New s-Block Metal Pyridinedicarboxylate Network Structures through Gas-Phase Thin-Film Synthesis

The combined atomic and molecular layer deposition (ALD/MLD) technique offers a unique way to build—both known and previously unknown—crystalline coordination polymer materials directly from gaseous precursors in a high-quality thin-film form. Here, we demonstrate the ALD/MLD of crystalline Li-, Na-, and K-based 3,5-pyridinedicarboxylate (3,5-PDC) thin films; the Li₂-3,5-PDC films are of the known Li-ULMOF-4 crystal structure whereas the other as-deposited crystalline films possess structures not previously reported. Another exciting possibility offered by ALD/MLD is the deposition of well-defined but amorphous metal–organic thin films, such as our Mg-, Ca-, Sr-, and Ba-based 3,5-PDC films, which can then be crystallized into water-containing structures through a post-deposition humidity treatment. All together, the new metal–organic structures realized in this study through ALD/MLD comprise a majority of the (anhydrous and water-containing) members of the s-block metal 3,5-pyridinedicarboxylate family.     

Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis,Modeling, and Application

Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe₂, NEt₂, where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)₃] 1 and [Yb(dpdmg)₃] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O₂) and water (H₂O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)₃] 1 was used for proof-of-principle ALD depositions of CeO₂ thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO₂ films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.     

Atomic/Molecular Layer Deposited Iron–Azobenzene Framework Thin Films for Stimuli‐Induced Gas Molecule Capture/Release

The atomic/molecular layer deposition (ALD/MLD) technique provides an elegant way to grow crystalline metal–azobenzene thin films directly from gaseous precursors; the photoactive azobenzene linkers thus form an integral part of the crystal framework. Reversible water capture/release behavior for these thin films can be triggered through the trans–cis photoisomerization reaction of the azobenzene moieties in the structure. The ALD/MLD approach could open up new horizons for example, for the emerging fields of remotely controlled drug delivery and gas storage.     

Insect Sex Pheromone Type Alkenes from the Seeds of Quercus robur

A combination of vacuum liquid chromatography and preparative thin layer chromatography of the combined n-hexane and dichloromethane extracts of the seeds of Quercus robur afforded two insect sex pheromone type alkenes, 5E-tetradecen-1-ol (1) and 6E-tetradecen-1-ol (2), none of which has ever been isolated from any plant sources. The structures of these alkenes were determined by spectroscopic techniques.     

Role of Anionic Backbone in NHC-Stabilized Coinage Metal Complexes: New Precursors for Atomic Layer Deposition**

Cu and Ag precursors that are volatile, reactive, and thermally stable are currently of high interest for their application in atomic-layer deposition (ALD) of thin metal films. In pursuit of new precursors for coinage metals, namely Cu and Ag, a series of new N-heterocyclic carbene (NHC)-based Cu^I and Ag^I complexes were synthesized. Modifications in the substitution pattern of diketonate-based anionic backbones led to five monomeric Cu complexes and four closely related Ag complexes with the general formula [M(^tBuNHC)(R)] (M=Cu, Ag; ^tBuNHC=1,3-di-tert-butyl-imidazolin-2-ylidene; R=diketonate). Thermal analysis indicated that most of the Cu complexes are thermally stable and volatile compared to the more fragile Ag analogs. One of the promising Cu precursors was evaluated for the ALD of nanoparticulate Cu metal deposits by using hydroquinone as the reducing agent at appreciably low deposition temperatures (145–160 °C). This study highlights the considerable impact of the employed ligand sphere on the structural and thermal properties of metal complexes that are relevant for vapor-phase processing of thin films.     

Optimizing the Atomic Layer Deposition of Alumina on Perovskite Nanocrystal Films by Using O2 As a Molecular Probe

Encapsulation methods have shown to be effective in imparting improved stability to metal-halide perovskite nanocrystals (NCs). Atomic layer deposition (ALD) of metal oxides is one of the promising approaches for such encapsulation, yet better control on the process parameters are required to achieve viable lifetimes for several optoelectronic and photocatalytic applications. Herein, we optimize the ALD process of amorphous aluminum oxide (AlO_x) as an encapsulating layer for CsPbBr₃ NC thin films by using oxygen (O₂) as a molecular diffusion probe to assess the uniformity of the deposited AlO_x layer. When O₂ reaches the NC surface, it extracts the photogenerated electrons, thus quenching the PL of the CsPbBr₃ NCs. As the quality of the ALD layer improves, less quenching is expected. We compare three different ALD deposition modes. We find that the low temperature/high temperature and the exposure modes improve the quality of the alumina as a gas barrier when compared with the low temperature mode. We attribute this result to a better diffusion of the ALD precursor throughout the NC film. We propose the low temperature/high temperature as the most suitable mode for future implementation of multilayered coatings.     

Atomic layer deposition of metal-oxide thin films on cellulose fibers

Abstract

Atomic layer deposition (ALD) is a vapor-phase technique capable of producing inorganic thin films with precise control over the thickness of the film. The ALD method offers high precision in the design of advanced 3D nanostructures. In this article, silica and alumina thin films have been grown over fibers of cellulose by the ALD process. The morphology and the chemical composition of the fabricated thin films are characterized, as well as their thermal durability through elevated temperatures. Moreover, XPS is used to confirm the phases of the alumina nanofilms and to further understand the deposition process on the cellulose microfibers.     

Atomic Layer Deposition of Iron Sulfide and Its Application as a Catalyst in the Hydrogenation of Azobenzenes

The atomic layer deposition (ALD) of iron sulfide (FeS_x ) is reported for the first time. The deposition process employs bis(N ,N′ ‐di‐tert‐butylacetamidinato)iron(II) and H₂S as the reactants and produces fairly pure, smooth, and well‐crystallized FeS_x thin films following an ideal self‐limiting ALD growth behavior. The FeS_x films can be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which highlights the broad applicability of this ALD process for engineering the surface of complex 3D nanostructures in general. Highly uniform nanoscale FeS_x coatings on porous γ‐Al₂O₃ powder were also prepared. This compound shows excellent catalytic activity and selectivity in the hydrogenation of azo compounds under mild reaction conditions, demonstrating the promise of ALD FeS_x as a catalyst for organic reactions.     

Photoactive Thin-Film Structures of Curcumin,TiO2 and ZnO

Curcumin is known as a biologically active compound and a possible antimicrobial agent. Here, we combine it with TiO₂ and ZnO semiconductors, known for their photocatalytic properties, with an eye towards synergistic photo-harvesting and/or antimicrobial effects. We deposit different nanoscale multi-layer structures of curcumin, TiO₂ and ZnO, by combining the solution-based spin-coating (S-C) technique and the gas-phase atomic layer deposition (ALD) and molecular layer deposition (MLD) thin-film techniques. As one of the highlights, we demonstrate for these multi-layer structures a red-shift in the absorbance maximum and an expansion of the absorbance edge as far as the longest visible wavelength region, which activates them for the visible light harvesting. The novel fabrication approaches introduced here should be compatible with, e.g., textile substrates, opening up new horizons for novel applications such as new types of protective masks with thin conformal antimicrobial coatings.     

Reduction in the operating temperature of solid oxide fuel cells—potential use in transport applications

The development of solid oxide fuel cells (SOFC) offers new perspectives, in particular as auxiliary power units for vehicle applications. The elaboration of thin electrolyte layers is the main challenge in order to reduce their operating temperature. A brief review of the deposition techniques and of the potential electrolytes is presented. A relatively new technique, Atomic Layer Deposition (ALD), allows to produce thin, dense and homogeneous layers, i.e. zirconia or zirconia-based thin layers can be deposited on different substrates. The interest of elaborating bi- or multi-layer electrolytes is outlined.     

Pentacoordinated Al3+‐Stabilized Active Pd Structures on Al2O3‐Coated Palladium Catalysts for Methane Combustion

Supported Pd catalysts are active in catalyzing the highly exothermic methane combustion reaction but tend to be deactivated owing to local hyperthermal environments. Herein we report an effective approach to stabilize Pd/SiO₂ catalysts with porous Al₂O₃ overlayers coated by atomic layer deposition (ALD). ²⁷Al magic angle spinning NMR analysis showed that Al₂O₃ overlayers on Pd particles coated by the ALD method are rich in pentacoordinated Al³⁺ sites capable of strongly interacting with adjacent surface PdO_x phases on supported Pd particles. Consequently, Al₂O₃‐decorated Pd/SiO₂ catalysts exhibit active and stable PdO_x and Pd–PdO_x structures to efficiently catalyze methane combustion between 200 and 850 °C. These results reveal the unique structural characteristics of Al₂O₃ overlayers on metal surfaces coated by the ALD method and provide a practical strategy to explore stable and efficient supported Pd catalysts for methane combustion.     

Low‐Temperature Atomic Layer Deposition of MoS2 Films

Wet chemical screening reveals the very high reactivity of Mo(NMe₂)₄ with H₂S for the low‐temperature synthesis of MoS₂. This observation motivated an investigation of Mo(NMe₂)₄ as a volatile precursor for the atomic layer deposition (ALD) of MoS₂ thin films. Herein we report that Mo(NMe₂)₄ enables MoS₂ film growth at record low temperatures—as low as 60 °C. The as‐deposited films are amorphous but can be readily crystallized by annealing. Importantly, the low ALD growth temperature is compatible with photolithographic and lift‐off patterning for the straightforward fabrication of diverse device structures.     

Atomic layer deposition of organic-inorganic hybrid materials based on saturated linear carboxylic acids

Atomic layer deposition (ALD) has successfully provided thin films of organic-inorganic hybrid materials based on saturated linear carboxylic acids and trimethylaluminium (TMA). Films were grown for seven carboxylic acids: oxalic, malonic, succinic, glutaric, pimelic, suberic and sebacic acid, i.e. ranging from 2 to 10 carbon atoms in the molecular structure. These processes show exceptionally high growth rates; up to 4.3 nm/cycle for the pimelic acid-TMA system. Quartz crystal microbalance measurements of the growth dynamics indicate that all systems are of a self limiting ALD-type. Nevertheless, temperature dependent growth was observed in several systems. The width of the ALD windows shows correlations with the length of the carbon chains. Fourier transform infrared spectroscopy clearly proved that the deposited films are of a hybrid character, where the carboxylic acids primarily form bidentate complexes, though bridging complexes may also form. All films are X-ray amorphous as deposited. The films were further analyzed by atomic force microscopy for surface roughness and topography, UV-Vis spectroscopy and ellipsometry for optical properties, and the goniometer method for measuring sessile drops for surface wetting properties. Apart from the oxalic and malonic acid-TMA systems, the films are stable in contact with water. The films are generally smooth, transparent and have a refractive index close to 1.5. The complete coverage and accurate growth control offered by the ALD technique is here proven to provide surface-functionalized hybrid materials resembling metal-organic frameworks (MOF), probably as rather dense structures, yet with substantial potential for applications.     

Synthesis and characterisation of zirconium-amido guanidinato complex: a potential precursor for ZrO2 thin films

A new zirconium complex, bis-(ethylmethylamido)-bis-(N,N'-diisopropyl-2-ethylmethylamidoguanidinato)-zirconium(iv) {[(N(i)Pr)(2)C(NEtMe)](2)Zr(NEtMe)(2)}, was synthesised by partial replacement of amide ligands with bidentate guanidinate ligands. The monomeric Zr complex was characterised by (1)H-NMR, (13)C-NMR, EI-MS, elemental analysis, and single crystal X-ray diffraction studies. The thermal properties of the compound was studied by thermogravimetric and differential thermal analysis (TG/DTA). The new Zr compound is thermally stable and can be sublimed quantitatively which renders it promising for thin film growth using vapor deposition techniques like chemical vapor deposition (CVD) and atomic layer deposition (ALD). The use of this complex for CVD of ZrO(2) on Si(100) substrates was attempted in combination with oxygen as the oxidant. Stoichiometric ZrO(2) films with preferred orientation at lower growth temperatures was obtained and the films were almost carbon free. The preliminary electrical characterisation of ZrO(2) films showed encouraging results for possible applications in dielectric oxide structures.     

Preparation of amino-functionalized mesoporous silica thin films with highly ordered large pore structures

Highly ordered amino-functionalized mesoporous silica thin films have been directly synthesized by co-condensation of tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTES) in the presence of triblock copolymer Pluronic P123 surfactant species under acidic conditions by sol-gel dip-coating. The effect of the sol aging on thin films organization is systematically studied, and the optimal sol aging time is obtained. The amino-functionalized mesoporous silica thin films exhibit a long-range ordering of 2D hexagonal (p6mm) mesostructure with a large pore size of 8.3 nm, a large Brunauer–Emmett–Teller (BET) specific surface area of 680 m² g⁻¹ and a large pore volume of 1.06 cm³ g⁻¹ following surfactant extraction as demonstrated by X-ray diffraction (XRD), Transmission electron microscope (TEM), and physical adsorption techniques. Based on BET surface area and weight loss, the surface coverage of amino-groups for the amino-functionalized mesoporous silica thin films is calculated to be 3.2 amino-groups per nm². Moreover, the functionalized thin films display improved properties for immobilization of cytochrome c in comparison with pure-silica mesoporous thin films.     

Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

Thermogravimetric Study of Volatile Precursors For Chemical Thin Film Deposition. Estimation of vapor pressures and source temperatures

Normal pressure thermogravimetry (TG) measurements were used to study the sublimation behavior of several volatile metal compounds, used as metal precursors in thin film fabrication by chemical vapor phase methods, like atomic layer deposition (ALD) and chemical vapor deposition (CVD). The results indicated that dynamic TG measurements may be used to find correct source temperatures to be used in an ALD reactor: a good correlation between the source temperatures used in ALD and temperatures corresponding to mass losses of 10 and 50% in TG was verified. It was also found that isothermal TG measurements offer a simple way for the vapor pressure measurements which otherwise are not trivial for solids with only moderate volatility. This revised version was published online in July 2006 with corrections to the Cover Date.     

Atomic layer deposition chemistry: recent developments and future challenges

New materials, namely high-k (high-permittivity) dielectrics to replace SiO(2), Cu to replace Al, and barrier materials for Cu, are revolutionizing modern integrated circuits. These materials must be deposited as very thin films on structured surfaces. The self-limiting growth mechanism characteristic to atomic layer deposition (ALD) facilitates the control of film thickness at the atomic level and allows deposition on large and complex surfaces. These features make ALD a very promising technique for future integrated circuits. Recent ALD research has mainly focused on materials required in microelectronics. Chemistry, in particular the selection of suitable precursor combinations, is the key issue in ALD; many interesting results have been obtained by smart chemistry. ALD is also likely to find applications in other areas, such as magnetic recording heads, optics, demanding protective coatings, and micro-electromechanical systems, provided that cost-effective processes can be found for the materials required.     

Atomic/molecular layer deposited thin-film alloys of Ti-4,4'-oxydianiline hybrid-TiO(2) with tunable properties

By combining atomic layer deposition (ALD) and molecular layer deposition (MLD) thin-film techniques, the latter being a variant of the former in which organic precursors are used, it is possible to deposit thin films containing precisely controlled portions of inorganic and organic constituents. This in turn enables the adjustment of material properties by changing the number of ALD and MLD cycles applied during the deposition. In this work, the properties of such thin-film "alloys" prepared by varying the portions of Ti-4,4'-oxydianiline (Ti-ODA) inorganic-organic hybrid and TiO(2) in the structure were investigated. The films were deposited at 280 °C using TiCl(4) and water as precursors for TiO(2), and TiCl(4) and ODA for the Ti-ODA hybrid. The results demonstrate excellent tunability of the film properties such as degree of crystallinity, roughness, refractive index, and hardness depending on the relative number of TiO(2) and Ti-ODA cycles employed.     

Three Dimensionally Ordered Mesoporous Carbon as a Stable,High‐Performance Li–O2 Battery Cathode

Enabled by the reversible conversion between Li₂O₂ and O₂, Li–O₂ batteries promise theoretical gravimetric capacities significantly greater than Li‐ion batteries. The poor cycling performance, however, has greatly hindered the development of this technology. At the heart of the problem is the reactivity exhibited by the carbon cathode support under cell operation conditions. One strategy is to conceal the carbon surface from reactive intermediates. Herein, we show that long cyclability can be achieved on three dimensionally ordered mesoporous (3DOm) carbon by growing a thin layer of FeO_x using atomic layer deposition (ALD). 3DOm carbon distinguishes itself from other carbon materials with well‐defined pore structures, providing a unique material to gain insight into processes key to the operations of Li–O₂ batteries. When decorated with Pd nanoparticle catalysts, the new cathode exhibits a capacity greater than 6000 mAh g_carbon⁻¹ and cyclability of more than 68 cycles.