Project description:Aluminum nitride (AlN) thin films were grown using thermal atomic layer deposition in the temperature range of 175-350 °C. The thin films were deposited using trimethyl aluminum (TMA) and hydrazine (N2H4) as a metal precursor and nitrogen source, respectively. Highly reactive N2H4, compared to its conventionally used counterpart, ammonia (NH3), provides a higher growth per cycle (GPC), which is approximately 2.3 times higher at a deposition temperature of 300 °C and, also exhibits a low impurity concentration in as-deposited films. Low temperature AlN films deposited at 225 °C with a capping layer had an Al to N composition ratio of 1:1.1, a close to ideal composition ratio, with a low oxygen content (7.5%) while exhibiting a GPC of 0.16 nm/cycle. We suggest that N2H4 as a replacement for NH3 is a good alternative due to its stringent thermal budget.
Project description:We report the growth of zirconium oxide (ZrO2) as a high-k gate dielectric for an inkjet-printed transistor using a low-temperature atomic layer deposition (ALD) from tetrakis(dimethylamido)zirconium (TDMAZr) and water precursors. All the samples are deposited at low-temperature ranges of 150-250 °C. The films are very uniform with RMS roughness less than 4% with respect to their thickness. The atomic force microscopy (AFM) shows a significant change in surface morphology from tapered posts to undulating mountain-like structures with several hundreds of ALD cycles. The results from X-ray diffraction (XRD) analysis exhibit an amorphous to the crystalline structure with temperature variation, which is independent of the thickness of the films. All our samples are hydrophilic as contact angles are less than 90°. The capacitance-voltage (C-V) and conductance-voltage (G p/ω-V) characteristics of ZrO2 dielectrics for silicon metal-oxide-semiconductor (MOS) capacitors are studied for different temperatures. For the n-type substrate MOS capacitors, the dielectric constants are estimated to be 7.5-11. Due to the low deposition temperature, a hydrophilic surface, and high k value, the ALD-ZrO2 dielectric can be compatible for printed transistors. The processes of fabrication and characterization of inkjet-printed graphene transistors is demonstrated using the ZrO2 dielectric. The possible solvents, surfactant, and the dielectric induced modifications in graphene flakes are demonstrated by Raman spectra. The graphene flakes spread uniformly on the ZrO2 surface. The functional inkjet-printed graphene transistor characteristics are demonstrated to illustrate the field effect behavior with the ALD-ZrO2 dielectric.
Project description:Transition-metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co-P films were deposited by using PH3 plasma as the phosphorus source and an extra H2 plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self-limited layer-by-layer growth, and the deposited Co-P films were highly pure and smooth. The Co-P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co-P films prepared by the traditional post-phosphorization method. Moreover, the deposition of ultrathin Co-P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three-dimensional (3D) architectures.
Project description:HfO2 was deposited at 80-250 °C by plasma-enhanced atomic layer deposition (PEALD), and properties were compared with those obtained by using thermal atomic layer deposition (thermal ALD). The ALD window, i.e., the region where the growth per cycle (GPC) is constant, shifted from high temperatures (150-200 °C) to lower temperatures (80-150 °C) in PEALD. HfO2 deposited at 80 °C by PEALD showed higher density (8.1 g/cm3) than those deposited by thermal ALD (5.3 g/cm3) and a smooth surface (RMS Roughness: 0.2 nm). HfO2 deposited at a low temperature by PEALD showed decreased contaminants compared to thermal ALD deposited HfO2. Values of refractive indices and optical band gap of HfO2 deposited at 80 °C by PEALD (1.9, 5.6 eV) were higher than those obtained by using thermal ALD (1.7, 5.1 eV). Transparency of HfO2 deposited at 80 °C by PEALD on polyethylene terephthalate (PET) was high (> 84%). PET deposited above 80 °C was unable to withstand heat and showed deformation. HfO2 deposited at 80 °C by PEALD showed decreased leakage current from 1.4 × 10-2 to 2.5 × 10-5 A/cm2 and increased capacitance of approximately 21% compared to HfO2 using thermal ALD. Consequently, HfO2 deposited at a low temperature by PEALD showed improved properties compared to HfO2 deposited by thermal ALD.
Project description:Phase-controlled synthesis of two-dimensional (2D) transition-metal chalcogenides (TMCs) at low temperatures with a precise thickness control has to date been rarely reported. Here, we report on a process for the phase-controlled synthesis of TiS2 (metallic) and TiS3 (semiconducting) nanolayers by atomic layer deposition (ALD) with precise thickness control. The phase control has been obtained by carefully tuning the deposition temperature and coreactant composition during ALD. In all cases, characteristic self-limiting ALD growth behavior with a growth per cycle (GPC) of ∼0.16 nm per cycle was observed. TiS2 was prepared at 100 °C using H2S gas as coreactant and was also observed using H2S plasma as a coreactant at growth temperatures between 150 and 200 °C. TiS3 was synthesized only at 100 °C using H2S plasma as the coreactant. The S2 species in the H2S plasma, as observed by optical emission spectroscopy, has been speculated to lead to the formation of the TiS3 phase at low temperatures. The control between the synthesis of TiS2 and TiS3 was elucidated by Raman spectroscopy, X-ray photoelectron spectroscopy, high-resolution electron microscopy, and Rutherford backscattering study. Electrical transport measurements showed the low resistive nature of ALD grown 2D-TiS2 (1T-phase). Postdeposition annealing of the TiS3 layers at 400 °C in a sulfur-rich atmosphere improved the crystallinity of the film and yielded photoluminescence at ∼0.9 eV, indicating the semiconducting (direct band gap) nature of TiS3. The current study opens up a new ALD-based synthesis route for controlled, scalable growth of transition-metal di- and tri-chalcogenides at low temperatures.
Project description:Rhodium (Rh) and palladium (Pd) thin films have been fabricated using an atomic layer deposition (ALD) process using Rh(acac)3 and Pd(hfac)2 as the respective precursors and using short-pulse low-concentration ozone as the co-reactant. This method of fabrication does away with the need for combustible reactants such as hydrogen or oxygen, either as a precursor or as an annealing agent. All previous studies using only ozone could not yield metallic films, and required post treatment using hydrogen or oxygen. In this work, it was discovered that the concentration level of ozone used in the ALD process was critical in determining whether the pure metal film was formed, and whether the metal film was oxidized. By controlling the ozone concentration under a critical limit, the fabrication of these noble metal films was successful. Rhodium thin films were deposited between 200 and 220 °C, whereas palladium thin films were deposited between 180 and 220 °C. A precisely controlled low ozone concentration of 1.22 g m-3 was applied to prevent the oxidation of the noble metallic film, and to ensure fast growth rates of 0.42 Å per cycle for Rh, and 0.22 Å per cycle for Pd. When low-concentration ozone was applied to react with ligand, no excess ozone was available to oxidize the metal products. The surfaces of deposited films obtained the RMS roughness values of 0.30 nm for Rh and 0.13 nm for Pd films. The resistivities of 18 nm Rh and 22 nm Pd thin films were 17 μΩ cm and 63 μΩ cm.
Project description:The decomposition of tetraisopropyl orthotitanate (TTIP), a representative precursor used in the atomic layer deposition (ALD) of titanium dioxide (TiO2) film, and the resulting changes in the thin film properties of the TiO2 film were investigated. TTIP was evaluated after exposure to thermal stress in an enclosed container. The vapor pressure results provide reasonable evidence that impurities are generated by the decomposition of TTIP under thermal stress. These impurities led to changes in the thermal properties of TTIP and changes in the growth rate, morphology, and composition of the thin film; in particular, these impurities increased the unstable oxidation states of Ti2+ (TiO) content in the TiO2 film. The changes in the properties of the TiO2 film resulting from the changes in the physical properties of TTIP led to a change in the properties of the device. We proved that the thermal stability of the precursor is a factor that can determine the reliability of the ALD process and the resulting thin film. Additionally, systematic evaluation of the precursor can provide useful information that can improve the development of the precursor and the consistency of the process.
Project description:Low-temperature epitaxial growth of AlN ultrathin films was realized by atomic layer deposition (ALD) together with the layer-by-layer, in-situ atomic layer annealing (ALA), instead of a high growth temperature which is needed in conventional epitaxial growth techniques. By applying the ALA with the Ar plasma treatment in each ALD cycle, the AlN thin film was converted dramatically from the amorphous phase to a single-crystalline epitaxial layer, at a low deposition temperature of 300 °C. The energy transferred from plasma not only provides the crystallization energy but also enhances the migration of adatoms and the removal of ligands, which significantly improve the crystallinity of the epitaxial layer. The X-ray diffraction reveals that the full width at half-maximum of the AlN (0002) rocking curve is only 144 arcsec in the AlN ultrathin epilayer with a thickness of only a few tens of nm. The high-resolution transmission electron microscopy also indicates the high-quality single-crystal hexagonal phase of the AlN epitaxial layer on the sapphire substrate. The result opens a window for further extension of the ALD applications from amorphous thin films to the high-quality low-temperature atomic layer epitaxy, which can be exploited in a variety of fields and applications in the near future.
Project description:An Al2O3 thin film has been grown by vapor deposition using different Al precursors. The most commonly used precursor is trimethylaluminum, which is highly reactive and pyrophoric. In the purpose of searching for a more ideal Al source, the non-pyrophoric aluminum tri-sec-butoxide ([Al(OsBu)3], ATSB) was introduced as a novel precursor for atomic layer deposition (ALD). After demonstrating the deposition of Al2O3 via chemical vapor deposition (CVD) and 'pulsed CVD' routes, the use of ATSB in an atomic layer deposition (ALD)-like process was investigated and optimized to achieve self-limiting growth. The films were characterized using spectral reflectance, ellipsometry and UV-Vis before their composition was studied. The growth rate of Al2O3 via the ALD-like process was consistently 0.12 nm/cycle on glass, silicon and quartz substrates under the optimized conditions. Scanning electron microscopy and transmission electron microscopy images of the ALD-deposited Al2O3 films deposited on complex nanostructures demonstrated the conformity, uniformity and good thickness control of these films, suggesting a potential of being used as the protection layer in photoelectrochemical water splitting.
Project description:The functionalization of fine primary particles by atomic layer deposition (particle ALD) provides for nearly perfect nanothick films to be deposited conformally on both external and internal particle surfaces, including nanoparticle surfaces. Film thickness is easily controlled from several angstroms to nanometers by the number of self-limiting surface reactions that are carried out sequentially. Films can be continuous or semi-continuous. This review starts with a short early history of particle ALD. The discussion includes agitated reactor processing, both atomic and molecular layer deposition (MLD), coating of both inorganic and polymer particles, nanoparticles, and nanotubes. A number of applications are presented, and a path forward, including likely near-term commercial products, is given.