Showing papers on "Thin film published in 2020"

Enhanced ferroelectricity in ultrathin films grown directly on silicon.

Abstract: Ultrathin ferroelectric materials could potentially enable low-power logic and nonvolatile memories1,2. As ferroelectric materials are made thinner, however, the ferroelectricity is usually suppressed. Size effects in ferroelectrics have been thoroughly investigated in perovskite oxides—the archetypal ferroelectric system3. Perovskites, however, have so far proved unsuitable for thickness scaling and integration with modern semiconductor processes4. Here we report ferroelectricity in ultrathin doped hafnium oxide (HfO2), a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to a thickness of one nanometre. Our results indicate not only the absence of a ferroelectric critical thickness but also enhanced polar distortions as film thickness is reduced, unlike in perovskite ferroelectrics. This approach to enhancing ferroelectricity in ultrathin layers could provide a route towards polarization-driven memories and ferroelectric-based advanced transistors. This work shifts the search for the fundamental limits of ferroelectricity to simpler transition-metal oxide systems—that is, from perovskite-derived complex oxides to fluorite-structure binary oxides—in which ‘reverse’ size effects counterintuitively stabilize polar symmetry in the ultrathin regime. Enhanced switchable ferroelectric polarization is achieved in doped hafnium oxide films grown directly onto silicon using low-temperature atomic layer deposition, even at thicknesses of just one nanometre.

Strain engineering and epitaxial stabilization of halide perovskites.

Abstract: Strain engineering is a powerful tool with which to enhance semiconductor device performance1,2. Halide perovskites have shown great promise in device applications owing to their remarkable electronic and optoelectronic properties3–5. Although applying strain to halide perovskites has been frequently attempted, including using hydrostatic pressurization6–8, electrostriction9, annealing10–12, van der Waals force13, thermal expansion mismatch14, and heat-induced substrate phase transition15, the controllable and device-compatible strain engineering of halide perovskites by chemical epitaxy remains a challenge, owing to the absence of suitable lattice-mismatched epitaxial substrates. Here we report the strained epitaxial growth of halide perovskite single-crystal thin films on lattice-mismatched halide perovskite substrates. We investigated strain engineering of α-formamidinium lead iodide (α-FAPbI3) using both experimental techniques and theoretical calculations. By tailoring the substrate composition—and therefore its lattice parameter—a compressive strain as high as 2.4 per cent is applied to the epitaxial α-FAPbI3 thin film. We demonstrate that this strain effectively changes the crystal structure, reduces the bandgap and increases the hole mobility of α-FAPbI3. Strained epitaxy is also shown to have a substantial stabilization effect on the α-FAPbI3 phase owing to the synergistic effects of epitaxial stabilization and strain neutralization. As an example, strain engineering is applied to enhance the performance of an α-FAPbI3-based photodetector. A method of deposition of mixed-cation hybrid perovskite films as lattice-mismatched substrates for an α-FAPbI3 film is described, giving strains of up to 2.4 per cent while also stabilizing the metastable α-FAPbI3 phase for several hundred days.

Production and processing of graphene and related materials

Abstract: © 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown.

Regulating strain in perovskite thin films through charge-transport layers

Abstract: Thermally-induced tensile strain that remains in perovskite films following annealing results in increased ion migration and is a known factor in the instability of these materials. Previously-reported strain regulation methods for perovskite solar cells (PSCs) have utilized substrates with high thermal expansion coefficients that limits the processing temperature of perovskites and compromises power conversion efficiency. Here we compensate residual tensile strain by introducing an external compressive strain from the hole-transport layer. By using a hole-transport layer with high thermal expansion coefficient, we compensate the tensile strain in PSCs by elevating the processing temperature of hole-transport layer. We find that compressive strain increases the activation energy for ion migration, improving the stability of perovskite films. We achieve an efficiency of 16.4% for compressively-strained PSCs; and these retain 96% of their initial efficiencies after heating at 85 °C for 1000 hours—the most stable wide-bandgap perovskites (above 1.75 eV) reported so far. Remnant tensile strain in the perovskite films induced in the thermal annealing step is a known source of material and device instabilities. Here Xue et al. use a thermal expandable hole transporting layer to compensate the strain and result in most stable wide-bandgap perovskite solar cells so far.

Understanding of perovskite crystal growth and film formation in scalable deposition processes

Abstract: Hybrid organic-inorganic perovskite photovoltaics (PSCs) have attracted significant attention during the past decade. Despite the stellar rise of laboratory-scale PSC devices, which have reached a certified efficiency over 25% to date, there is still a large efficiency gap when transiting from small-area devices to large-area solar modules. Efficiency losses would inevitably arise from the great challenges of homogeneous coating of large-area high quality perovskite films. To address this problem, we provide an in-depth understanding of the perovskite nucleation and crystal growth kinetics, including the LaMer and Ostwald ripening models, which advises us that fast nucleation and slow crystallization are essential factors in forming high-quality perovskite films. Based on these cognitions, a variety of thin film engineering approaches will be introduced, including the anti-solvent, gas-assisted and solvent annealing treatments, Lewis acid-base adduct incorporation, etc., which are able to regulate the nucleation and crystallization steps. Upscaling the photovoltaic devices is the following step. We summarize the currently developed scalable deposition technologies, including spray coating, slot-die coating, doctor blading, inkjet printing and vapour-assisted deposition. These are more appealing approaches for scalable fabrication of perovskite films than the spin coating method, in terms of lower material/solution waste, more homogeneous thin film coating over a large area, and better morphological control of the film. The working principles of these techniques will be provided, which direct us that the physical properties of the precursor solutions and surface characteristics/temperature of the substrate are both dominating factors influencing the film morphology. Optimization of the perovskite crystallization and film formation process will be subsequently summarized from these aspects. Additionally, we also highlight the significance of perovskite stability, as it is the last puzzle to realize the practical applications of PSCs. Recent efforts towards improving the stability of PSC devices to environmental factors are discussed in this part. In general, this review, comprising the mechanistic analysis of perovskite film formation, thin film engineering, scalable deposition technologies and device stability, provides a comprehensive overview of the current challenges and opportunities in the field of PSCs, aiming to promote the future development of cost-effective up-scale fabrication of highly efficient and ultra-stable PSCs for practical applications.

Hydrothermal deposition of antimony selenosulfide thin films enables solar cells with 10% efficiency

Abstract: Antimony selenosulfide, Sb2(S,Se)3, has attracted attention over the last few years as a light-harvesting material for photovoltaic technology owing to its phase stability, earth abundancy and low toxicity. However, the lack of a suitable material processing approach to obtain Sb2(S,Se)3 films with optimal optoelectronic properties and morphology severely hampers prospects for efficiency improvement. Here we demonstrate a hydrothermal approach to deposit high-quality Sb2(S,Se)3 films. By varying the Se/S ratio and the temperature of the post-deposition annealing, we improve the film morphology, increase the grain size and reduce the number of defects. In particular, we find that increasing the Se/S ratio leads to a favourable orientation of the (Sb4S(e)6)n ribbons (S(e) represents S or Se). By optmizing the hydrothermal deposition parameters and subsequent annealing, we report a Sb2(S,Se)3 cell with a certified 10.0% efficiency. This result highlights the potential of Sb2(S,Se)3 as an emerging photovoltaic material. Antimony chalcogenides are emerging photovoltaic materials, yet difficulties in fabricating high-quality films limit device performance. We show that hydrothermal synthesis affords good morphology and reduced defects in antimony selenosulfide films, enabling solar cells with an efficiency of 10%.

Recent progress on the electronic structure, defect, and doping properties of Ga2O3

Abstract: Gallium oxide (Ga2O3) is an emerging wide bandgap semiconductor that has attracted a large amount of interest due to its ultra-large bandgap of 4.8 eV, a high breakdown field of 8 MV/cm, and high thermal stability. These properties enable Ga2O3 a promising material for a large range of applications, such as high power electronic devices and solar-blind ultraviolet (UV) photodetectors. In the past few years, a significant process has been made for the growth of high-quality bulk crystals and thin films and device optimizations for power electronics and solar blind UV detection. However, many challenges remain, including the difficulty in p-type doping, a large density of unintentional electron carriers and defects/impurities, and issues with the device process (contact, dielectrics, and surface passivation), and so on. The purpose of this article is to provide a timely review on the fundamental understanding of the semiconductor physics and chemistry of Ga2O3 in terms of electronic band structures, optical properties, and chemistry of defects and impurity doping. Recent progress and perspectives on epitaxial thin film growth, chemical and physical properties of defects and impurities, p-type doping, and ternary alloys with In2O3 and Al2O3 will be discussed.

A fabrication process for flexible single-crystal perovskite devices

Abstract: Organic–inorganic hybrid perovskites have electronic and optoelectronic properties that make them appealing in many device applications1–4. Although many approaches focus on polycrystalline materials5–7, single-crystal hybrid perovskites show improved carrier transport and enhanced stability over their polycrystalline counterparts, due to their orientation-dependent transport behaviour8–10 and lower defect concentrations11,12. However, the fabrication of single-crystal hybrid perovskites, and controlling their morphology and composition, are challenging12. Here we report a solution-based lithography-assisted epitaxial-growth-and-transfer method for fabricating single-crystal hybrid perovskites on arbitrary substrates, with precise control of their thickness (from about 600 nanometres to about 100 micrometres), area (continuous thin films up to about 5.5 centimetres by 5.5 centimetres), and composition gradient in the thickness direction (for example, from methylammonium lead iodide, MAPbI3, to MAPb0.5Sn0.5I3). The transferred single-crystal hybrid perovskites are of comparable quality to those directly grown on epitaxial substrates, and are mechanically flexible depending on the thickness. Lead–tin gradient alloying allows the formation of a graded electronic bandgap, which increases the carrier mobility and impedes carrier recombination. Devices based on these single-crystal hybrid perovskites show not only high stability against various degradation factors but also good performance (for example, solar cells based on lead–tin-gradient structures with an average efficiency of 18.77 per cent). A solution-based lithography-assisted epitaxial-growth-and-transfer method is used to fabricate single-crystal hybrid perovskites on any surface, with precise control of the thickness, area and chemical composition gradient.

Platinum single atoms on tin oxide ultrathin films for extremely sensitive gas detection

Abstract: Single atom Pt functionalized SnO2 ultrathin films are synthesized by atomic layer deposition (ALD) for application as sensing layers in resistive gas sensors. Here it is shown that the electronic conductivity of the SnO2 ultrathin films is very sensitive to the exposure to triethylamine (TEA), and that the thickness of the SnO2 films (from 4 to 18 nm) has a crucial effect on the sensor response. The 9 nm thick SnO2 film shows the best response to TEA, while a further decrease in the film thickness, i.e., 4 nm, leads to a very weak response due to the two orders of magnitude lower carrier concentration. Single atom Pt catalysts deposited on the 9 nm SnO2 film result in an unexpectedly high enhancement in the sensor response and also a decrease of the sensor working temperature. Consequently, Pt/SnO2 thin film sensors show the highest response of 136.2 to 10 ppm TEA at an optimal temperature of 200 °C (that of a pristine SnO2 film sensor is 260 °C), which is improved by a factor of 9 compared to that of pristine SnO2. Moreover, the Pt/SnO2 sensor exhibits an ultrahigh sensitivity of 8.76 ppm−1 and an extremely low limit of detection (LOD) of 7 ppb, which to our best knowledge are far superior to any previous report. Very fast response and recovery times (3/6 s) are also recorded, thus making our sensor platform highly suitable for highly-demanding applications. Mechanistic investigations reveal that the outstanding sensing performances originate from the synergistic combination of the optimized film thickness comparable to the Debye length of SnO2 and the spillover activation of oxygen by single atom Pt catalysts, as well as the oxygen vacancies in the SnO2 films.

Oxygen Vacancies Enabled Porous SnO2 Thin Films for Highly Sensitive Detection of Triethylamine at Room Temperature.

Abstract: Detection of volatile organic compounds (VOCs) at room temperature (RT) currently remains a challenge for metal oxide semiconductor (MOS) gas sensors. Herein, for the first time, we report on the utilization of porous SnO2 thin films for RT detection of VOCs by defect engineering of oxygen vacancies. The oxygen vacancies in the three-dimensional-ordered SnO2 thin films, prepared by a colloidal template method, can be readily manipulated by thermal annealing at different temperatures. It is found that oxygen vacancies play an important role in the RT sensing performances, which successfully enables the sensor to respond to triethylamine (TEA) with an ultrahigh response, for example, 150.5-10 ppm TEA in a highly selective manner. In addition, the sensor based on oxygen vacancy-rich SnO2 thin films delivers a fast response and recovery speed (53 and 120 s), which can be further shortened to 10 and 36 s by elevating the working temperature to 120 °C. Notably, a low detection limit of 110 ppb has been obtained at RT. The overall performances surpass most previous reports on TEA detection at RT. The outstanding sensing properties can be attributed to the porous structure with abundant oxygen vacancies, which can improve the adsorption of molecules. The oxygen vacancy engineering strategy and the on-chip fabrication of porous MOS thin film sensing layers deliver great potential for creating high-performance RT sensors.

Irradiation induced modification of structural and optical properties of potassium sodium niobate thin films

Abstract: In the present study, the effects of swift heavy ion induced modification on the structural, morphological and optical properties of potassium sodium niobate (KNN) thin films have been investigated. KNN thin films were deposited using RF magnetron sputtering onto Si and quartz substrates. Subsequently, as-deposited films were annealed at 700 °C in air ambience for crystallization. Eventually, these crystalline films were irradiated using 100 MeV Ag ions at various fluences ranging from 1 × 1012 to 1 × 1013 ions/cm2. The crystalline and irradiated films were characterized using various techniques such as X-ray diffraction (XRD), atomic force microscopy (AFM), Raman spectroscopy, and UV–Vis spectroscopy. XRD results reveal that the crystallinity of films decreases drastically upon irradiation and almost disappeared at 1 × 1013 ions/cm2. Raman spectra show the different vibration modes of NbO6 octahedra. Raman peaks intensity is decreased and the peaks get broadened due to irradiation which indicates the amorphous nature of films. Variation in surface morphology and roughness of films before and after irradiation is studied using AFM. The minimum value of roughness is observed at 5 × 1012 ions/cm2. Ion beam irradiation results in the variation of transmittance and optical band gap of the films. The optical band gap of crystalline KNN film is found to be 3.82 eV which decreased to 3.72 eV upon irradiation at 5 × 1012 ions/cm2. The monotonous decrease in the refractive index and packing density of films is also observed with ion fluence.

Inkjet-Printed Micrometer-Thick Perovskite Solar Cells with Large Columnar Grains

Abstract: Transferring the high power conversion efficiencies (PCEs) of spin-coated perovskite solar cells (PSCs) on the laboratory scale to large-area photovoltaic modules requires a significant advance in scalable fabrication methods. Digital inkjet printing promises scalable, material, and cost-efficient deposition of perovskite thin films on a wide range of substrates and in arbitrary shapes. In this work, high-quality inkjet-printed triple-cation (methylammonium, formamidinium, and cesium) perovskite layers with exceptional thicknesses of >1 μm are demonstrated, enabling unprecedentedly high PCEs > 21% and stabilized power output efficiencies > 18% for inkjet-printed PSCs. In-depth characterization shows that the thick inkjet-printed perovskite thin films deposited using the process developed herein exhibit a columnar crystal structure, free of horizontal grain boundaries, which extend over the entire thickness. A thin film thickness of around 1.5 μm is determined as optimal for PSC for this process. Up to this layer thickness X-ray photoemission spectroscopy analysis confirms the expected stoichiometric perovskite composition at the surface and shows strong deviations and inhomogeneities for thicker thin films. The micrometer-thick perovskite thin films exhibit remarkably long charge carrier lifetimes, highlighting their excellent optoelectronic characteristics. They are particularly promising for next-generation inkjet-printed perovskite solar cells, photodetectors, and X-ray detectors.

Area-Selective Deposition: Fundamentals, Applications, and Future Outlook

Abstract: This article provides an overview of area-selective thin film deposition (ASD) with primary focus on vapor-phase thin film formation via chemical vapor deposition (CVD) and atomic layer deposition ...

Evaporated tellurium thin films for p-type field-effect transistors and circuits

Abstract: There is an emerging need for semiconductors that can be processed at near ambient temperature with high mobility and device performance. Although multiple n-type options have been identified, the development of their p-type counterparts remains limited. Here, we report the realization of tellurium thin films through thermal evaporation at cryogenic temperatures for fabrication of high-performance wafer-scale p-type field-effect transistors. We achieve an effective hole mobility of ~35 cm2 V-1 s-1, on/off current ratio of ~104 and subthreshold swing of 108 mV dec-1 on an 8-nm-thick film. High-performance tellurium p-type field-effect transistors are fabricated on a wide range of substrates including glass and plastic, further demonstrating the broad applicability of this material. Significantly, three-dimensional circuits are demonstrated by integrating multi-layered transistors on a single chip using sequential lithography, deposition and lift-off processes. Finally, various functional logic gates and circuits are demonstrated.

Aspects of the synthesis of thin film superconducting infinite-layer nickelates

Abstract: The recent observation of superconductivity in Nd0.8Sr0.2NiO2 calls for further investigation and optimization of the synthesis of this infinite-layer nickelate structure. Here, we present our current understanding of important aspects of the growth of the parent perovskite compound via pulsed laser deposition on SrTiO3 (001) substrates and the subsequent topotactic reduction. We find that to achieve single-crystalline, single-phase superconducting Nd0.8Sr0.2NiO2, it is essential that the precursor perovskite Nd0.8Sr0.2NiO3 thin film is stabilized with no visible impurity phases; in particular, a Ruddlesden–Popper-type secondary phase is often observed. We have further investigated the evolution of the soft-chemistry topotactic reduction conditions to realize full transformation to the infinite-layer structure with no film decomposition or formation of other phases. We find that capping the nickelate film with a subsequent SrTiO3 layer provides an epitaxial template to the top region of the nickelate film, much like the substrate. Thus, for currently optimized growth conditions, we can stabilize superconducting single-phase Nd0.8Sr0.2NiO2 (001) epitaxial thin films up to ∼10 nm.

Understanding chemical and physical mechanisms in atomic layer deposition.

Abstract: Atomic layer deposition (ALD) is a powerful tool for achieving atomic level control in the deposition of thin films. However, several physical and chemical phenomena can occur which cause deviation from "ideal" film growth during ALD. Understanding the underlying mechanisms that cause these deviations is important to achieving even better control over the growth of the deposited material. Herein, we review several precursor chemisorption mechanisms and the effect of chemisorption on ALD growth. We then follow with a discussion on diffusion and its impact on film growth during ALD. Together, these two fundamental processes of chemisorption and diffusion underlie the majority of mechanisms which contribute to material growth during a given ALD process, and the recognition of their role allows for more rational design of ALD parameters.

Review of Growth Defects in Thin Films Prepared by PVD Techniques

Abstract: The paper summarizes current knowledge of growth defects in physical vapor deposition (PVD) coatings. A detailed historical overview is followed by a description of the types and evolution of growth defects. Growth defects are microscopic imperfections in the coating microstructure. They are most commonly formed by overgrowing of the topographical imperfections (pits, asperities) on the substrate surface or the foreign particles of different origins (dust, debris, flakes). Such foreign particles are not only those that remain on the substrate surface after wet cleaning procedure, but also the ones that are generated during ion etching and deposition processes. Although the origin of seed particles from external pretreatment of substrate is similar to all PVD coatings, the influence of ion etching and deposition techniques is rather different. Therefore, special emphasis is given on the description of the processes that take place during ion etching of substrates and the deposition of coating. The effect of growth defects on the functional properties of PVD coatings is described in the last section. How defects affect the quality of optical coatings, thin layers for semiconductor devices, as well as wear, corrosion, and oxidation resistant coatings is explained. The effect of growth defects on the permeation and wettability of the coatings is also shortly described.

Methanol and Humidity Capacitive Sensors Based on Thin Films of MOF Nanoparticles.

Abstract: The successful development of modern gas sensing technologies requires high sensitivity and selectivity coupled to cost effectiveness, which implies the necessity to miniaturize devices while reducing the amount of sensing material. The appealing alternative of integrating nanoparticles of a porous metal-organic framework (MOF) onto capacitive sensors based on interdigitated electrode (IDE) chips is presented. We report the deposition of MIL-96(Al) MOF thin films via the Langmuir-Blodgett (LB) method on the IDE chips, which allowed the study of their gas/vapor sensing properties. First, sorption studies of several organic vapors like methanol, toluene, chloroform, etc. were conducted on bulk MOF. The sorption data revealed that MIL-96(Al) presents high affinity toward water and methanol. Later on, ordered LB monolayer films of MIL-96(Al) particles of ∼200 nm were successfully deposited onto IDE chips with homogeneous coverage of the surface in comparison to conventional thin film fabrication techniques such as drop-casting. The sensing tests showed that MOF LB films were selective for water and methanol, and short response/recovery times were achieved. Finally, chemical vapor deposition (CVD) of a porous thin film of Parylene C (thickness ∼250-300 nm) was performed on top of the MOF LB films to fabricate a thin selective layer. The sensing results showed an increase in the water selectivity and sensitivity, while those of methanol showed a huge decrease. These results prove the feasibility of the LB technique for the fabrication of ordered MOF thin films onto IDE chips using very small MOF quantities.

Two-Dimensional Boronate Ester Covalent Organic Framework Thin Films with Large Single Crystalline Domains for a Neuromorphic Memory Device.

Abstract: Despite the recent progress in the synthesis of crystalline boronate ester covalent organic frameworks (BECOFs) in powder and thin-film through solvothermal method and on-solid-surface synthesis, respectively, their applications in electronics, remain less explored due to the challenges in thin-film processability and device integration associated with the control of film thickness, layer orientation, stability and crystallinity. Moreover, although the crystalline domain sizes of the powder samples can reach micrometer scale (up to ≈1.5 μm), the reported thin-film samples have so far rather small crystalline domains up to 100 nm. Here we demonstrate a general and efficient synthesis of crystalline two-dimensional (2D) BECOF films composed of porphyrin macrocycles and phenyl or naphthyl linkers (named as 2D BECOF-PP or 2D BECOF-PN) by employing a surfactant-monolayer-assisted interfacial synthesis (SMAIS) on the water surface. The achieved 2D BECOF-PP is featured as free-standing thin film with large single-crystalline domains up to ≈60 μm2 and tunable thickness from 6 to 16 nm. A hybrid memory device composed of 2D BECOF-PP film on silicon nanowire-based field-effect transistor is demonstrated as a bio-inspired system to mimic neuronal synapses, displaying a learning-erasing-forgetting memory process.

Effects of deposition conditions on the ferroelectric properties of (Al1−xScx)N thin films

Abstract: The ferroelectricity of (Al1−xScx)N (x = 0–0.34) thin films with various thicknesses was investigated. (Al1−xScx)N films were prepared at 400 °C on (111)Pt/TiOx/SiO2/(001)Si substrates by the radio frequency dual-source reactive magnetron sputtering method using Al and Sc targets under pure N2 gas or a mixture of N2 and Ar gases. The film deposited under N2 gas showed larger remanent polarization than those under N2 + Ar mixture. Ferroelectricity was observed for films with x = 0.10–0.34 for about 140-nm-thick films deposited under N2 gas. The x = 0.22 films showed ferroelectricity down to 48 nm in thickness from the polarization–electric field curves and the positive-up-negative-down measurement. The ferroelectricity of the 9 nm-thick film also was ascertained from scanning nonlinear dielectric microscopy measurement. These results reveal that ferroelectric polarization can switch for films with much broader compositions and thicknesses than those in the previous study.

Characterization of e-beam evaporated Ge, YbF3, ZnS, and LaF3 thin films for laser-oriented coatings.

Abstract: Thin films of Ge, ZnS, YbF3, and LaF3 produced using e-beam evaporation on ZnSe and Ge substrates were characterized in the range of 0.4–12 µm. It was found that the Sellmeier model provides the best fit for refractive indices of ZnSe substrate, ZnS, and LaF3 films; the Cauchy model provides the best fit for YbF3 film. Optical constants of Ge substrate and Ge film as well as extinction coefficients of ZnS, YbF3, LaF3, and ZnSe substrate are presented in the frame of a non-parametric model. For the extinction coefficient of ZnS, the exponential model is applicable. Stresses in Ge, ZnS, YbF3, and LaF3 were estimated equal to (−50)MPa, (−400)MPa, 140 MPa, and 380 MPa, respectively. The surface roughness does not exceed 5 nm for all films and substrates.

Solution‐Processed Centimeter‐Scale Highly Aligned Organic Crystalline Arrays for High‐Performance Organic Field‐Effect Transistors

Abstract: Solution-printed organic single-crystalline films hold great potential for achieving low-cost manufacturing of large-area and flexible electronics. For practical applications, organic field-effect transistor arrays must exhibit high performance and small device-to-device variation. However, scalable fabrication of highly aligned organic crystalline arrays is rather difficult due to the lack of control over the crystallographic orientation, crystal uniformity, and thickness. Here, a facile solution-printing method to fabricate centimeter-sized highly aligned organic crystalline arrays with a thickness of a few molecular layers is reported. In this study, the solution shearing technique is used to produce large-area, organic highly crystalline thin films. Water-soluble ink is printed on the hydrophobic surface of organic crystalline films, to selectively protect it, followed by etching. It is shown that the addition of a surfactant dramatically changes the fluid drying dynamics and increases the contact line friction of the aqueous solution to the underlying nonwetting organic crystalline film. As a result, centimeter-scale highly aligned organic crystalline arrays are successfully prepared on different substrates. The devices based on organic crystalline arrays show good performance and uniformity. This study demonstrates that solution printing is close to industrial application and also expands its applicability to various printed flexible electronics.

The epitaxy of 2D materials growth

Abstract: Two dimensional (2D) materials consist of one to a few atomic layers, where the intra-layer atoms are chemically bonded and the atomic layers are weakly bonded. The high bonding anisotropicity in 2D materials make their growth on a substrate substantially different from the conventional thin film growth. Here, we proposed a general theoretical framework for the epitaxial growth of a 2D material on an arbitrary substrate. Our extensive density functional theory (DFT) calculations show that the propagating edge of a 2D material tends to align along a high symmetry direction of the substrate and, as a conclusion, the interplay between the symmetries of the 2D material and the substrate plays a critical role in the epitaxial growth of the 2D material. Based on our results, we have outlined that orientational uniformity of 2D material islands on a substrate can be realized only if the symmetry group of the substrate is a subgroup of that of the 2D material. Our predictions are in perfect agreement with most experimental observations on 2D materials' growth on various substrates known up to now. We believe that this general guideline will lead to the large-scale synthesis of wafer-scale single crystals of various 2D materials in the near future.

Investigation on tailoring physical properties of Nickel Oxide thin films grown by dc magnetron sputtering

Abstract: We report a comprehensive study on influence of oxygen partial pressure on NiO thin films grown on glass substrates in a combined argon and oxygen ambience by reactive dc magnetron sputtering. In this present article, we have discussed the dependence of oxygen pressure on structural, chemical, morphological, optical and electrical properties of the sputtered NiO films. Glancing angle x-ray diffraction reveals that the deposited films were polycrystalline in nature with FCC phase. The preferred orientation changes from (200)to (111)in a higher O2 flow rate environment and an average particle size was estimated using Scherrer relation. The surface morphology of films was studied by using atomic force microscopy. The x-ray photoelectron spectroscopy analysis demonstrates the core level Ni 2p spectra over a range of 850 eV to 885 eV of binding energy and observed Ni 2p3/2, Ni 2p1/2 domains along with their satellite peaks. It infers the presence of both Ni+2 and Ni+3 oxidation states in the sputtered films. Additionally, Raman spectroscopy was carried out to confirm the structural defects level and crystalline nature of the films. The optical results show that deposited films were semi-transparent and the evaluated optical band gap of the material lies in the range 3.36 eV to 3.52 eV. The extracted electrical properties infer either n-type or p-type conductivity depending on the processing conditions of the films.

Optical characterizations and refractive index dispersion parameters of annealed TiO2 thin films synthesized by RF-sputtering technique at different flow rates of the reactive oxygen gas

Abstract: Optical Characterizations of annealed TiO2 thin films have been discussed. Samples have prepared by sputtering technique at different reactive oxygen gas rates, R ( 1.00 % ≤ R ≤ 30.00 % ) . The pressure within the sputtering room was fixed at 7.5 × 10−7 Pa by controlling the rate of introducing pure Ar and O2 gases. All film-samples were annealed in vacuum at 500 °C for 2 h. X-ray diffractograms revealed that annealed samples have polycrystalline nature of tetragonal anatase phase. Optical transmission and reflection were employed to study optical properties. Optical energy-gap values decrease from 3.38 eV to 2.91 eV for direct transition and from 3.12 eV to 2.10 eV for indirect transition, respectively. While, Urbach's energy values increase from 686 meV to 884 meV as R-value increased. Wemplee Di-Domenico model and Sellemeier postulate were utilized to study the refractive index dispersion and oscillator parameters. All estimated optical parameters are strongly dependent upon the flow rate of oxygen.

MoS2 hybrid heterostructure thin film decorated with CdTe quantum dots for room temperature NO2 gas sensor

Abstract: Molybdenum disulfide (MoS2) is a very promising candidate for room temperature (RT) gas sensing applications. However, the limitation of synthesis techniques, incomplete recovery, and selectivity at RT are prime drawbacks. In this report, MoS2 nanoworms (NWs) thin film and CdTe quantum dots (QDs) decorated MoS2 NWs hybrid heterostructure thin film (CdTe QDs/MoS2 NWs) have been fabricated by scalable sputtering technique on the p-Si substrate and tested for RT NO2 gas sensing applications. The proposed CdTe QDs/MoS2 NWs hybrid heterostructure thin film sensor manifests an excellent sensor response (∼40 %), fast response time = 16 s, complete recovery (recovery time = 114 s) and highly selective towards 10 ppm NO2 at room temperature in comparison to pristine MoS2 NWs thin film sensor (response ∼26 %, response/recovery time ∼23 s/incomplete recovery). This superior gas sensing performance may be attributed to the combined effect of factors such as hybrid heteronanostructure with unique morphology, catalytic activity, synergistic effects, and p-n heterojunctions. The approach employed here may lead to the development of RT operable MoS2-based heterojunction gas sensors.