Atomic Layer Deposition on Dispersed Materials in Liquid Phase by Stoichiometrically Limited Injections

Atomic layer deposition (ALD) is a well‐established vapor‐phase technique for depositing thin films with high conformality and atomically precise control over thickness. Its industrial development has been largely confined to wafers and low‐surface‐area materials because deposition on high‐surface‐area materials and powders remains extremely challenging. Challenges with such materials include long deposition times, extensive purging cycles, and requirements for large excesses of precursors and expensive low‐pressure equipment. Here, a simple solution‐phase deposition process based on subsequent injections of stoichiometric quantities of precursor is performed using common laboratory synthesis equipment. Precisely measured precursor stoichiometries avoid any unwanted reactions in solution and ensure layer‐by‐layer growth with the same precision as gas‐phase ALD, without any excess precursor or purging required. Identical coating qualities are achieved when comparing this technique to Al₂O₃ deposition by fluidized‐bed reactor ALD (FBR‐ALD). The process is easily scaled up to coat >150 g of material using the same inexpensive laboratory glassware without any loss in coating quality. This technique is extended to sulfides and phosphates and can achieve coatings that are not possible using classic gas‐phase ALD, including the deposition of phosphates with inexpensive but nonvolatile phosphoric acid.     

2D Mechanical Metamaterials with Widely Tunable Unusual Modes of Thermal Expansion

Most natural materials expand uniformly in all directions upon heating. Artificial, engineered systems offer opportunities to tune thermal expansion properties in interesting ways. Previous reports exploit diverse design principles and fabrication techniques to achieve a negative or ultralow coefficient of thermal expansion, but very few demonstrate tunability over different behaviors. This work presents a collection of 2D material structures that exploit bimaterial serpentine lattices with micrometer feature sizes as the basis of a mechanical metamaterials system capable of supporting positive/negative, isotropic/anisotropic, and homogeneous/heterogeneous thermal expansion properties, with additional features in unusual shearing, bending, and gradient modes of thermal expansion. Control over the thermal expansion tensor achieved in this way provides a continuum‐mechanics platform for advanced strain‐field engineering, including examples of 2D metamaterials that transform into 3D surfaces upon heating. Integrated electrical and optical sources of thermal actuation provide capabilities for reversible shape reconfiguration with response times of less than 1 s, as the basis of dynamically responsive metamaterials.     

Atomic layer deposition on polymer based flexible packaging materials: Growth characteristics and diffusion barrier properties

One of the most promising areas for the industrial application of atomic layer deposition (ALD) is for gas barrier layers on polymers. In this work, a packaging material system with improved diffusion barrier properties has been developed and studied by applying ALD on flexible polymer based packaging materials. Nanometer scale metal oxide films have been applied to polymer-coated papers and their diffusion barrier properties have been studied by means of water vapor and oxygen transmission rates. The materials for the study were constructed in two stages: the paper was firstly extrusion coated with polymer film, which was then followed by the ALD deposition of oxide layer. The polymers used as extrusion coatings were polypropylene, low and high density polyethylene, polylactide and polyethylene terephthalate. Water vapor transmission rates (WVTRs) were measured according to method SCAN-P 22:68 and oxygen transmission rates (O₂TRs) according to a standard ASTM D 3985. According to the results a 10 nm oxide layer already decreased the oxygen transmission by a factor of 10 compared to uncoated material. WVTR with 40 nm ALD layer was better than the level currently required for most common dry flexible packaging applications. When the oxide layer thickness was increased to 100 nm and above, the measured WVTRs were limited by the measurement set up. Using an ALD layer allowed the polymer thickness on flexible packaging materials to be reduced. Once the ALD layer was 40 nm thick, WVTRs and O₂TRs were no longer dependent on polymer layer thickness. Thus, nanometer scale ALD oxide layers have shown their feasibility as high quality diffusion barriers on flexible packaging materials.     

Low‐Temperature Wafer‐Scale Deposition of Continuous 2D SnS2 Films

Semiconducting 2D materials, such as SnS₂, hold immense potential for many applications ranging from electronics to catalysis. However, deposition of few‐layer SnS₂ films has remained a great challenge. Herein, continuous wafer‐scale 2D SnS₂ films with accurately controlled thickness (2 to 10 monolayers) are realized by combining a new atomic layer deposition process with low‐temperature (250 °C) postdeposition annealing. Uniform coating of large‐area and 3D substrates is demonstrated owing to the unique self‐limiting growth mechanism of atomic layer deposition. Detailed characterization confirms the 1T‐type crystal structure and composition, smoothness, and continuity of the SnS₂ films. A two‐stage deposition process is also introduced to improve the texture of the films. Successful deposition of continuous, high‐quality SnS₂ films at low temperatures constitutes a crucial step toward various applications of 2D semiconductors.     

Extrusion‐Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL^?1) can be readily achieved. The shear‐thinning behavior of the aqueous hGO ink enables extrusion‐based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4–25 nm through‐holes on hGO sheets), microscale (tens of micrometer‐sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high‐performance energy storage devices that rely on interfacial reactions to promote full active‐site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive‐free architectures are demonstrated as the first 3D printed lithium–oxygen (Li–O₂) cathodes and characterized alongside 3D printed GO‐based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high‐energy‐density battery systems.     

Ultrathin oxide films by atomic layer deposition on graphene

In this paper, a method is presented to create and characterize mechanically robust, free-standing, ultrathin, oxide films with controlled, nanometer-scale thickness using atomic layer deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 ± 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes, and flexible electronics.     

Multiple Functionalities of Polyelectrolyte Multilayer Films: New Biomedical Applications

The design of advanced functional materials with nanometer‐ and micrometer‐scale control over their properties is of considerable interest for both fundamental and applied studies because of the many potential applications for these materials in the fields of biomedical materials, tissue engineering, and regenerative medicine. The layer‐by‐layer deposition technique introduced in the early 1990s by Decher, Moehwald, and Lvov is a versatile technique, which has attracted an increasing number of researchers in recent years due to its wide range of advantages for biomedical applications: ease of preparation under “mild” conditions compatible with physiological media, capability of incorporating bioactive molecules, extra‐cellular matrix components and biopolymers in the films, tunable mechanical properties, and spatio‐temporal control over film organization. The last few years have seen a significant increase in reports exploring the possibilities offered by diffusing molecules into films to control their internal structures or design “reservoirs,” as well as control their mechanical properties. Such properties, associated with the chemical properties of films, are particularly important for designing biomedical devices that contain bioactive molecules. In this review, we highlight recent work on designing and controlling film properties at the nanometer and micrometer scales with a view to developing new biomaterial coatings, tissue engineered constructs that could mimic in vivo cellular microenvironments, and stem cell “niches.”     

Vacuum‐Drying Processed Micrometer‐Thick Stable CsPbBr3 Perovskite Films with Efficient Blue‐To‐Green Photoconversion

Metal halide perovskite materials have attracted great attention owing to their fascinating optoelectronic characteristics and low cost fabrication via facile solution processing. One of the potential applications of these materials is to employ them as color‐conversion layers (CCLs) for visible blue light to achieve full‐color displays. However, obtaining thick perovskite films to realize complete color conversion is a key challenge. Here, the fabrication of micrometer‐level thick CsPbBr₃ perovskite films is presented through a facile vacuum drying approach. An efficient green photoconversion is realized in a 3.8 µm thick film from blue light @ 463 nm. For a back luminance of 1000 cd m^?2, the brightness of the resulting green emission can reach as high as 200 cd m^?2. Furthermore, only ≈2% of decay in brightness is observed when the films are tested after 18 days of exposure to ambient environment. In addition, a potential design is also proposed for full‐color displays with perovskite materials incorporated as CCLs.     

Atom‐by‐Atom Fabrication of Monolayer Molybdenum Membranes

Fabrication of materials in the monolayer regime to acquire fascinating physical properties has attracted enormous interest during the past decade, and remarkable success has been achieved for layered materials adopting weak interlayer van der Waals forces. However, the fabrication of monolayer metal membranes possessing strong intralayer bonding remains elusive. Here, suspended monolayer Mo membranes are fabricated from monolayer MoSe₂ films via selective electron beam (e‐beam) ionization of Se atoms by scanning transmission electron microscopy (STEM). The nucleation and subsequent growth of the Mo membranes are triggered by the formation and aggregation of Se vacancies as seen by atomic resolution sequential STEM imaging. Various novel structural defects and intriguing self‐healing characteristics are unveiled during the growth. In addition, the monolayer Mo membrane is highly robust under the e‐beam irradiation. It is likely that other metal membranes can be fabricated in a similar manner, and these pure metal‐based 2D materials add to the diversity of 2D materials and introduce profound novel physical properties.     

Reaktives Magnetronsputtern von Dünnschichtsolarzellen

Reactive Magnetron Sputtering of Thin Film Solar Cells We show that reactive magnetron sputtering is well suited to deposit CuInS₂‐thin film absorber layers of high electronic quality. Using metallic targets and substrate temperatures below 500 °C, compact films with grain sizes in the micrometer range can be obtained. The structural and electronic properties of these layers are comparable to CuInS₂ thin films prepared by a 2‐step sulfurization process, which is being commercialized at present. In particular, the reactively sputtered films show minority carrier diffusion lengths larger than the layer thickness (≈ 2μm). This results in solar cells with conversion efficiences larger than 10 %, comparable to the best conversion efficiencies for CuInS₂‐solar cells obtained from other deposition processes. These results are promising for the potential application of magnetron sputtering as a large area deposition process for absorber layers in thin film solar cells.     

Controlling the crystallinity and roughness of atomic layer deposited titanium dioxide films

The surface roughness of thin films is an important parameter related to the sticking behaviour of surfaces in the manufacturing of microelectomechanical systems (MEMS). In this work, TiO2 films made by atomic layer deposition (ALD) with the TiCl4-H2O process were characterized for their growth, roughness and crystallinity as function of deposition temperature (110-300 degrees C), film thickness (up to approximately 100 nm) and substrate (thermal SiO2, RCA-cleaned Si, Al2O3). TiO2 films got rougher with increasing film thickness and to some extent with increasing deposition temperature. The substrate drastically influenced the crystallization behaviour of the film: for films of about 20 nm thickness, on thermal SiO2 and RCA-cleaned Si, anatase TiO2 crystal diameter was about 40 nm, while on Al2O3 surface the diameter was about a micrometer. The roughness could be controlled from 0.2 nm up to several nanometers, which makes the TiO2 films candidates for adhesion engineering in MEMS.     

Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High‐Performance Cathode

A novel two‐step surface modification method that includes atomic layer deposition (ALD) of TiO₂ followed by post‐annealing treatment on spinel LiNi_0.5Mn_1.5O₄ (LNMO) cathode material is developed to optimize the performance. The performance improvement can be attributed to the formation of a TiMn₂O₄ (TMO)‐like spinel phase resulting from the reaction of TiO₂ with the surface LNMO. The Ti incorporation into the tetrahedral sites helps to combat the impedance growth that stems from continuous irreversible structural transition. The TMO‐like spinel phase also alleviates the electrolyte decomposition during electrochemical cycling. 25 ALD cycles of TiO₂ growth are found to be the optimized parameter toward capacity, Coulombic efficiency, stability, and rate capability enhancement. A detailed understanding of this surface modification mechanism has been demonstrated. This work provides a new insight into the atomic‐scale surface structural modification using ALD and post‐treatment, which is of great importance for the future design of cathode materials.     

Electrokinetic Energy Conversion in Self‐Assembled 2D Nanofluidic Channels with Janus Nanobuilding Blocks

Inspired by the microstructure of nacre, material design, and large‐scale integration of artificial nanofluidic devices step into a completely new stage, termed 2D nanofluidics, in which mass and charge transportation are confined in the interstitial space between reconstructed 2D nanomaterials. However, all the existing 2D nanofluidic systems are reconstituted from homogeneous nanobuilding blocks. Herein, this paper reports the bottom‐up construction of 2D nanofluidic materials with kaolinite‐based Janus nanobuilding blocks, and demonstrates two types of electrokinetic energy conversion through the network of 2D nanochannels. Being different from previous 2D nanofluidic systems, two distinct types of sub‐nanometer‐ and nanometer‐wide fluidic channels of about 6.8 and 13.8 Å are identified in the reconstructed kaolinite membranes (RKM), showing prominent surface‐governed ion transport behaviors and nearly perfect cation‐selectivity. The RKMs exhibit superior capability in osmotic and hydraulic energy conversion, compared to graphene‐based membranes. The mineral‐based 2D nanofluidic system opens up a new avenue to self‐assemble asymmetric 2D nanomaterials for energy, environmental, and healthcare applications.     

Anisotropic Imprint of Amorphization and Phase Separation in Manganite Thin Films via Laser Interference Irradiation

Materials with mesoscopic structural and electronic phase separation, either inherent from synthesis or created via external means, are known to exhibit functionalities absent in the homogeneous counterparts. One of the most notable examples is the colossal magnetoresistance discovered in mixed‐valence manganites, where the coexistence of nano‐ to micrometer‐sized phase‐separated domains dictates the magnetotransport. However, it remains challenging to pattern and process such materials into predesigned structures and devices. In this work, a direct laser interference irradiation (LII) method is employed to produce periodic stripes in thin films of a prototypical phase‐separated manganite Pr_0.65(Ca_0.75Sr_0.25)_0.35MnO₃ (PCSMO). LII induces selective structural amorphization within the crystalline PCSMO matrix, forming arrays with dimensions commensurate with the laser wavelength. Furthermore, because the length scale of LII modification is compatible to that of phase separation in PCSMO, three orders of magnitude of increase in magnetoresistance and significant in‐plane transport anisotropy are observed in treated PCSMO thin films. Our results show that LII is a rapid, cost‐effective and contamination‐free technique to tailor and improve the physical properties of manganite thin films, and it is promising to be generalized to other functional materials.     

Using fence post designs to speed the atomic layer deposition of optical thin films

Atomic layer deposition (ALD) at this time is much slower than conventional optical thin-film deposition techniques. A more rapid ALD process for SiO(2) has been developed than for other ALD materials. A fence post design for optical thin films has thin layers of high-index posts standing above a broad low-index ground. If a design for ALD can be predominantly composed of SiO(2) layers with thin high-index layers, the deposition times can be correspondingly shortened, and it is shown that the required performance can still be nearly that of more conventional designs with high- and low-index layers of equal thickness. This combination makes the ALD benefits of conformal coating and precise thickness control more practical for optical thin-film applications.     

Properties of atomic layer deposited HfO2 thin films

The growth, composition and morphology of HfO₂ films that have been deposited by atomic layer deposition (ALD) are examined in this article. The films are deposited using two different ALD chemistries: i) tetrakis ethylmethyl amino hafnium and H₂O at 250° and ii) tetrakis dimethyl amino hafnium and H₂O at 275 °C. The growth rates are 1.2 Å/cycle and 1.0 Å/cycle respectively. The main impurities detected both by X-ray Photoelectron Spectroscopy and Fourier transform infrared spectroscopy (FTIR) are bonded carbon (~ 3 at.%) and both bulk and terminal OH species that are partially desorbed after high temperature inert anneals up to 900 °C. Atomic Force Microscopy reveals increasing surface roughness as a function of increasing film thickness. X-ray diffraction shows that the morphology of the as-deposited films is thickness dependent; films with thickness around 30 nm for both processes are amorphous while ~ 70 nm films show the existence of crystallites. These results are correlated with FTIR measurements in the far IR region where the HfO₂ peaks are found to provide an easy and reliable technique for the determination of the crystallinity of relatively thick HfO₂ films. The index of refraction for all films is very close to that for bulk crystalline HfO₂.     

3D optomechanical metamaterials

Ideally, many materials should have a “knob” that allows for changing its properties at will, including the possibility to flip the sign of its behavior. This “knob” could be used to continuously tune the properties or in the sense of a digital switch. Such extreme level of stimulus–responsiveness has come into reach with recently increased possibilities of manufacturing complex rationally designed artificial materials called metamaterials on the micrometer scale. Here, we present mechanical metamaterials composed of liquid–crystal elastomers, whose director field is arranged into a designed complex three-dimensional (3D) pattern during the 3D laser printing process. External light from a blue LED, with intensities in the range of 10–30 W/cm², serves as the stimulus. In the first example, we repeatedly flip the sign of the Poisson’s ratio of an achiral architecture within classical elasticity. In the second example, we flip the sign of the twist per strain in a chiral metamaterial beyond classical elasticity. The presented examples overcome major limitations in responsive mechanical metamaterials and we foresee many possible three-dimensional responsive micro-architectures manufactured along these lines.     

Confinement Catalysis with 2D Materials for Energy Conversion

The unique electronic and structural properties of 2D materials have triggered wide research interest in catalysis. The lattice of 2D materials and the interface between 2D covers and other substrates provide intriguing confinement environments for active sites, which has stimulated a rising area of “confinement catalysis with 2D materials.” Fundamental understanding of confinement catalysis with 2D materials will favor the rational design of high‐performance 2D nanocatalysts. Confinement catalysis with 2D materials has found extensive applications in energy‐related reaction processes, especially in the conversion of small energy‐related molecules such as O₂, CH₄, CO, CO₂, H₂O, and CH₃OH. Two representative strategies, i.e., 2D lattice‐confined single atoms and 2D cover‐confined metals, have been applied to construct 2D confinement catalytic systems with superior catalytic activity and stability. Herein, the recent advances in the design, applications, and structure–performance analysis of two 2D confinement catalytic systems are summarized. The different routes for tuning the electronic states of 2D confinement catalysts are highlighted and perspectives on confinement catalysis with 2D materials toward energy conversion and utilization in the future are provided.     

Electroplating to visualize defects in Al2O3 thin films grown using atomic layer deposition

Thin films grown using atomic layer deposition (ALD) are known for being continuous and nearly pinhole-free. These characteristics enable ALD films to be important in many applications such as gas or copper diffusion barriers, gate dielectrics, surface modification and functionalization layers. Few methods have been demonstrated to characterize defects in ALD films. In this study, a method to render the defects visible in Al₂O₃ ALD thin films on conductive substrates has been developed by growing copper bumps locally at the defect sites using electroplating. The electroplated copper can be easily observed or inspected using conventional optical- or electron-microscopy. Using this approach, the defect density in Al₂O₃ ALD thin films grown on nickel substrates has been shown to be as low as 38 /cm².     

Atomic layer deposition of palladium films on Al2O3 surfaces

We examined the atomic layer deposition (ALD) of Pd films using sequential exposures of Pd(II) hexafluoroacetylacetonate (Pd(hfac)₂) and formalin and discovered that formalin enables the efficient nucleation of Pd ALD on Al₂O₃. In situ quartz crystal microbalance measurements revealed that the Pd nucleation is hampered by the relatively slow reaction of the adsorbed Pd(hfac)₂ species, but is accelerated using larger initial Pd(hfac)₂ and formalin exposures. Pd nucleation proceeds via coalescence of islands and leaves hfac contamination at the Al₂O₃ interface. Pd films were deposited on the thermal oxide of silicon, glass and mesoporous anodic alumina following the ALD of a thin Al₂O₃ seed layer and analyzed using a variety of techniques. We measured a Pd ALD growth rate of 0.2 Å/cycle following a nucleation period of slower growth. The deposited films are cubic Pd with a roughness of 4.2 nm and a resistivity of 11 μΩ cm at 42 nm thickness. Using this method, Pd deposits conformally on the inside of mesoporous anodic alumina membranes with aspect ratio ∼1500 yielding promising hydrogen sensors.