Low-temperature controllable synthesis of monolayer-to-multilayer thick MoS2 with tuneable morphology is demonstrated by using plasma enhanced atomic layer deposition (PEALD). The characteristic self-limiting ALD growth with a growth-per-cycle of 0.1 nm per cycle and digital thickness control down to a monolayer are observed with excellent wafer scale uniformity. The as-deposited films are found to be polycrystalline in nature showing the signature Raman and photoluminescence signals for the mono-to-few layered regime. Furthermore, a transformation in film morphology from in-plane to out-of-plane orientation of the 2-dimensional layers as a function of growth temperature is observed. An extensive study based on high-resolution transmission electron microscopy is presented to unravel the nucleation mechanism of MoS2 on SiO2/Si substrates at 450 °C. In addition, a model elucidating the film morphology transformation (at 450 °C) is hypothesized. Finally, the out-of-plane oriented films are demonstrated to outperform the in-plane oriented films in the hydrogen evolution reaction for water splitting applications.
Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiOx and HfOx and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiNx and HfNx films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiOx were slightly improved whereas those of SiNx were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed.
In this work, we present an extensive characterization of plasma-assisted atomic-layer-deposited SnO2 layers, with the aim of identifying key material properties of SnO2 to serve as an efficient electron transport layer in perovskite solar cells (PSCs). Electrically resistive SnO2 films are fabricated at 50 °C, while a SnO2 film with a low electrical resistivity of 1.8 × 10–3 Ω cm, a carrier density of 9.6 × 1019 cm–3, and a high mobility of 36.0 cm2/V s is deposited at 200 °C. Ultraviolet photoelectron spectroscopy indicates a conduction band offset of ∼0.69 eV at the 50 °C SnO2/Cs0.05(MA0.17FA0.83)0.95Pb(I2.7Br0.3) interface. In contrast, a negligible conduction band offset is found between the 200 °C SnO2 and the perovskite. Surprisingly, comparable initial power conversion efficiencies (PCEs) of 17.5 and 17.8% are demonstrated for the champion cells using 15 nm thick SnO2 deposited at 50 and 200 °C, respectively. The latter gains in fill factor but loses in open-circuit voltage. Markedly, PSCs using the 200 °C compact SnO2 retain their initial performance at the maximum power point over 16 h under continuous one-sun illumination in inert atmosphere. Instead, the cell with the 50 °C SnO2 shows a decrease in PCE of approximately 50%.
Plasma-enhanced atomic layer deposition (PEALD) has obtained a prominent position in the synthesis of nanoscale films with precise growth control. Apart from the well-established contribution of highly reactive neutral radicals towards film growth in PEALD, the ions generated by the plasma can also play a significant role. In this work, we report on the measurements of ion energy and flux characteristics on grounded and biased substrates during plasma exposure to investigate their role in tailoring material properties. Insights from such measurements are essential toward understanding how a given PEALD process at different operating conditions can be influenced by energetic ions. Ion flux-energy distribution functions (IFEDFs) of reactive plasmas typically used for PEALD (O 2 , H 2 , N 2 ) were measured in a commercial 200 mm remote inductively coupled plasma ALD system equipped with RF substrate biasing. IFEDFs were obtained using a gridded retarding field energy analyzer and the effect of varying ICP power, pressure and bias conditions on the ion energy and flux characteristics of the three reactive plasmas were investigated. The properties of three material examples-TiO x , HfN x and SiN x -deposited using these plasmas were investigated on the basis of the energy and flux parameters derived from IFEDFs. Material properties were analyzed in terms of the total ion energy dose delivered to a growing film in every ALD cycle, which is a product of the mean ion energy, total ion flux and plasma exposure time. The properties responded differently to the ion energy dose depending on whether it was controlled with RF substrate biasing where ion energy was enhanced, or without any biasing where plasma exposure time was increased. This indicated that material properties were influenced by whether or not ion energies exceeded energy barriers related to physical atom displacement or activation of ion-induced chemical reactions during PEALD. Furthermore, once ion energies were enhanced beyond these threshold barriers with RF substrate biasing, material properties became a function of both the enhanced ion energy and the duration for which the ion energy was enhanced during plasma exposure. These results have led to a better insight into the relation between energetic ions and the ensuing material properties, e.g. by providing energy maps of material properties in terms of the ion energy dose during PEALD. It serves to demonstrate how the measurement and control of ion energy and flux characteristics during PEALD can provide a platform for synthesizing nanoscale films with the desired material properties.
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