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 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.

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-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.

Atomic layer deposition of TiO_(2) on carbon-nanotubes membrane for capacitive deionization removal of chromium from water

Chromium(Cr)is a common heavy metal that has severe impacts on the ecosystem and human health.Capacitive deionization(CDI)is an environment-friendly and energy-efficient electrochemical purification technology to remove Cr from polluted water.The performance of CDI systems relies primarily on the properties of electrodes.Carbon-nanotubes(CNTs)membranes are promising candidates in creating advanced CDI electrodes and processes.However,the low electrosorption capacity and high hydrophobicity of CNTs greatly impede their applications in water systems.In this study,we employ atomic layer deposition(ALD)to deposit TiO_(2) nanoparticulates on CNTs membranes for preparing electrodes with hydrophilicity.The TiO_(2)-deposited CNTs membranes display preferable electrosorption performance and reusability in CDI processes after only 20 ALD cycles deposition.The total Cr and Cr(VI)removal efficiencies are significantly improved to 92.1%and 93.3%,respectively.This work demonstrates that ALD is a highly controllable and simple method to produce advanced CDI electrodes,and broadens the application of metal oxide/carbon composites in the electrochemical processes.

Characteristics and properties of metal aluminum thin films prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum （A1） thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited A1 films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.

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.

Fabrication of Nanoscale Step Height Structure Using Atomic Layer Deposition Combined with Wet Etching

The current techniques used for the fabrication of nanosteps are normally done by layer growth and then ion beam thinning. There are also extra films grown on the step surfaces in order to reduce the roughness. So the whole process is time consuming. In this paper, a nanoscale step height structure is fabricated by atomic layer deposition （ALD） and wet etching techniques. According to the traceable of the step height value, the fabrication process is controllable. Because ALD technology can grow a variety of materials, aluminum oxide （Al2O3） is used to fabricate the nanostep. There are three steps of Al2O3 in this structure including 8 nm, 18 nm and 44 inn. The thickness of Al2O3 film and the height of the step are measured by anellipsometer. The experimental results show that the thickness of Al2O3 film is consistent with the height of the step. The height of the step is measured by AFM. The measurement results show that the height is related to the number of cycles of ALD and the wet etching time. The bottom and the sidewall surface roughness are related to the wet etching time. The step height is calibrated by Physikaliseh-Technische Bundesanstalt （PTB） and the results were 7.5±1.5 nm, 15.5±2.0 nm and 41.8±2.1 nm, respectively. This research provides a method for the fabrication of step height at nanoscale and the nanostep fabricated is potential used for standard references.

High-performance LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) cathode by nanoscale lithium sulfide coating via atomic layer deposition

The commercialization of nickel-rich LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811) has been hindered by its continuous loss of practical capacity and reduction in average working voltage.To address these issues,surface modification has been well-recognized as an effective strategy.Different from the coatings reported in literature to date,in this work,we for the first time report a sulfide coating,amorphous Li_(2)S via atomic layer deposition (ALD).Our study revealed that the conformal nano-Li_(2)S coating shows exceptional protection over the NMC811 cathodes,accounting for the dramatically boosted capacity retention from~11.6%to~71%and the evidently mitigated voltage reduction from 0.39 to 0.18 V after 500 charge–discharge cycles.In addition,the Li_(2)S coating remarkably improved the rate capability of the NMC811 cathode.Our investigation further revealed that all these beneficial effects of the ALD-deposited nano-Li_(2)S coating lie in the following aspects:(i) maintain the mechanical integrity of the NMC811 electrode:(ii) stabilize the NMC electrode/electrolyte interface:and (iii) suppress the irreversible phase transition of NMC structure.Particularly,this study also has revealed that the nano-Li_(2)S coating has played some unique role not associated with traditional non-sulfide coatings such as oxides.In this regard,we disclosed that the Li_(2)S layer has reacted with the released O_(2) from the NMC lattices,and thereby has dramatically mitigated electrolyte oxidation and electrode corrosion.Thus,this study is significant and has demonstrated that sulfides may be an important class of coating materials to tackle the issues of NMCs and other layered cathodes in lithium batteries.

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.

Atomic layer deposition enabling higher efficiency solar cells:A review

Atomic layer deposition(ALD)can synthesise materials with atomic-scale precision.The ability to tune the material composition,film thickness with excellent conformality,allow low-temperature processing,and in-situ real-time monitoring makes this technique very appealing for a wide range of applications.In this review,we focus on the application of ALD layers in a wide range of solar cells.We focus on industrial silicon,thin film,organic and quantum dot solar cells.It is shown that the merits of ALD have already been exploited in a wide range of solar cells at the lab scale and that ALD is already applied in high-volume manufacturing of silicon solar cells.

The Effect of Oxygen Partial Pressure during Active Layer Deposition on Bias Stability of a-InGaZnO TFTs

The effect of oxygen partial pressure （Po2） during the channel layer deposition on bias stability of amorphous indium-gallium-zinc oxide （a-IGZO） thin film transistors （TFTs） is investigated. As Po2 increases from 10% to 30%, it is found that the device shows enhanced bias stress stability with significantly reduced threshold voltage drift under positive gate bias stress. Based on the x-ray photoelectron spectroscopy measurement, the concentration of oxygen vacancies （Or） within the a-IGZO layer is suppressed by increasing Po2. Meanwhile, the low-frequency noise analysis indicates that the average trap density near the channel/dielectric interface continuously drops with increasing Po2. Therefore, the improved interface quality with increasing Po2 during the channel layer deposition can be attributed to the reduction of interface Ov-related defects, which agrees with the enhanced bias stress stability of the a-IGZO TFTs.

Influence of annealing temperature on passivation performance of thermal atomic layer deposition Al_2O_3 films

Chemical and field-effect passivation of atomic layer deposition （ALD） Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy （TEM） and X-ray photoelectron spectroscopy （XPS）, respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.

Influences of different structures on the characteristics of H_2O-based and O_3-based La_xAl_yO films deposited by atomic layer deposition

H_2O-based and O_3-based La_xAl_yO nanolaminate films were deposited on Si substrates by atomic layer deposition（ALD）. Structures and performances of the films were changed by different barrier layers. The effects of different structures on the electrical characteristics and physical properties of the La_xAl_yO films were studied. Chemical bonds in the La_xAl_yO films grown with different structures and different oxidants were also investigated with x-ray photoelectron spectroscopy（XPS）. The preliminary testing results indicate that the La_xAl_yO films with different structures and different oxidants show different characteristics, including dielectric constant, equivalent oxide thickness（EOT）, electrical properties, and stability.

AlO_x prepared by atomic layer deposition for high efficiency-type crystalline silicon solar cell

The influence of atomic layer deposition parameters on the negative charge density in AlOx film is investigated by the corona-charge measurement. Results show that the charge density can reach up to -1.56×10^12 cm%-2 when the thickness of the film is 2.4 nm. The influence of charge density on cell conversion efficiency is further simulated using solar cell analyzing software （PC1D）. With AlOx passivating the rear surface of the silicon, the cell efficiency of 20.66% can be obtained.

Atomic layer deposition of copper thin film and feasibility of deposition on inner walls of waveguides

Copper thin films were deposited by plasma-enhanced atomic layer deposition at low temperature, using copper（I）-N,N′-di-sec-butylacetamidinate as a precursor and hydrogen as a reductive gas. The influence of temperature, plasma power, mode of plasma, and pulse time, on the deposition rate of copper thin film, the purity of the film and the step coverage were studied.The feasibility of copper film deposition on the inner wall of a carbon fibre reinforced plastic waveguide with high aspect ratio was also studied. The morphology and composition of the thin film were studied by atomic force microscopy and x-ray photoelectron spectroscopy,respectively. The square resistance of the thin film was also tested by a four-probe technique. On the basis of on-line diagnosis, a growth mechanism of copper thin film was put forward, and it was considered that surface functional group played an important role in the process of nucleation and in determining the properties of thin films. A high density of plasma and high free-radical content were helpful for the deposition of copper thin films.

Effect of source temperature on phase and metal–insulator transition temperature of vanadium oxide films grown by atomic layer deposition

Vanadium oxide films were grown by atomic layer deposition using the tetrakis[ethylmethylamino] vanadium as the vanadium precursor and H2O as the oxide source. The effect of the source temperature on the quality of vanadium oxide films and valence state was investigated. The crystallinity, surface morphology, film thickness, and photoelectric properties of the films were characterized by x-ray diffraction, atomic force microscope, scanning electron microscope, I–V characteristics curves, and UV–visible spectrophotometer. By varying the source temperature, the content of V6O11, VO2, and V6O13 in the vanadium oxide film increased, that is, as the temperature increased, the average oxidation state generally decreased to a lower value, which is attributed to the rising of the vapor pressure and the change of the ionization degree for organometallics. Meanwhile, the root-mean-square roughness decreased and the metal–insulator transition temperature reduced. Our study is great significance for the fabrication of vanadium oxide films by atomic layer deposition.

Characterization and application in XRF of HfO_(2)-coated glass monocapillary based on atomic layer deposition

Coating a glass monocapillary x-ray optics with high-density film is a promising way to improve transmission characteristics. For a long time, it has been a challenge to coat a high-density film in the inside of monocapillary with an extremely high length-to-diameter ratio. In this work, Hf O2 film is deposited on the inner wall of a tapered glass monocapillary with length 9.9 cm, entrance diameter 596.4 μm, and exit diameter 402.3 μm by atomic layer deposition. The coated and uncoated monocapillaries are studied by the transmission process of x-rays with energy from 5 ke V to 100 ke V and the x-ray fluorescence(XRF) spectra of a Mo sample are detected. Improved transmission characteristics have been obtained for the Hf O2-coated monocapillary. The energy upper limit of focused x-rays increases from 18.1 ke V to 33.0 ke V and the ‘penetration halo’ is suppressed to some extent. The XRF spectrum presents two stronger peaks at ~ 17.4 ke V and~ 19.6 ke V which are considered as the characteristic x-rays of Mo Kα and Mo Kβ. These results reveal that more higher energy x-rays from the W x-ray tube are totally reflected on the inner wall of the Hf O2-coated glass monocapillary due to the increase of total reflection critical angle. This work is significant for more applications of monocapillary in higher energy x-ray field.