection site reactions. No serious adverse events, and no vaccine-related severe adverse events, were reported. H56:IC31 induced a CD4+ T-cell response for Ag85B and ESAT-6, with ESAT-6 being immunodominant, which persisted through six months after the last vaccination. There was some evidence of CD8+ T-cell responses for both Ag85B and ESAT-6, but to a lesser extent than CD4+ responses. H56:IC31 was associated with an acceptable safety profile, and induced a predominant CD4+ T-cell response, in adults recently treated for drug-susceptible, uncomplicated pulmonary TB. ClinicalTrials.gov, NCT02375698.

Dynamical evolution of CO2 and H2O on garnet electrolyte elucidated by ambient pressure X-ray spectroscopies

Garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZO) is considered a promising solid electrolyte, but the surface degradation in air hinders its application for all-solid-state battery. Recent studies have mainly focused on the final products of the LLZO surface reactions due to lacking of powerful in situ characterization methods. Here, we use ambient pressure X-ray spectroscopies to in situ investigate the dynamical evolution of LLZO surface in different gas environments. The newly developed ambient pressure mapping of resonant Auger spectroscopy clearly distinguishes the lithium containing species, including LiOH, Li2O, Li2CO3 and lattice oxygen. The reaction of CO2 with LLZO to form Li2CO3 is found to be a thermodynamically favored self-limiting reaction. On the contrary, the reaction of H2O with LLZO lags behind that of CO2, but intensifies at high pressure. More interestingly, the results provide direct spectroscopic evidence for the existence of Li+/H+ exchange and reveal the importance of the initial layer formed on clean electrolyte surface in determining their air stability. This work demonstrates that the newly developed in situ technologies pave a new way to investigate the oxygen evolution and surface degradation mechanism in energy materials.

Herb-drug interactions: A short review on central and peripheral nervous system drugs.

Herbal medicines are widely perceived as natural and safe remedies. However, their concomitant use with prescribed drugs is a common practice, often undertaken without full awareness of the potential risks and frequently without medical supervision. This practice introduces a tangible risk of herb-drug interactions, which can manifest as a spectrum of consequences, ranging from acute, self-limited reactions to unpredictable and potentially lethal scenarios. This review offers a comprehensive overview of herb-drug interactions, with a specific focus on medications targeting the Central and Peripheral Nervous Systems. Our work draws upon a broad range of evidence, encompassing preclinical data, animal studies, and clinical case reports. We delve into the intricate pharmacodynamics and pharmacokinetics underpinning each interaction, elucidating the mechanisms through which these interactions occur. One pressing issue that emerges from this analysis is the need for updated guidelines and sustained pharmacovigilance efforts. The topic of herb-drug interactions often escapes the attention of both consumers and healthcare professionals. To ensure patient safety and informed decision-making, it is imperative that we address this knowledge gap and establish a framework for continued monitoring and education. In conclusion, the use of herbal remedies alongside conventional medications is a practice replete with potential hazards. This review not only underscores the real and significant risks associated with herb-drug interactions but also underscores the necessity for greater awareness, research, and vigilant oversight in this often-overlooked domain of healthcare.

Nanoparticles for stimulation of neutrophil extracellular trap-mediated immunity.

Neutrophil extracellular traps (NETs) have been identified as triggers for a self-limited inflammatory reaction upon contact with nanoparticles within our bodies. This typically results in entrapping potentially harmful nano- or micro-objects following an immune burst. The demand for potent adjuvants has led to research on particulate-based adjuvants, particularly those that act via NET formation. Various particles, including hydrophobic nanoparticles, needle-like microparticles, and other natural and artificial crystals, have been shown to induce NET formation, eliciting a robust humoral and cellular immune response toward co-injected antigens. The NET formation was found to be the basis of the efficient use of alum as a vaccine adjuvant. Thus, nanoparticles with specific surface properties serve as NET-stimulating adjuvants. In this mini-review, we aim to summarize the current knowledge about the surface properties of particulate objects and the molecular pathways involved in inducing NET formation by neutrophils. Additionally, we discuss the potential use of nanoparticles for activating neutrophils in the tissues and the exploitation of such activation for enhancing vaccine adjuvants.

Coherent X-ray Spectroscopy Elucidates Nanoscale Dynamics of Plasma-Enhanced Thin-Film Growth.

Sophisticated thin film growth techniques increasingly rely on the addition of a plasma component to open or widen a processing window, particularly at low temperatures. Taking advantage of continued increases in accelerator-based X-ray source brilliance, this real-time study uses X-ray Photon Correlation Spectroscopy (XPCS) to elucidate the nanoscale surface dynamics during Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of an epitaxial indium nitride film. Ultrathin films are synthesized from repeated cycles of alternating self-limited surface reactions induced by temporally separated pulses of the material precursor and plasma reactant, allowing the influence of each on the evolving morphology to be examined. During the heteroepitaxial 3D growth examined here, sudden changes in the surface structure during initial film growth, consistent with numerous overlapping stress-relief events, are observed. When the film becomes continuous, the nanoscale surface morphology abruptly becomes long-lived with a correlation time spanning the period of the experiment. Throughout the growth experiment, there is a consistent repeating pattern of correlations associated with the cyclic growth process, which is modeled as transitions between different surface states. The plasma exposure does not simply freeze in a structure that is then built upon in subsequent cycles, but rather, there is considerable surface evolution during all phases of the growth cycle.

Performance Enhancement of Nickel Manganese Cobalt Oxide Cathodic Material for Solid-State Battery Technology by Surface Engineering

Batteries as any other electronic devices are affected by parasitic phenomena including physical processes and chemical reactions occurring within the battery materials as well as their interfaces. The phenomena lead to degradation in performance, impose operation restrictions and potentially make devices unsafe.Solid-state, lithium-metal-based, batteries show promise to meet electric vehicle market requirements, but technical challenges to overcome rapid degradation and cost-effective processing remains. Cathode/electrolyte interfacial side reactions can lead to passivating layer formation, thus increasing cell resistance, unwanted additional overvoltage, and ultimately capacity loss. These phenomena are exacerbated in solid-to-solid contact between solid state electrolytes, active materials, and electronic conductive agents. Therefore, electrode manufacturing design is required to mitigate these issues.Within this work we have evaluated Spray Drying (SD) and Atomic Layer Deposition (ALD) coating processes to engineer the cathode/ electrolyte interface of SSBs, thus improving performance and overall cell cycle life. Cathode materials coating is utilised as an effective strategy to mitigate the degradation of the interface. SD is classically utilised in the food and pharma industries, and it has recently been expanded to include the synthesis/shaping of battery electrode materials as a versatile and robust methodology that can be easily scaled up. ALD is a widely exploited technique in the semiconductor (SC) industry based on self-limiting chemical reactions to deposit stoichiometrically-fixed, defect-free and nanometric-thick materials on surfaces. As such, the application of ALD to coat powders in the battery community is innovative and currently under development.Cathodic materials such as NMC (Nickel Manganese Cobalt Oxides) have been investigated, as the need for improving the capacity retention is strong for high-content (>80%) nickel cathodes. Indeed, ALD utilised to coat NMC powder provides a nanometric thick layer of a dielectric but ionic conductive metal oxide. Optimisation of aluminium oxide shell on a core of polycrystalline high nickel material has been investigated with surface engineering. In parallel, we have been exploring the benefit of SD to create an NMC811 powder showing a decorated structure using two different approaches. Indeed, we have either used preformed metal oxide nanoparticles dispersed in an NMC suspension or synthesised a metal oxide layer on top of the NMC in-situ by a chemical reaction during the spray process.Morphological and chemical characterisation of the products have been crucial to develop the coating processes. Electrochemical Impedance Spectroscopy (EIS) probed the engineered cathode/ electrolyte interface within half- and full-coin cell configuration. Rate performance and long-term cycling evaluation has driven the design of an oxide-based lithium metal solid state battery.Alumina coated powder NMC showed longer capacity retention than raw materials when tested in coin cell batteries. The cells were assembled using thin lithium metal anode, Lithium-Lanthanum Zirconium Oxide (LLZO) electrolyte, and surface-engineered NMC811 supported by aluminium current collector. Key words:Surface Engineering, Coatings, Solid-State Batteries (SSB), Spray Dry, Atomic Layer Deposition (ALD), Preformed Nanoparticles, Nickel Manganese Cobalt Oxide (NMC), NMC811, Lithium Lanthanum Zirconium Oxide (LLZO), Interfaces.

Solution ALD Processing of Halide Perovskite Thin Films Yields Superior Functional Quality and Stability Than Classical Processing

The range of materials accessible by classical ALD is limited by the volatility requirement applied to the precursors. However, solution ALD (sALD) transfers the self-limiting surface reaction principle of ALD into the solution processing realm and allows for the same level of control in the deposition of ionic or molecular solids, such as polymers, metal-organic frameworks, and halide perovskites, which cannot be delivered from the gas phase.We have developed an sALD procedure for the direct deposition of the prototypical halide perovskite compound, methylammonium triiodoplumbate(IV), (H3CNH3)(PbI3), also referred to as methylammonium lead iodide or MAPI. The process saturates upon dosage variation to a self-limiting growth rate. The material is obtained in crystalline and highly pure, stoichiometric form at room temperature. All analytical techniques confer to indicate the absence of any lead iodide trace. The MAPI layers generated by sALD can be integrated into planar heterojunction stacks and yield functional solar cells.The direct comparison of films of several thickness values prepared in pairs by sALD and by a state-of-the-art spin-coating method shows that the sALD films always overperform their spin-coated counterparts both in terms of charge carrier lifetimes and in terms of stability towards decomposition under thermal, radiative or vacuum stress.Thus, experimental atomic-level control of solution-processed semiconductors is accessible for the first time. It can now be applied to the accurate investigation of halide perovskite photophysics and photochemistry fundamentals as they pertain to transport and interface phenomena.

Chemical Vapor Functionalization of Polymer Membranes for Water Treatment

Polymer membranes are used extensively in water purification to filter and remove particulate and molecular contaminants. Ideally, these membranes should exhibit high permeance, selectivity, and fouling resistance, but these attributes are rarely achieved simultaneously. One approach to improve membrane performance is to modify the polymer using reactive chemical vapors to impart the desired physiochemical properties. In this presentation, I will describe recent work at Argonne using atomic layer deposition (ALD), sequential infiltration synthesis (SIS), and vapor-phase grafting to modify polymer membranes used for ultra- and nano-filtration in water treatment. These techniques rely on self-limiting chemical reactions between gaseous precursors and a solid surface to grow material in an atomically controlled fashion. We have used ALD to produce ultrathin and conformal inorganic layers allowing the membrane pore size and pore wall composition to be precisely tuned, SIS for the bulk modification of polymers by creating an organic-inorganic hybrid material, and vapor-phase grafting of small molecules to achieve additional control over the membrane surface properties. Our studies employ a suite of in-situ and in-operando measurements to elucidate the surface chemistry for these processes and extensive ex-situ characterization and testing to understand the effects of chemical vapor treatment on polymers and how they impact membrane performance.

Chemical Vapor Treatment to Develop Solid-Electrolyte-Interphase and Remove Residual Lithium Compounds

Lithium metal anode (LMA) is considered a promising material for next-generation lithium metal batteries (LMBs). The poor cycling performance of LMBs is due to the presence of residual lithium compounds (RLCs) on the LMA surface, unstable solid-electrolyte interphase (SEI), and lithium dendrite growth. In this study, an atomic layer deposition(ALD)-like process, chemical vapor treatment (CVT) has been utilized to remove RLCs such as LiOH and Li2CO3 from the surface of LMA and develop stable & robust SEI. The XPS investigation shows the conversion of LiOH and Li2CO3 surface contaminants into Li3PO4 via self-limiting surface chemical reactions. Chemical vapor-treated lithium (CVTL) symmetrical cells, and CVTL paired with high capacity/voltage cathodes demonstrated stable cycling, lower voltage hysteresis, and higher-rate capability compared to the bare LMA during electrochemical cycling. The removal of RLCs improves the Li-ion transport and the formation of robust SEI inhibits the continuous side reaction and suppresses the Li dendrite growth. Keywords: chemical vapor treatment, lithium metal anode, solid-electrolyte-interphase, residual lithium compounds, fast charging.