Stabilized Nickel-Rich-Layered Oxide Electrodes for High-Performance Lithium-Ion Batteries

This work made use of the Aalto University Otanano-Nanomicroscopy Center and RAMI infrastructures.Financial support from Business Finland NextGenBat[grant number 211849]is greatly acknowledged.The tomography experiment was performed at the beamline ID16B of the European Synchrotron Radiation Facility(ESRF),Grenoble,France,in the frame of proposal CH-6644.The patent titled“Stabilized Positive Electrode Material to Enable High Energy and Power Density Lithium-Ion Batteries”(IPD3173)is pertinent to this manuscript.It was filed by Zahra Ahaliabadeh and Tanja Kallio,and the patent rights are held by Aalto University.

Atomic layer deposition in advanced display technologies:from photoluminescence to encapsulation

Driven by the growing demand for next-generation displays,the development of advanced luminescent materials with exceptional photoelectric properties is rapidly accelerating,with such materials including quantum dots and phosphors,etc.Nevertheless,the primary challenge preventing the practical application of these luminescent materials lies in meeting the required durability standards.Atomic layer deposition(ALD)has,therefore,been employed to stabilize luminescent materials,and as a result,flexible display devices have been fabricated through material modification,surface and interface engineering,encapsulation,cross-scale manufacturing,and simulations.In addition,the appropriate equipment has been developed for both spatial ALD and fluidized ALD to satisfy the low-cost,high-efficiency,and high-reliability manufacturing requirements.This strategic approach establishes the groundwork for the development of ultra-stable luminescent materials,highly efficient light-emitting diodes(LEDs),and thin-film packaging.Ultimately,this significantly enhances their potential applicability in LED illumination and backlighted displays,marking a notable advancement in the display industry.

Improved Efficiency and Stability of Organic Solar Cells by Interface Modification Using Atomic Layer Deposition of Ultrathin Aluminum Oxide

The interfacial contacts between the electron transporting layers(ETLs)and the photoactive layers are crucial to device performance and stability for OSCs with inverted architecture.Herein,atomic layer deposition(ALD)fabricated ultrathin Al_(2)O_(3)layers are applied to modify the ETLs/active blends(PM6:BTP-BO-4F)interfaces of OSCs,thus improving device performance.The ALD-Al_(2)O_(3)thin layers on ZnO significantly improved its surface morphology,which led to the decreased work function of ZnO and reduced recombination losses in devices.The simultaneous increase in open-circuit voltage(V_(OC)),short-circuit current density(J_(SC))and fill factor(FF)were achieved for the OSCs incorporated with ALD-Al_(2)O_(3)interlayers of a certain thickness,which produced a maximum PCE of 16.61%.Moreover,the ALD-Al_(2)O_(3)interlayers had significantly enhanced device stability by suppressing degradation of the photoactive layers induced by the photocatalytic activity of ZnO and passivating surface defects of ZnO that may play the role of active sites for the adsorption of oxygen and moisture.

Preparation of palladium-based catalyst by plasma-assisted atomic layer deposition and its applications in CO_(2) hydrogenation reduction

Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al_(2)O_(3)or Fe_(2)O_(3)/γ-Al_(2)O_(3)support,using palladium hexafluoroacetylacetonate as the Pd precursor and H_(2)plasma as counter-reactant.Scanning transmission electron microscopy exhibits that highdensity Pd nanoparticles are uniformly dispersed over Fe_(2)O_(3)/γ-Al_(2)O_(3)support with an average diameter of 4.4 nm.The deposited Pd-Fe_(2)O_(3)/γ-Al_(2)O_(3)shows excellent catalytic performance for CO_(2)hydrogenation in a dielectric barrier discharge reactor.Under a typical condition of H_(2)to CO_(2)ratio of 4 in the feed gas,the discharge power of 19.6 W,and gas hourly space velocity of10000 h^(-1),the conversion of CO_(2)is as high as 16.3% with CH_(3)OH and CH4selectivities of 26.5%and 3.9%,respectively.

Atomic layer deposition for nanoscale oxide semiconductor thin film transistors:review and outlook

Since the first report of amorphous In–Ga–Zn–O based thin film transistors,interest in oxide semiconductors has grown.They offer high mobility,low off-current,low process temperature,and wide flexibility for compositions and processes.Unfortunately,depositing oxide semiconductors using conventional processes like physical vapor deposition leads to problematic issues,especially for high-resolution displays and highly integrated memory devices.Conventional approaches have limited process flexibility and poor conformality on structured surfaces.Atomic layer deposition(ALD)is an advanced technique which can provide conformal,thickness-controlled,and high-quality thin film deposition.Accordingly,studies on ALD based oxide semiconductors have dramatically increased recently.Even so,the relationships between the film properties of ALD-oxide semiconductors and the main variables associated with deposition are still poorly understood,as are many issues related to applications.In this review,to introduce ALD-oxide semiconductors,we provide:(a)a brief summary of the history and importance of ALD-based oxide semiconductors in industry,(b)a discussion of the benefits of ALD for oxide semiconductor deposition(in-situ composition control in vertical distribution/vertical structure engineering/chemical reaction and film properties/insulator and interface engineering),and(c)an explanation of the challenging issues of scaling oxide semiconductors and ALD for industrial applications.This review provides valuable perspectives for researchers who have interest in semiconductor materials and electronic device applications,and the reasons ALD is important to applications of oxide semiconductors.

Oxidative Molecular Layer Deposition Tailoring Eco-Mimetic Nanoarchitecture to Manipulate Electromagnetic Attenuation and Self-Powered Energy Conversion

Advanced electromagnetic devices,as the pillars of the intelligent age,are setting off a grand transformation,redefining the structure of society to present pluralism and diversity.However,the bombardment of electromagnetic radiation on society is also increasingly serious along with the growing popularity of"Big Data".Herein,drawing wisdom and inspiration from nature,an eco-mimetic nanoarchitecture is constructed for the first time,highly integrating the advantages of multiple components and structures to exhibit excellent electromagnetic response.Its electromagnetic properties and internal energy conversion can be flexibly regulated by tailoring microstructure with oxidative molecular layer deposition(oMLD),providing a new cognition to frequency-selective microwave absorption.The optimal reflection loss reaches≈−58 dB,and the absorption frequency can be shifted from high frequency to low frequency by increasing the number of oMLD cycles.Meanwhile,a novel electromagnetic absorption surface is designed to enable ultra-wideband absorption,covering almost the entire K and Ka bands.More importantly,an ingenious self-powered device is constructed using the eco-mimetic nanoarchitecture,which can convert electromagnetic radiation into electric energy for recycling.This work offers a new insight into electromagnetic protection and waste energy recycling,presenting a broad application prospect in radar stealth,information communication,aerospace engineering,etc.

Atomic layer deposition of thin films:from a chemistry perspective

Atomic layer deposition(ALD)has become an indispensable thin-film technology in the contemporary microelectronics industry.The unique self-limited layer-by-layer growth feature of ALD has outstood this technology to deposit highly uniform conformal pinhole-free thin films with angstrom-level thickness control,particularly on 3D topologies.Over the years,the ALD technology has enabled not only the successful downscaling of the microelectronic devices but also numerous novel 3D device structures.As ALD is essentially a variant of chemical vapor deposition,a comprehensive understanding of the involved chemistry is of crucial importance to further develop and utilize this technology.To this end,we,in this review,focus on the surface chemistry and precursor chemistry aspects of ALD.We first review the surface chemistry of the gas–solid ALD reactions and elaborately discuss the associated mechanisms for the film growth;then,we review the ALD precursor chemistry by comparatively discussing the precursors that have been commonly used in the ALD processes;and finally,we selectively present a few newly-emerged applications of ALD in microelectronics,followed by our perspective on the future of the ALD technology.

Atomic layer deposition to heterostructures for application in gas sensors

Atomic layer deposition(ALD) is a versatile technique to deposit metals and metal oxide sensing materials at the atomic scale to achieve improved sensor functions. This article reviews metals and metal oxide semiconductor(MOS) heterostructures for gas sensing applications in which at least one of the preparation steps is carried out by ALD. In particular, three types of MOS-based heterostructures synthesized by ALD are discussed, including ALD of metal catalysts on MOS, ALD of metal oxides on MOS and MOS core–shell(C–S) heterostructures.The gas sensing performances of these heterostructures are carefully analyzed and discussed.Finally, the further developments required and the challenges faced by ALD for the synthesis of MOS gas sensing materials are discussed.

Atomic-scale engineering of advanced catalytic and energy materials via atomic layer deposition for eco-friendly vehicles

Zero-emission eco-friendly vehicles with partly or fully electric powertrains have exhibited rapidly increased demand for reducing the emissions of air pollutants and improving the energy efficiency. Advanced catalytic and energy materials are essential as the significant portions in the key technologies of eco-friendly vehicles, such as the exhaust emission control system,power lithium ion battery and hydrogen fuel cell. Precise synthesis and surface modification of the functional materials and electrodes are required to satisfy the efficient surface and interface catalysis, as well as rapid electron/ion transport. Atomic layer deposition(ALD), an atomic and close-to-atomic scale manufacturing method, shows unique characteristics of precise thickness control, uniformity and conformality for film deposition, which has emerged as an important technique to design and engineer advanced catalytic and energy materials. This review has summarized recent process of ALD on the controllable preparation and modification of metal and oxide catalysts, as well as lithium ion battery and fuel cell electrodes. The enhanced catalytic and electrochemical performances are discussed with the unique nanostructures prepared by ALD. Recent works on ALD reactors for mass production are highlighted. The challenges involved in the research and development of ALD on the future practical applications are presented, including precursor and deposition process investigation, practical device performance evaluation, large-scale and efficient production, etc.

Atomic layer deposition of ultrathin layered TiO_2 on Pt/C cathode catalyst for extended durability in polymer electrolyte fuel cells

This study shows the preparation of a TiO2 coated Pt/C（TiO2/Pt/C） by atomic layer deposition（ALD）,and the examination of the possibility for TiO2/Pt/C to be used as a durable cathode catalyst in polymer electrolyte fuel cells（PEFCs）. Cyclic voltammetry results revealed that TiO2/Pt/C catalyst which has 2 nm protective layer showed similar activity for the oxygen reduction reaction compared to Pt/C catalysts and they also had good durability. TiO2/Pt/C prepared by 10 ALD cycles degraded 70% after 2000 Accelerated degradation test, while Pt/C corroded 92% in the same conditions. TiO2 ultrathin layer by ALD is able to achieve a good balance between the durability and activity, leading to TiO2/Pt/C as a promising cathode catalyst for PEFCs. The mechanism of the TiO2 protective layer used to prevent the degradation of Pt/C is discussed.

Secondary electron yield of air-exposed ALD-Al_(2)O_(3) coating on Ag-plated aluminum alloy

Secondary electron yield(SEY)of air-exposed metals tends to be increased because of air-formed oxide,hydrocarbon,and other contaminants.This enhances the possibility of secondary electron multipacting in high-power microwave systems,resulting in undesirable occurrence of discharge damage.Al_(2)O_(3) coatings have been utilized as passive and protective layers on device packages to provide good environmental stability.We employed atomic layer deposition(ALD)to produce a series of uniform Al_(2)O_(3) coatings with appropriate thickness on Ag-plated aluminum alloy.The secondary electron emission characteristics and their variations during air exposure were observed.The escape depth of secondary electron needs to exceed the coating thickness to some extent in order to demonstrate SEY of metallic substrates.Based on experimental and calculated results,the maximum SEY of Ag-plated aluminum alloy had been maintained at 2.45 over 90 days of exposure without obvious degradation by applying 1 nm Al_(2)O_(3) coatings.In comparison,the peak SEY of untreated Ag-plated aluminum alloy grew from an initial 2.33 to 2.53,exceeding that of the 1 nm Al_(2)O_(3) sample.The ultra-thin ALDAl_(2)O_(3) coating substantially enhanced the SEY stability of metal materials,with good implications for the environmental dependability of spacecraft microwave components.

Implementation of sub-100 nm vertical channel-all-around(CAA) thin-film transistor using thermal atomic layer deposited IGZO channel

In-Ga-Zn-O(IGZO) channel based thin-film transistors(TFT), which exhibit high on-off current ratio and relatively high mobility, has been widely researched due to its back end of line(BEOL)-compatible potential for the next generation dynamic random access memory(DRAM) application. In this work, thermal atomic layer deposition(TALD) indium gallium zinc oxide(IGZO) technology was explored. It was found that the atomic composition and the physical properties of the IGZO films can be modulated by changing the sub-cycles number during atomic layer deposition(ALD) process. In addition, thin-film transistors(TFTs) with vertical channel-all-around(CAA) structure were realized to explore the influence of different IGZO films as channel layers on the performance of transistors. Our research demonstrates that TALD is crucial for high density integration technology, and the proposed vertical IGZO CAA-TFT provides a feasible path to break through the technical problems for the continuous scale of electronic equipment.

Continuous Lithium-Ion Extraction From Seawater and Mine Water With a Fuel Cell System and Ceramic Membranes

The demand for electronic devices that utilize lithium is steadily increasing in this rapidly advancing technological world.Obtaining high-purity lithium in an environmentally friendly way is challenging by using commercialized methods.Herein,we propose the first fuel cell system for continuous lithium-ion extraction using a lithium superionic conductor membrane and advanced electrode.The fuel cell system for extracting lithium-ion has demonstrated a twofold increase in the selectivity of Li^(+)/Na^(+)while producing electricity.Our data show that the fuel cell with a titania-coated electrode achieves 95%lithium-ion purity while generating 10.23 Wh of energy per gram of lithium.Our investigation revealed that using atomic layer deposition improved the electrode's uniformity,stability,and electrocatalytic activity.After 2000 cycles determined by cyclic voltammetry,the electrode preserved its stability.

Application of atomic layer deposition in fabricating high-efficiency electrocatalysts

Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition(ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core–shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.

Atomic-Scale Layer-by-Layer Deposition of Fe SiAl@ZnO@Al_(2)O_(3) Hybrid with Threshold Anti-Corrosion and Ultra-High Microwave Absorption Properties in Low-Frequency Bands

Developing highly efficient magnetic microwave absorb-ers(MAs)is crucial,and yet challenging for anti-corrosion properties in extremely humid and salt-induced foggy environments.Herein,a dual-oxide shell of ZnO/Al_(2)O_(3) as a robust barrier to FeSiAl core is introduced to mitigate corrosion resistance.The FeSiAl@ZnO@Al_(2)O_(3) layer by layer hybrid structure is realized with atomic-scale precision through the atomic layer deposition technique.Owing to the unique hybrid structure,the FeSiAl@ZnO@Al_(2)O_(3) exhibits record-high micro-wave absorbing performance in low-frequency bands covering L and S bands with a minimum reflection loss(RLmin)of-50.6 dB at 3.4 GHz.Compared with pure FeSiAl(RLmin of-13.5 dB,a bandwidth of 0.5 GHz),the RLmin value and effective bandwidth of this designed novel absorber increased up to~3.7 and~3 times,respectively.Fur-thermore,the inert ceramic dual-shells have improved 9.0 times the anti-corrosion property of FeSiAl core by multistage barriers towards corrosive medium and obstruction of the electric circuit.This is attributed to the large charge transfer resistance,increased impedance modulus|Z|0.01 Hz,and frequency time constant of FeSiAl@ZnO@Al_(2)O_(3).The research demonstrates a promising platform toward the design of next-generation MAs with improved anti-corrosion properties.

Single atom catalyst by atomic layer deposition technique

Noble single‐atom catalysts have rapidly been attracting attention due to their unique catalytic properties and maximized utilization.Atomic layer deposition(ALD)is an emerging powerful technique for large‐scale synthesis of stable single atom.In this review,we summarize recent developments of single atom synthesized by ALD as well as explore future research direction and trends.

Atomic layer deposition: Catalytic preparation and modification technique for the next generation

Atomic layer deposition(ALD)attracts great attention nowadays due to its ability for designing and modifying catalytic systems at the molecular level.There are several reported review papers published recently discussing this technique in catalysis.However,the mechanism on how the deposited materials improve the catalyst stability and tune the reaction selectivity is still unclear.Herein,catalytic systems created via ALD on stepwise preparation and/or modification under self-limiting reaction conditions are summarized.The effects of deposited materials in terms of electronic/geometry modification over the catalytic nanoparticles(NPs)are discussed.These effects explain the mechanism of the catalytic stability improvement and the selectivity modification.The unique properties of ALD for designing new catalytic systems are further investigated for building up photocatalytic reaction nanobowls,tandem catalyst and bi-active-component metallic catalytic systems.

Highly Enhanced Visible-Light-Driven Photoelectrochemical Performance of ZnO-Modified In_2S_3 Nanosheet Arrays by Atomic Layer Deposition

Photoanodes based on In_2S_3/ZnO heterojunction nanosheet arrays(NSAs) have been fabricated by atomic layer deposition of ZnO over In_2S_3 NSAs, which were in situ grown on fluorine-doped tin oxide glasses via a facile solvothermal process. The as-prepared photoanodes show dramatically enhanced performance for photoelectrochemical(PEC) water splitting, compared to single semiconductor counterparts. The optical and PEC properties of In_2S_3/ZnO NSAs have been optimized by modulating the thickness of the Zn O overlayer. After pairing with ZnO, the NSAs exhibit a broadened absorption range and an increased light absorptance over a wide wavelength region of 250–850 nm. The optimized sample of In_2S_3/ZnO-50 NSAs shows a photocurrent density of 1.642 m A cm^(-2)(1.5 V vs. RHE) and an incident photonto-current efficiency of 27.64% at 380 nm(1.23 V vs.RHE), which are 70 and 116 times higher than those of the pristine In_2S_3 NSAs, respectively. A detailed energy band edge analysis reveals the type-II band alignment of the In_2S_3/ZnO heterojunction, which enables efficient separation and collection of photogenerated carriers,especially with the assistance of positive bias potential, and then results in the significantly increased PEC activity.

Atomic layer deposition for quantum dots based devices

Quantum dots(QDs)are promising candidates for the next-generation optical and electronic devices due to the outstanding photoluminance efficiency,tunable bandgap and facile solution synthesis.Nevertheless,the limited optoelectronic performance and poor lifetime of QDs devices hinder their further applications.As a gas-phase surface treatment method,atomic layer deposition(ALD)has shown the potential in QDs surface modification and device construction owing to the atomic-level control and excellent uniformity/conformality.In this perspective,the attempts to utilize ALD techniques in QDs modification to improve the photoluminance efficiency,stability,carrier mobility,as well as interfacial carrier utilization are introduced.ALD proves to be successful in the photoluminance quantum yield(PLQY)enhancement due to the elimination of QDs surface dangling bonds and defects.The QDs stability and devices lifetime are improved greatly through the introduction of ALD barrier layers.Furthermore,the carrier transport is ameliorated efficiently by infilling interstitial spaces during ALD process.Attributed to the ultra-thin and dense coating on the interface,the improvement on optoelectronic performance is achieved.Finally,the challenges of ALD applications in QDs at present and several prospects including ALD process optimization,in-situ characterization and computational simulations are proposed.

FeOx Coating on Pd/C Catalyst by Atomic Layer Deposition Enhances the Catalytic Activity in Dehydrogenation of Formic Acid

Hydrogen generation from formic acid （FA） has received significant attention. The challenge is to obtain a highly active catalyst under mild conditions for practical applications. Here atomic layer deposition （ALD） of FeOx was performed to deposit an ultrathin oxide coating layer to a Pd/C catalyst, therein the FeOx coverage was precisely controlled by ALD cycles. Transmission electron microscopy and powder X-ray diffraction measurements suggest that the FeOx coating layer improved the thermal stability of Pd nanoparticles （NPs）. X-ray photoelectron spectroscopy measurement showed that deposition of FeOx on the Pd NPs caused a positive shift of Pd3d binding energy. In the FA dehydrogenation reaction, the ultrathin FeOx layer on the Pd/C could considerably improve the catalytic activity, and Pd/C coated with 8 cycles of FeOx showed an optimized activity with turnover frequency being about 2 times higher than the uncoated one. shape as a function of the number of FeOx ALD The improved activities were in a volcanocycles, indicating the coverage of FeOx is critical for the optimized activity. In summary, simultaneous improvements of activity and thermal stability of Pd/C catalyst by ultra-thin FeOx overlayer suggest to be an effective way to design active catalysts for the FA dehydrogenation reaction.