Abstract: Photovoltaic technologies have shown efficiencies of over 40%, however, manufacturing costs have prevented a more significant energy market penetration. To bridge the gap between the high efficiency technology and low cost manufacturing, a research and development tool and process was built and tested. This fully automated single vacuum photovoltaic manufacturing tool utilizes multiple inline close space sublimation (CSS) sources with automated substrate control. This maintains the proven scalability of the CSS technology and CSS source design but with the added versatility of independent substrate motion. This combination of a scalable deposition technology with increased cell fabrication flexibility has allowed for high efficiency cells to be manufactured and studied. The single vacuum system is capable of fabricating a 3.1 × 3.6 in. substrate every 45 min with a cell efficiency of 12% with a standard deviation of 0.6% as measured over 36 months. The substrate is generally scribed into 25 small area devices allowing for over 250 small area devices to be fabricated each day. The system can operate uninterrupted for maintenance for over 21 days.

Abstract: Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl4) and titanium tetra-isopropoxide [Ti(OCH(CH3)2)4, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO2 film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO2 on SiO2 before substantial growth takes place on Si–H. On both Si–H and Si–OH, the surface reactions proceed during the first few TiCl4/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-are...

Abstract: An understanding of the aging and oxidation of the (0001) surface of Bi2Se3 is critical to a comprehensive physical picture of its topologically protected surface states. Here, the authors contribute new experimental observations about the aging and oxidation process. The authors find that surface aging in ambient conditions occurs in two major steps. Within 2 h of exfoliation, a series of ∼3.2 A high islands are observed by atomic force microscopy over approximately 10% of the surface. Subsequently, patch growth stops, and oxidation begins after the 2 h and continues until one quintuple layer has been oxidized. X-ray photoelectron spectroscopy shows no sign of oxidation before ∼120 min of exposure to air, and the oxygen 1 s peak, as well as oxidized Se 3d and Bi 4d peaks, are clearly present after ∼190 min of ambient exposure. Variable angle spectroscopic ellipsometry indicates that the oxidation of a full quintuple layer occurs on the time scale of days. These results are in good agreement with the time...

Abstract: Ultrathin copper (Cu) layers are in continuous demand in several areas, such as within microelectronics and space, as well as in instrumentation technology requiring an electrical resistivity as low as possible. However, the performance of modern copper connections is limited by the size-dependent value of the film resistivity, which is known to increase when the layer thickness is reduced to a few tens of nanometer. In this work, the authors have successfully deposited Cu thin films from 20 to 800 nm exhibiting reduced electrical resistivity by using a high power impulse magnetron sputtering (HiPIMS) process. The electrical and microstructural properties of such films were compared to samples deposited by conventional direct current magnetron sputtering (DCMS) within the same thickness range. For films as thin as 30 nm, the electrical resistivity was reduced by ∼30% when deposited by HiPIMS compared to DCMS, being only three times larger than the copper bulk value. The HiPIMS Cu films exhibit larger grai...

Abstract: The growth conditions of tungsten thin films were investigated using various substrates including Si, Si/SiO2, GaAs, MgO, and Al2O3, and recipes were discovered for the optimal growth conditions of thick metastable β-phase tungsten films on Si, GaAs, and Al2O3 substrates, which is an important material in spin orbit torque studies. For the Si/SiO2 substrate, the crystal phase of the tungsten films was different depending upon the tungsten film thickness, and the transport properties were found to dramatically change with the thickness owing to a change in phase from the α + β phase to the α-phase. It is shown that the crystal phase changes are associated with residual stress in the tungsten films and that the resistivity is closely related to the grain sizes.

Abstract: The authors report on the fabrication of TiO2 and Al2O3 nanostructured gratings with an aspect ratio of up to 50. The gratings were made by a combination of atomic layer deposition (ALD) and dry etch techniques. The workflow included fabrication of a Si template using deep reactive ion etching followed by ALD of TiO2 or Al2O3. Then, the template was etched away using SF6 in an inductively coupled plasma tool, which resulted in the formation of isolated ALD coatings, thereby achieving high aspect ratio grating structures. SF6 plasma removes silicon selectively without any observable influence on TiO2 or Al2O3, thus revealing high selectivity throughout the fabrication. Scanning electron microscopy was used to analyze every fabrication step. Due to nonreleased stress in the ALD coatings, the top parts of the gratings were observed to bend inward as the Si template was removed, thus resulting in a gradual change in the pitch value of the structures. The pitch on top of the gratings is 400 nm, and it graduall...

Abstract: The investigation of mechanical properties of atomic layer deposition HfO2 films is important for implementing these layers in microdevices. The mechanical properties of films change as a function of composition and structure, which accordingly vary with deposition temperature and post-annealing. This work describes elastic modulus, hardness, and wear resistance of as-grown and annealed HfO2. From nanoindentation measurements, the elastic modulus and hardness remained relatively stable in the range of 163–165 GPa and 8.3–9.7 GPa as a function of deposition temperature. The annealing of HfO2 caused significant increase in hardness up to 14.4 GPa due to film crystallization and densification. The structural change also caused increase in the elastic modulus up to 197 GPa. Wear resistance did not change as a function of deposition temperature, but improved upon annealing.

Abstract: Large-scale classical molecular dynamics simulations of epitaxial TiN/TiN(001) thin film growth at 1200 K are carried out using incident flux ratios N/Ti = 1, 2, and 4. The films are analyzed as a function of composition, island size distribution, island edge orientation, and vacancy formation. Results show that N/Ti = 1 films are globally understoichiometric with dispersed Ti-rich surface regions which serve as traps to nucleate 111-oriented islands, leading to local epitaxial breakdown. Films grown with N/Ti = 2 are approximately stoichiometric and the growth mode is closer to layer-by-layer, while N/Ti = 4 films are stoichiometric with N-rich surfaces. As N/Ti is increased from 1 to 4, island edges are increasingly polar, i.e., 110-oriented, and N-terminated to accommodate the excess N flux, some of which is lost by reflection of incident N atoms. N vacancies are produced in the surface layer during film deposition with N/Ti = 1 due to the formation and subsequent desorption of N2 molecules composed of a N adatom and a N surface atom, as well as itinerant Ti adatoms pulling up N surface atoms. The N vacancy concentration is significantly reduced as N/Ti is increased to 2; with N/Ti = 4, Ti vacancies dominate. Overall, our results show that an insufficient N/Ti ratio leads to surface roughening via nucleation of small dispersed 111 islands, whereas high N/Ti ratios result in surface roughening due to more rapid upper-layer nucleation and mound formation. The growth mode of N/Ti = 2 films, which have smoother surfaces, is closer to layer-by-layer.

Abstract: Silicon nitride spacer etching realization is considered today as one of the most challenging processes for the fully depleted silicon on insulator devices realization. For this step, the atomic etch precision to stop on silicon or silicon germanium with a perfect anisotropy (no foot formation) is required. In a recent study, the authors demonstrated the benefit of an alternative etch chemistry based on silicon nitride film modification by H2 or He plasma followed by a removal step of this modified layer using hydrofluoric acid based wet cleaning. In this paper, the authors investigate the silicon nitride modified layer removal by mixing fluorine based gas (NF3) with hydrogen based gas (NH3) performed in a remote plasma followed by an annealing step. The interaction mechanisms between modified silicon nitride and the NF3-NH3 plasma have been understood, thanks to x-ray photoelectron spectroscopy and infrared spectroscopy analyses. Finally, the efficiency of the best NF3-NH3 plasma process to remove the modified silicon nitride layer has been evaluated on pattern structures.

Abstract: Atomic layer deposition (ALD) of conformal AlF3 coatings onto both flat silicon substrates and high-voltage LiNi0.5Mn0.3Co0.2O2 (NMC) Li-ion battery cathode powders was investigated using a Al(CH3)3/TaF5 precursor combination. This optimized approach employs easily handled ALD precursors, while also obviating the use of highly toxic HF(g). In studies conducted on planar Si wafers, the film's growth mode was dictated by a competition between the desorption and decomposition of Ta reaction byproducts. At T ≥ 200 °C, a rapid decomposition of the Ta reaction byproducts to TaC led to continuous deposition and high concentrations of TaC in the films. A self-limited ALD growth mode was found to occur when the deposition temperature was reduced to 125 °C, and the TaF5 exposures were followed by an extended purge. The lower temperature process suppressed conversion of TaFx(CH3)5−x to nonvolatile TaC, and the long purges enabled nearly complete TaFx(CH3)5−x desorption, leaving behind the AlF3 thin films. NMC cathod...

Abstract: The authors developed a high throughput (70 A/min) and scalable space-divided atomic layer deposition (ALD) system for thin film encapsulation (TFE) of flexible organic light-emitting diode (OLED) displays at low temperatures (<100 °C). In this paper, the authors report the excellent moisture barrier properties of Al2O3 films deposited on 2G glass substrates of an industrially relevant size (370 × 470 mm2) using the newly developed ALD system. This new ALD system reduced the ALD cycle time to less than 1 s. A growth rate of 0.9 A/cycle was achieved using trimethylaluminum as an Al source and O3 as an O reactant. The morphological features and step coverage of the Al2O3 films were investigated using field emission scanning electron microscopy. The chemical composition was analyzed using Auger electron spectroscopy. These deposited Al2O3 films demonstrated a good optical transmittance higher than 95% in the visible region based on the ultraviolet visible spectrometer measurements. Water vapor transmission r...

Abstract: This paper presents a study on plasma enhanced atomic layer deposition (ALD) of TiO2 and WO3 films on silicon substrates. At low temperatures, ALD processes, which are not feasible at high temperatures, could be possible. For example, temperatures at 180 °C and above allow no WO3 ALD process with WF6 as a precursor because etching processes hinder film growth. Further low temperature deposition techniques are needed to coat temperature sensitive materials. For the deposition, WF6 and TiCl4 are used as metal precursors and O2 and H2O as oxygen sources. The depositions were accomplished in the temperature range of 30 °C up to 180 °C for both metal oxides. Spectroscopic ellipsometry, x-ray reflection, and grazing incidence diffraction were used to investigate the deposited ALD thin films. Film growth, density, crystallinity, and roughness are discussed as functions of temperature after ensuring the ALD requirement of self-saturating adsorption. Growth rates and measured material properties are in good agreem...

Abstract: 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...

Abstract: Atomic layer deposition (ALD) represents one of the most fundamental techniques capable of satisfying the strict technological requirements imposed by the rapidly evolving electronic components industry. The actual scaling trend is rapidly leading to the fabrication of nanoscaled devices able to overcome limits of the present microelectronic technology, of which the memristor is one of the principal candidates. Since their development in 2008, TiO2 thin film memristors have been identified as the future technology for resistive random access memories because of their numerous advantages in producing dense, low power-consuming, three-dimensional memory stacks. The typical features of ALD, such as self-limiting and conformal deposition without line-of-sight requirements, are strong assets for fabricating these nanosized devices. This work focuses on the realization of memristors based on low-temperature ALD TiO2 thin films. In this process, the oxide layer was directly grown on a polymeric photoresist, thus...

Abstract: Spatial atomic layer deposition (SALD) is a promising technology with the aim of combining the advantages of excellent uniformity and conformity of temporal atomic layer deposition (ALD), and an industrial scalable and continuous process. In this manuscript, an experimental and numerical combined model of atmospheric SALD system is presented. To establish the connection between the process parameters and the growth efficiency, a quantitative model on reactant isolation, throughput, and precursor utilization is performed based on the separation gas flow rate, carrier gas flow rate, and precursor mass fraction. The simulation results based on this model show an inverse relation between the precursor usage and the carrier gas flow rate. With the constant carrier gas flow, the relationship of precursor usage and precursor mass fraction follows monotonic function. The precursor concentration, regardless of gas velocity, is the determinant factor of the minimal residual time. The narrow gap between precursor injecting heads and the substrate surface in general SALD system leads to a low Peclet number. In this situation, the gas diffusion act as a leading role in the precursor transport in the small gap rather than the convection. Fluid kinetics from the numerical model is independent of the specific structure, which is instructive for the SALD geometry design as well as its process optimization.

Abstract: NiO films were prepared with different O2/Ar reactive sputtering gas ratios. The morphology, crystalline structure, and optical properties of the as-deposited films are dependent on sputtering gas ratios. The NiO/GaN heterojunction diode was fabricated with NiO film obtained at medium O content (25%). Compared with the Ni/GaN Schottky diode, the NiO/GaN heterojunction diode shows a relatively higher turn-on voltage and lower reverse leakage current. The temperature-dependent current–voltage characteristics demonstrate that the thermionic emission dominated the reverse leakage current of the NiO/GaN diode.

Abstract: A radio frequency argon microplasma jet at atmospheric-pressure is characterized using Langmuir probes. While optical methods are the typical diagnostic for these small scale plasmas, the simplicity and low cost of Langmuir probes makes them an attractive option. The plasma density and electron temperature are measured using existing high-pressure Langmuir probe theories developed for flames and arcs. The density and temperature vary from 1 × 1016 to 1 × 1019 m−3 and 2.3 to 4.4 eV, respectively, depending on the operating condition. The density decreases while the electron temperature increases with axial distance from the jet exit. The applicability of the probe theories as well as the effect of collisionality and jet mixing is discussed.

Abstract: Al2O3 [20 nm, atomic layer deposition (ALD)] and SiO films' [25 nm, physical vacuum deposition (PVD)] single barriers as well as hybrid barriers of the Al2O3/SiO or SiO/Al2O3 have been deposited onto single 100 nm thick tris-(8-hydroxyquinoline) aluminum (AlQ3) organic films made onto silicon wafers. The defects in the different barrier layers could be easily observed as nonfluorescent AlQ3 black spots, under ultraviolet light on the different systems stored into accelerated aging conditions (85 °C/85% RH, ∼2000 h). It has been observed that all devices containing an Al2O3 layer present a lag time τ from which defect densities of the different systems start to increase significantly. This is coherent with the supposed pinhole-free nature of fresh, ALD-deposited, Al2O3 films. For t > τ, the number of defect grows linearly with storage time. For devices with the single Al2O3 barrier layer, τ has been estimated to be 64 h. For t > τ, the defect occurrence rate has been calculated to be 0.268/cm2/h. Then, a t...

Abstract: Chemoresistive sensors based on multiwalled carbon nanotubes (MWCNTs) functionalized with SnO2 nanocrystals (NCs) have great potential for detecting trace gases at low concentrations (single ppm levels) at room temperature, because the SnO2 nanocrystals act as active sites for the chemisorption of gas molecules, and carbon nanotubes (CNTs) act as an excellent current carrying platform, allowing the adsorption of gas on SnO2 to modulate the resistance of the CNTs. However, uniform conjugation of SnO2 NCs with MWCNTs is challenging. An effective atomic layer deposition based approach to functionalize the surface of MWCNTs with SnO2 NCs, resulting in a novel CH4 sensor with 10 ppm sensitivity, is presented in this paper. Scanning electron microscopy, transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy, and Raman spectroscopy were implemented to study the morphology, elemental composition, and the crystal quality of SnO2 functionalized MWCNTs. High resolution TEM images showed that th...

Abstract: Thin films of complex alkali oxides are frequently investigated due to the large range of electric effects that are found in this class of materials. Their piezo- and ferroelectric properties also place them as sustainable lead free alternatives in optoelectronic devices. Fully gas-based routes for deposition of such compounds are required for integration into microelectronic devices that need conformal thin films with high control of thickness- and composition. The authors here present a route for deposition of materials in the (K,Na)(Nb,Ta)O3-system, including the four end members NaNbO3, KNbO3, NaTaO3, and KTaO3, using atomic layer deposition with emphasis on control of stoichiometry in such mixed quaternary and quinary compunds.

Abstract: Core–shell powders consisting of a tungsten particle core and thin alumina shell have been synthesized using atomic layer deposition in a rotary reactor. Standard atomic layer deposition of trimethylaluminum/water at 150 °C utilizing a microdosing technique was performed on four different batches of powder with different average particle sizes. The particle size of the powders studied ranges from ∼25 to 1500 nm. The high mass-thickness contrast between alumina and tungsten in transmission electron microscopy images demonstrates that the particle core/shell interface is abrupt. This allows for the uncomplicated measurement of alumina thickness and therefore the accurate determination of growth per cycle. In agreement with prior works, the highest growth per cycle of ∼2 A/cycle occurred on the batch of powder with the smallest average particle size and the growth per cycle decreased with increasing average particle size of a powder batch. However, the growth per cycle of the alumina film on an individual pa...

Abstract: Indium-gallium-zinc-oxide (IGZO) Schottky diodes exhibit excellent performance in comparison with conventional devices used in future flexible high frequency electronics. In this work, a high performance Pt IGZO Schottky diode was presented by using a new fabrication process. An argon/oxygen mixture gas was introduced during the deposition of the Pt layer to reduce the oxygen deficiency at the Schottky interface. The diode showed a high barrier height of 0.92 eV and a low ideality factor of 1.36 from the current–voltage characteristics. Even the radius of the active area was 0.1 mm, and the diode showed a cut-off frequency of 6 MHz in the rectifier circuit. Using the diode as a demodulator, a potential application was also demonstrated in this work.

Abstract: Copper(II) oxide thin films were grown by atomic layer deposition (ALD) using bis-(dimethylamino-2-propoxide)copper [Cu(dmap)2] and ozone in a temperature window of 80–140 °C. A thorough characterization of the films was performed using x-ray diffraction, x-ray reflectivity, UV‐Vis spectrophotometry, atomic force microscopy, field emission scanning electron microscopy, x-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis techniques. The process was found to produce polycrystalline copper(II) oxide films with a growth rate of 0.2–0.3 A per cycle. Impurity content in the films was relatively small for a low temperature ALD process.

Abstract: Inspired by the need to discover environmentally friendly, lead-free ferroelectric materials, here the authors report the atomic layer deposition of tin titanate (SnTiOx) aiming to obtain the theoretically predicted perovskite structure that possesses ferroelectricity. In order to establish the growth conditions and probe the film structure and ferroelectric behavior, the authors grew SnTiOxfilms on the commonly used Si(100) substrate. Thin films of SnTiOx have been successfully grown at a deposition temperature of 200 °C, with a Sn/Ti atomic layer deposition(ALD) cycle ratio of 2:3 and postdeposition heat treatments under different conditions. X-ray photoelectron spectroscopy revealed excellent composition tunability of ALD.X-ray diffraction spectra suggested anatase phase for all films annealed at 650 and 350 °C, with peak positions shifted toward lower 2-theta angles indicating enlarged unit cell volume. The film annealed in O2 at 350 °C exhibited piezoresponse amplitude and phase hysteresis loops, indicative of the existence of switchable polarization.

Abstract: A plasma-enhanced chemical vapor deposition system was used to fabricate ultraviolet (UV) photodetectors based on polar and nonpolar zinc oxide (ZnO) thin films combined with interdigitated platinum top electrodes. The performance of photodetectors was demonstrated by current–voltage characteristics and time-dependent photoresponse measurements. Both polar and nonpolar detectors showed a prominent photocurrent gain under UV light illumination, compared with dark conditions. However, the response and recovery times for the nonpolar detectors were significantly faster compared to the polar detectors. These variations in response and recovery times can be explained by the dipole effect between the electrode and sensing thin film, which is due to the adsorption and desorption of gas molecules on polar and nonpolar ZnO thin film surfaces.

Abstract: Experimental data for benzene adsorption on chemical vapor deposited graphene/Cu and graphene/SiO2 studied at ultrahigh vacuum conditions are discussed and compared with prior work on physical vapor deposited graphene/Ru(0001). Two widely considered topics, namely, the transparency of graphene and support effects of epitaxial graphene are investigated. Graphene is nearly transparent for benzene adsorption on both copper and silica supports opposed to Ru(0001). In addition, the desorption energy for benzene on epitaxial graphene depends on the reactivity of the support.

Abstract: A one-dimensional steady-state hydrodynamic model of electron beam generated plasmas produced in Ar-SF6 mixtures at low pressure in a constant magnetic field was developed. Simulations were performed for a range of SF6 partial pressures at constant 30 mTorr total gas pressure to determine the spatial distribution of species densities and fluxes. With the addition of small amount of SF6 (∼1%), the confining electrostatic field sharply decreases with respect to the pure argon case. This effect is due to the applied magnetic field inhibiting electron diffusion. The hallmark of electronegative discharge plasmas, positive ion—negative ion core and positive ion—electron edge, was not observed. Instead, a plasma with large electronegativity (∼100) is formed throughout the volume, and only a small fraction (≈30%) of the parent SF6 molecules were dissociated to F2, SF2, and SF4. Importantly, F radical densities were found to be very low, on the order of the ion density. Model predictions for the electron density, ...

Abstract: The process parameters' impact of the plasma-enhanced atomic layer deposition (PE-ALD) method on the oxygen to nitrogen (O/N) ratio in titanium oxynitride (TiOxNy) films was studied. Titanium(IV)isopropoxide in combination with NH3 plasma and tetrakis(dimethylamino)titanium by applying N2 plasma processes were investigated. Samples were characterized by the in situ spectroscopic ellipsometry, x-ray photoelectron spectroscopy, and electrical characterization (current–voltage: I-V and capacitance–voltage: C-V) methods. The O/N ratio in the TiOxNy films is found to be very sensitive for their electric properties such as conductivity, dielectric breakdown, and permittivity. Our results indicate that these PE-ALD film properties can be tuned, via the O/N ratio, by the selection of the process parameters and precursor/coreactant combination.

Abstract: Iron(II,III) oxide (Fe3O4) nanoparticles have shown great promise in many magnetic-related applications such as magnetic resonance imaging, hyperthermia treatment, and targeted drug delivery. Nevertheless, these nanoparticles are vulnerable to oxidation and magnetization loss under ambient conditions, and passivation is usually required for practical applications. In this work, a home-built rotating fluidized bed (RFB) atomic layer deposition (ALD) reactor was employed to form dense and uniform nanoscale Al2O3 passivation layers on Fe3O4 nanoparticles. The RFB reactor facilitated the precursor diffusion in the particle bed and intensified the dynamic dismantling of soft agglomerates, exposing every surface reactive site to precursor gases. With the aid of in situ mass spectroscopy, it was found that a thicker fluidization bed formed by larger amount of particles increased the residence time of precursors. The prolonged residence time allowed more thorough interactions between the particle surfaces and the...