Realizing the Heteromorphic Superlattice: Repeated Heterolayers of Amorphous Insulator and Polycrystalline Semiconductor with Minimal Interface Defects.

An unconventional "heteromorphic" superlattice (HSL) is realized, comprised of repeated layers of different materials with differing morphologies: semiconducting pc-In2 O3 layers interleaved with insulating a-MoO3 layers. Originally proposed by Tsu in 1989, yet never fully realized, the high quality of the HSL heterostructure demonstrated here validates the intuition of Tsu, whereby the flexibility of the bond angle in the amorphous phase and the passivation effect of the oxide at interfacial bonds serve to create smooth, high-mobility interfaces. The alternating amorphous layers prevent strain accumulation in the polycrystalline layers while suppressing defect propagation across the HSL. For the HSL with 7:7 nm layer thickness, the observed electron mobility of 71 cm2  Vs-1 , matches that of the highest quality In2 O3 thin films. The atomic structure and electronic properties of crystalline In2 O3 /amorphous MoO3 interfaces are verified using ab-initio molecular dynamics simulations and hybrid functional calculations. This work generalizes the superlattice concept to an entirely new paradigm of morphological combinations.

High-Resolution Colloidal Quantum Dot Film Photolithography via Atomic Layer Deposition of ZnO.

High-resolution patterning of quantum dot (QD) films is one of the preconditions for the practical use of QD-based emissive display platforms. Recently, inkjet printing and transfer printing have been actively developed; however, high-resolution patterning is still limited owing to nozzle-clogging issues and coffee ring effects during the inkjet printing and kinetic parameters such as pickup and peeling speed during the transfer process. Consequently, employing direct optical lithography would be highly beneficial owing to its well-established process in the semiconductor industry; however, exposing the photoresist (PR) on top of the QD film deteriorates the QD film underneath. This is because a majority of the solvents for PR easily dissolve the pre-existing QD films. In this study, we present a conventional optical lithography process to obtain solvent resistance by reacting the QD film surface with diethylzinc (DEZ) precursors using atomic layer deposition. It was confirmed that, by reacting the QD surface with DEZ and coating PR directly on top of the QD film, a typical photolithography process can be performed to generate a red/green/blue pixel of 3000 ppi or more. QD electroluminescence devices were fabricated with all primary colors of QDs; moreover, compared to reference QD-LED devices, the patterned QD-LED devices exhibited enhanced brightness and efficiency.

Cs2SnI6-Encapsulated Multidye-Sensitized All-Solid-State Solar Cells.

The design of a dye-sensitized solar cell (DSSC) based on the simultaneous incorporation of multiple dyes is examined. By investigating the use of the porphyrin-based YD2-o-C8 and YDD6, and the organic chromophore TTAR, which can act as complementary absorbers, we are able to enhance the capture of incoming light across the solar spectrum. This is demonstrated first by using a conventional DSSC architecture with a liquid electrolyte and performed a power conversion efficiency (PCE) of 11.2%, representing an improvement over cells based on each of the independent dyes. Next, we used Cs2SnI6 as an encapsulating layer over the sensitizing molecules to reduce charge leakage across the dye layers and also added to the absorption of longer wavelengths up to one micron. Finally, we fabricated a cell utilizing a Cs2SnI6/succinonitrile solid hole-transport electrolyte and achieved a PCE of ∼8.5%. It is expected that the all solid-state design will go a long way toward improving long-term device stability.

Effect of Growth Temperature during the Atomic Layer Deposition of the SrTiO3 Seed Layer on the Properties of RuO2/SrTiO3/Ru Capacitors for Dynamic Random Access Memory Applications.

The atomic layer deposition process of SrTiO3 (STO) films at 230 °C was studied with Sr(iPr3Cp)2 and Ti(CpMe5)(OMe)3 (Pr, Cp, and Me are propyl, cyclopentadienyl, and methyl groups, respectively) on Ru substrates. The growth behavior and properties of STO films grown at 230 °C were compared with those deposited at 370 °C. With the limited over-reaction of the Sr precursor during the initial growth stage at a lower temperature, the cation composition was more controllable, and the surface morphology after crystallization annealing at 650 °C had more uniform grains with fewer defects. Here, the excess reaction of the Sr precursor means the chemical-vapor-deposition-like growth of the SrO component mediated through the thermal decomposition of the adsorbed Sr precursor molecules. It was by the reaction of the Sr precursor with the oxygen supplied from the partly oxidized Ru substrate. The second STO was grown at 370 °C (main layer) on the annealed first STO layer (crystallized seed layer) to lead to the in situ crystallization of the main layer. Due to the improved microstructure of STO films induced by the seed layer deposited at 230 °C, the bulk dielectric constant of 167 was obtained for the main layer, which was higher than the value of 101 where the seed layer was deposited at 370 °C, even though the crystallization annealing condition of the seed layer and the deposition condition of the main layer were consistent. The seed layer grown at 230 °C, however, had a lower dielectric constant of only ∼49, whereas the high-temperature seed layer had a dielectric constant of ∼106. Therefore, the low-temperature seed layer posed a severe limitation in acquiring an advanced capacitor property with the involvement of a low-dielectric interfacial layer.

Quantitative Analysis of the Incorporation Behaviors of Sr and Ti Atoms During the Atomic Layer Deposition of SrTiO3 Thin Films.

The atomic layer deposition (ALD) of multication oxide films is complicated because the deposition behaviors of the component oxides are not independent of one another. In this study, the Ti and Sr atom incorporation behaviors during the ALD of SrTiO3 films were quantitatively examined via the carefully designed ALD process sequences. H2O and O3 were adopted as the oxygen sources of the SrO subcycles, whereas only O3 was used for the TiO2 ALD subcycles. Apart from the general conjecture on the roles of the different types of oxygen sources, the oxygen source that was adopted for the subcycles of the other component oxide had almost complete control of the metal atom incorporation behaviors. This means that the first half-cycle of ALD played a dominant role in determining the metal incorporation rate, which revealed the critical role of the steric hindrance effect during the metal precursor injection for the ALD rate. O3 had almost doubled its reactivity toward the Ti and Sr precursors compared with H2O. Although these are the expected results from the common knowledge on ALD, the quantitative analysis of the incorporation behaviors of each metal atom provided insightful viewpoints for the ALD process of this technically important oxide material. Furthermore, the SrTiO3 films with a bulk dielectric constant as high as 236 were obtained by the Ru-SrTiO3-RuO2 capacitor structure.

Surface and grain boundary energy as the key enabler of ferroelectricity in nanoscale hafnia-zirconia: a comparison of model and experiment.

The unexpected ferroelectric properties of nanoscale hafnia-zirconia are considered to be promising for a wealth of applications including ferroelectric memory, field effect transistors, and energy-related applications. However, the reason why the unexpected ferroelectric Pca21 phase can be stabilized has not been clearly understood although numerous extensive theoretical and experimental results have been reported recently. The ferroelectric orthorhombic phase is not a stable phase under processing conditions from the viewpoint of bulk free energy. Although the possibility of stabilization of the ferroelectric phase due to the surface energy effect has been theoretically suggested, such a theoretical model has not been systematically compared with actual experimental results. In this study, the experimental observations on polymorphism in nanoscale HfO2-ZrO2 solid solution thin films of a wide range of film compositions and thicknesses are comprehensively related to the theoretical predictions based on a thermodynamic surface energy model. The theoretical model can semi-quantitatively explain the experimental results on the phase-evolution, but there were non-negligible discrepancies between the two results. To understand these discrepancies, various factors such as the film stress, the role of a TiN capping layer, and the kinetics of crystallization are systematically studied. This work also reports on the evolution of electrical properties of the film, i.e. dielectric, ferroelectric, anti-ferroelectric, and morphotropic phase changes, as a function of the film composition and thickness. The in-depth analyses of the phase change are expected to provide an important guideline for subsequent studies.

Resistance switching behavior of atomic layer deposited SrTiO3 film through possible formation of Sr2Ti6O13 or Sr1Ti11O20 phases.

Identification of microstructural evolution of nanoscale conducting phase, such as conducting filament (CF), in many resistance switching (RS) devices is a crucial factor to unambiguously understand the electrical behaviours of the RS-based electronic devices. Among the diverse RS material systems, oxide-based redox system comprises the major category of these intriguing electronic devices, where the local, along both lateral and vertical directions of thin films, changes in oxygen chemistry has been suggested to be the main RS mechanism. However, there are systems which involve distinctive crystallographic phases as CF; the Magnéli phase in TiO2 is one of the very well-known examples. The current research reports the possible presence of distinctive local conducting phase in atomic layer deposited SrTiO3 RS thin film. The conducting phase was identified through extensive transmission electron microscopy studies, which indicated that oxygen-deficient Sr2Ti6O13 or Sr1Ti11O20 phase was presumably present mainly along the grain boundaries of SrTiO3 after the unipolar set switching in Pt/TiN/SrTiO3/Pt structure. A detailed electrical characterization revealed that the samples showed typical bipolar and complementary RS after the memory cell was unipolar reset.

Evaluating the top electrode material for achieving an equivalent oxide thickness smaller than 0.4 nm from an Al-doped TiO2 film.

The effects of Pt and RuO2 top electrodes on the electrical properties of capacitors with Al-doped TiO2 (ATO) films grown on the RuO2 bottom electrode by an atomic layer deposition method were examined. The rutile phase ATO films with high bulk dielectric constant (>80) were well-grown because of the local epitaxial relationship with the rutile structured RuO2 bottom electrode. However, the interface between top electrode and ATO was damaged during the sputtering process of the top electrode, resulting in the decrease in the dielectric constant. Postmetallization annealing at 400 °C was performed to mitigate the sputtering damage. During the postmetallization annealing, the ATO layer near the RuO2 top electrode/ATO interface was well-crystallized because of the structural compatibility between RuO2 and rutile ATO, while the ATO layer near the Pt top electrode/ATO interface still exhibited an amorphous-like structure. Despite the same thickness of the ATO films, therefore, the capacitors with RuO2 top electrodes showed higher capacitance compared to the capacitors with Pt top electrodes. Eventually, an extremely low equivalent oxide thickness of 0.37 nm with low enough leakage current density (<1 × 10(-7) A/cm(2) at 0.8 V) and physical thickness of 8.7 nm for the next-generation dynamic random access memory was achieved from ATO films with RuO2 top electrodes.

Structure and electrical properties of Al-doped HfO2 and ZrO2 films grown via atomic layer deposition on Mo electrodes.

The effects of Al doping in atomic-layer-deposited HfO2 (AHO) and ZrO2 (AZO) films on the evolutions of their crystallographic phases, grain sizes, and electric properties, such as their dielectric constants and leakage current densities, were examined for their applications in high-voltage devices. The film thickness and Al-doping concentration were varied in the ranges of 60-75 nm and 0.5-9.7%, respectively, for AHO and 55-90 nm and 1.0-10.3%, respectively, for AZO. The top and bottom electrodes were sputtered Mo films. The detailed structural and electrical property variations were examined as functions of the Al concentration and film thickness. The AHO films showed a transition from the monoclinic phase (Al concentration up to 1.4%) to the tetragonal/cubic phase (Al concentration 2.0-3.5%), and finally, to the amorphous phase (Al concentration >4.7%), whereas the AZO films remained in the tetragonal/cubic phase up to the Al concentration of 6.4%. For both the AHO and AZO films, the monoclinic and amorphous phases had dielectric constants of 20-25, and the tetragonal/cubic phases had dielectric constants of 30-35. The highest electrical performance levels for the application to the high-voltage charge storage capacitors in flat panel displays were achieved with the 4.7-9.7% Al-doped AHO films and the 2.6% Al-doped AZO films.

Controlling the Al-doping profile and accompanying electrical properties of rutile-phased TiO2 thin films.

The role of Al dopant in rutile-phased TiO2 films in the evaluation of the mechanism of leakage current reduction in Al-doped TiO2 (ATO) was studied in detail. The leakage current of the ATO film was strongly affected by the Al concentration at the interface between the ATO film and the RuO2 electrode. The conduction band offset of the interface increased with the increase in the Al dopant concentration in the rutile TiO2, which reduced the leakage current in the voltage region pertinent to the next-generation dynamic random access memory application. However, the Al doping in the anatase TiO2 did not notably increase the conduction band offset even with a higher Al concentration. The detailed analyses of the leakage conduction mechanism based on the quantum mechanical transfer-matrix method showed that Schottky emission and Fowler-Nordheim tunneling was the dominant leakage conduction mechanism in the lower and higher voltage regions, respectively. The chemical analyses using X-ray photoelectron spectroscopy corroborated the electrical test results.

Nanoscale characterization of TiO(2) films grown by atomic layer deposition on RuO(2) electrodes.

Topography and leakage current maps of TiO2 films grown by atomic layer deposition on RuO2 electrodes using either a TiCl4 or a Ti(O-i-C3H7)4 precursor were characterized at nanoscale by conductive atomic force microscopy (CAFM). For both films, the leakage current flows mainly through elevated grains and not along grain boundaries. The overall CAFM leakage current is larger and more localized for the TiCl4-based films (0.63 nm capacitance equivalent oxide thickness, CET) compared to the Ti(O-i-C3H7)4-based films (0.68 nm CET). Both films have a physical thickness of ∼20 nm. The nanoscale leakage currents are consistent with macroscopic leakage currents from capacitor structures and are correlated with grain characteristics observed by topography maps and transmission electron microscopy as well as with X-ray diffraction.

Impact of bimetal electrodes on dielectric properties of TiO2 and Al-doped TiO2 films.

Rutile structured Al-doped TiO(2) (ATO) and TiO(2) films were grown on bimetal electrodes (thin Ru/thick TiN, Pt, and Ir) for high-performance capacitors. The work function of the top Ru layer decreased on TiN and increased on Pt and Ir when it was thinner than ~2 nm, suggesting that the lower metal within the electrodes influences the work function of the very thin Ru layer. The use of the lower electrode with a high work function for bottom electrode eventually improves the leakage current properties of the capacitor at a very thin Ru top layer (≤2 nm) because of the increased Schottky barrier height at the interface between the dielectric and the bottom electrode. The thin Ru layer was necessary to achieve the rutile structured ATO and TiO(2) dielectric films.