Atomic layer deposition (ALD) relies on alternated, self-limiting reactions between gaseous reactants and an exposed solid surface to deposit highly conformal coatings with a thickness controlled at the submonolayer level. These advantages have rendered ALD a mainstream technique in microelectronics and have triggered growing interest in ALD for a variety of nanotechnology applications, including energy technologies. Often, the choice for ALD is related to the need for a conformal coating on a 3D nanostructured surface, making the conformality of ALD processes a key factor in actual applications. In this work, we aim to review the current status of knowledge about the conformality of ALD processes. We describe the basic concepts related to the conformality of ALD, including an overview of relevant gas transport regimes, definitions of exposure and sticking probability, and a distinction between different ALD growth types observed in high aspect ratio structures. In addition, aiming for a more standardized and direct comparison of reported results concerning the conformality of ALD processes, we propose a new concept, Equivalent Aspect Ratio (EAR), to describe 3D substrates and introduce standard ways to express thin film conformality. Other than the conventional aspect ratio, the EAR provides a measure for the ease of coatability by referring to a cylindrical hole as the reference structure. The different types of high aspect ratio structures and characterization approaches that have been used for quantifying the conformality of ALD processes are reviewed. The published experimental data on the conformality of thermal, plasma-enhanced, and ozone-based ALD processes are tabulated and discussed. Besides discussing the experimental results of conformality of ALD, we will also give an overview of the reported models for simulating the conformality of ALD. The different classes of models are discussed with special attention for the key assumptions typically used in the different modelling approaches. The influence of certain assumptions on simulated deposition thickness profiles is illustrated and discussed with the aim of shedding light on how deposition thickness profiles can provide insights into factors governing the surface chemistry of ALD processes. We hope that this review can serve as a starting point and reference work for new and expert researchers interested in the conformality of ALD and, at the same time, will trigger new research to further improve our understanding of this famous characteristic of ALD processes.

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Conformality in atomic layer deposition : current status overview of analysis and modelling

Nanostructures in silicon (Si) induced by phase transformations have been investigated during the past 50 years. Performances of nanostructures are improved compared to that of bulk counterparts. Nevertheless, the confinement and loading conditions are insufficient to machine and fabricate high-performance devices. As a consequence, nanostructures fabricated by nanoscale deformation at loading speeds of m/s have not been demonstrated yet. In this study, grinding or scratching at a speed of 40.2 m/s was performed on a custom-made setup by an especially designed diamond tip (calculated stress under the diamond tip in the order of 5.11 GPa). This leads to a novel approach for the fabrication of nanostructures by nanoscale deformation at loading speeds of m/s. A new deformation-induced nanostructure was observed by transmission electron microscopy (TEM), consisting of an amorphous phase, a new tetragonal phase, slip bands, twinning superlattices, and a single crystal. The formation mechanism of the new phase was elucidated by ab initio simulations at shear stress of about 2.16 GPa. This approach opens a new route for the fabrication of nanostructures by nanoscale deformation at speeds of m/s. Our findings provide new insights for potential applications in transistors, integrated circuits, diodes, solar cells, and energy storage systems.

New Deformation-Induced Nanostructure in Silicon.

Stability of Cu(In,Ga)Se2 solar cells: A literature review

Degradation mechanisms of high capacity 18650 cells containing Si-graphite anode and nickel-rich NMC cathode

The tuning of structural, optical, and electrical properties of Al-doped ZnO films deposited by atomic layer deposition technique is reported in this work. With the increasing Al doping level, the evolution from (002) to (100) diffraction peaks indicates the change in growth mode of ZnO films. Spectroscopic ellipsometry has been applied to study the thickness, optical constants, and band gap of AZO films. Due to the increasing carrier concentration after Al doping, a blue shift of band gap and absorption edge can be observed, which can be interpreted by Burstein-Moss effect. The carrier concentration and resistivity are found to vary significantly among different doping concentration, and the optimum value is also discussed. The modulations and improvements of properties are important for Al-doped ZnO films to apply as transparent conductor in various applications.

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Effects of Al Doping on the Properties of ZnO Thin Films Deposited by Atomic Layer Deposition

Thermal atomic layer etching (ALE) of crystalline aluminum nitride (AlN) films was demonstrated using sequential, self-limiting reactions with hydrogen fluoride (HF) and tin(II) acetylacetonate [Sn(acac)2] as the reactants. Film thicknesses were monitored versus number of ALE reaction cycles at 275 °C using in situ spectroscopic ellipsometry (SE). A low etch rate of ∼0.07 A/cycle was measured during etching of the first 40 A of the film. This small etch rate corresponded with the AlOxNy layer on the AlN film. The etch rate then increased to ∼0.36 A/cycle for the pure AlN films. In situ SE experiments established the HF and Sn(acac)2 exposures that were necessary for self-limiting surface reactions. In the proposed reaction mechanism for thermal AlN ALE, HF fluorinates the AlN film and produces an AlF3 layer on the surface. The metal precursor, Sn(acac)2, then accepts fluorine from the AlF3 layer and transfers an acac ligand to the AlF3 layer in a ligand-exchange reaction. The possible volatile etch produc...

Thermal atomic layer etching of crystalline aluminum nitride using sequential, self-limiting hydrogen fluoride and Sn(acac)2 reactions and enhancement by H2 and Ar plasmas

Spatial atomic layer deposition (ALD) is a new version of ALD based on the separation of reactant gases in space instead of time. In this paper, the authors present results for spatial ALD on flexible substrates using a modular rotating cylinder reactor. The design for this reactor is based on two concentric cylinders. The outer cylinder remains fixed and contains a series of slits. These slits can accept a wide range of modules that attach from the outside. The modules can easily move between the various slit positions and perform precursor dosing, purging, or pumping. The inner cylinder rotates with the flexible substrate and passes underneath the various spatially separated slits in the outer cylinder. Trimethyl aluminum and ozone were used to grow Al2O3 ALD films at 40 °C on metallized polyethylene terephthalate (PET) substrates to characterize this spatial ALD reactor. Spectroscopic ellipsometry measurements revealed a constant Al2O3 ALD growth rate of 1.03 A/cycle with rotation speeds from 40 to 100...

Spatial atomic layer deposition on flexible substrates using a modular rotating cylinder reactor

In this work, an optical modeling study on electron scattering mechanisms in plasma-deposited ZnO layers is presented. Because various applications of ZnO films pose a limit on the electron carrier density due to its effect on the film transmittance, higher electron mobility values are generally preferred instead. Hence, insights into the electron scattering contributions affecting the carrier mobility are required. In optical models, the Drude oscillator is adopted to represent the free-electron contribution and the obtained optical mobility can be then correlated with the macroscopic material properties. However, the influence of scattering phenomena on the optical mobility depends on the considered range of photon energy. For example, the grain-boundary scattering is generally not probed by means of optical measurements and the ionized-impurity scattering contribution decreases toward higher photon energies. To understand this frequency dependence and quantify contributions from different scattering phenomena to the mobility, several case studies were analyzed in this work by means of spectroscopic ellipsometry and Fourier transform infrared (IR) spectroscopy. The obtained electrical parameters were compared to the results inferred by Hall measurements. For intrinsic ZnO (i-ZnO), the in-grain mobility was obtained by fitting reflection data with a normal Drude model in the IR range. For Al-doped ZnO (Al:ZnO), besides a normal Drude fit in the IR range, an Extended Drude fit in the UV-vis range could be used to obtain the in-grain mobility. Scattering mechanisms for a thickness series of Al:ZnO films were discerned using the more intuitive parameter “scattering frequency” instead of the parameter “mobility”. The interaction distance concept was introduced to give a physical interpretation to the frequency dependence of the scattering frequency. This physical interpretation furthermore allows the prediction of which Drude models can be used in a specific frequency range.

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Optical modeling of plasma-deposited ZnO films: Electron scattering at different length scales

Novel approach to thin film polycrystalline silicon on glass

Spatial atomic layer deposition (S-ALD) was examined on flexible porous substrates utilizing a rotating cylinder reactor to perform the S-ALD. S-ALD was first explored on flexible polyethylene terephthalate polymer substrates to obtain S-ALD growth rates on flat surfaces. ZnO ALD with diethylzinc and ozone as the reactants at 50 °C was the model S-ALD system. ZnO S-ALD was then performed on nanoporous flexible anodic aluminum oxide (AAO) films. ZnO S-ALD in porous substrates depends on the pore diameter, pore aspect ratio, and reactant exposure time that define the gas transport. To evaluate these parameters, the Zn coverage profiles in the pores of the AAO films were measured using energy dispersive spectroscopy (EDS). EDS measurements were conducted for different reaction conditions and AAO pore geometries. Substrate speeds and reactant pulse durations were defined by rotating cylinder rates of 10, 100, and 200 revolutions per minute (RPM). AAO pore diameters of 10, 25, 50, and 100 nm were utilized with...

K. Sharma

Papers

Thermal atomic layer etching of crystalline aluminum nitride using sequential, self-limiting hydrogen fluoride and Sn(acac)2 reactions and enhancement by H2 and Ar plasmas

Spatial atomic layer deposition on flexible substrates using a modular rotating cylinder reactor

Optical modeling of plasma-deposited ZnO films: Electron scattering at different length scales

Novel approach to thin film polycrystalline silicon on glass

Spatial atomic layer deposition on flexible porous substrates: ZnO on anodic aluminum oxide films and Al2O3 on Li ion battery electrodes