A study was undertaken to determine the efficacy of various underlayers for the nucleation and growth of atomic layer deposited HfO2 films. These were compared to films grown on hydrogen terminated Si. The use of a chemical oxide underlayer results in almost no barrier to film nucleation, enables linear and predictable growth at constant film density, and the most two-dimensionally continuous HfO2 films. The ease of nucleation is due to the large concentration of OH groups in the hydrous, chemical oxide. HfO2 grows on chemical oxide at a coverage rate of about 14% of a monolayer per cycle, and films are about 90% of the theoretical density of crystalline HfO2. Growth on hydrogen terminated Si is characterized by a large barrier to nucleation and growth, resulting in three-dimensional, rough, and nonlinear growth. Thermal oxide/oxynitride underlayers result in a small nucleation barrier, and nonlinear growth at low HfO2 coverages. The use of chemical oxide underlayers clearly results in the best HfO2 layers. Further, the potential to minimize the chemical oxide thickness provides an important research opportunity for high-κ gate dielectric scaling below 1.0 nm effective oxide thickness.
In search of a proper passivation for high-k Ge metal-oxide-semiconductor devices, the authors have deposited high-k dielectric layers on GeO2, grown at 350–450°C in O2. ZrO2, HfO2, and Al2O3 were deposited by atomic layer deposition (ALD). GeO2 and ZrO2 or HfO2 intermix during ALD, together with partial reduction of Ge4+. Almost no intermixing or reduction occurs during Al2O3 ALD. Capacitors show well-behaved capacitance-voltage characteristics on both n- and p-Ge, indicating efficient passivation of the Ge∕GeOx interface. The density of interface states is typically in the low to mid-1011cm−2eV−1 range, approaching state-of-the-art Si∕HfO2∕matal gate devices.
For almost sixty years, solar energy for space applications has relied on inorganic photovoltaics, evolving from solar cells made of single crystalline silicon to triple junctions based on germanium and III-V alloys. The class of organic-based photovoltaics, which ranges from all-organic to hybrid perovskites, has the potential of becoming a disruptive technology in space applications, thanks to the unique combination of appealing intrinsic properties (e.g. record high specific power, tunable absorption window) and processing possibilities. Here, we report on the launch of the stratospheric mission OSCAR, which demonstrated for the first time organic-based solar cell operation in extraterrestrial conditions. This successful maiden flight for organic-based photovoltaics opens a new paradigm for solar electricity in space, from satellites to orbital and planetary space stations.Nevertheless, already in the fields of aerospace[3] and of organic and hybrid semiconductors [4,5], the specific power (W/kg) was proposed as a valid figure of merit to evaluate PV technologies for space missions. In this regard, Organic Solar Cells (OSCs) and hybrid organic-inorganic Perovskite Solar Cells (PSCs) -termed together as HOPV, Hybrid and Organic PhotoVoltaicsgreatly outperform their inorganic counterparts [4,5]. They represent two novel branches of PV technologies, which saw their rise during the last decade (last few years in the case of PSCs) thanks to their potentially very low production costs. The high absorbance of the photo-active layers in HOPVs allows for efficient light collection within a few hundred nanometers of material, which leads to thicknesses one or two orders of magnitude lower than those of inorganic thin PVs. The rest of the layers making up the solar cell stacks are either as thin as or thinner than the absorbers, and the only thickness (and hence mass) limitation comes from substrate and encapsulation, which can consist of micrometers thick flexible plastic foil [4,5]. The specific power reached to date for perovskite (23 kW/kg) [4] and organic (10 kW/kg)[5] solar cells is thus over 20
Atomic layer deposition (ALD) is used in applications where inorganic material layers with uniform thickness down to the nanometer range are required. For such thicknesses, the growth mode, defining how the material is arranged on the surface during the growth, is of critical importance. In this work, the growth mode of the zirconium tetrachloride∕water and the trimethyl aluminum∕water ALD process on hydrogen-terminated silicon was investigated by combining information on the total amount of material deposited with information on the surface fraction of the material. The total amount of material deposited was measured by Rutherford backscattering, x-ray fluorescence, and inductively coupled plasma–optical emission spectroscopy, and the surface fractions by low-energy ion scattering. Growth mode modeling was made assuming two-dimensional growth or random deposition (RD), with a “shower model” of RD recently developed for ALD. Experimental surface fractions of the ALD-grown zirconium oxide and aluminum oxide films were lower than the surface fractions calculated assuming RD, suggesting the occurrence of island growth. Island growth was confirmed with transmission electron microscopy (TEM) measurements, from which the island size and number of islands per unit surface area could also be estimated. The conclusion of island growth for the aluminum oxide deposition on hydrogen-terminated silicon contradicts earlier observations. In this work, physical aluminum oxide islands were observed in TEM after 15 ALD reaction cycles. Earlier, thicker aluminum oxide layers have been analyzed, where islands have not been observed because they have already coalesced to form a continuous film. The unreactivity of hydrogen-terminated silicon surface towards the ALD reactants, except for reactive defect areas, is proposed as the origin of island growth. Consequently, island growth can be regarded as “undesired surface-selective ALD.”
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