In situ formation of inhibitor species through catalytic surface reactions during area-selective atomic layer deposition of TaN.

Small molecule inhibitors (SMIs) have been gaining attention in the field of area-selective atomic layer deposition (ALD) because they can be applied in the vapor-phase. A major challenge for SMIs is that vapor-phase application leads to a disordered inhibitor layer with lower coverage as compared to self-assembled monolayers, SAMs. A lower coverage of SMIs makes achieving high selectivity for area-selective ALD more challenging. To overcome this challenge, mechanistic understanding is required for the formation of SMI layers and the resulting precursor blocking. In this study, reflection adsorption infrared spectroscopy measurements are used to investigate the performance of aniline as an SMI. Our results show that aniline undergoes catalytic surface reactions, such as hydrogenolysis, on a Ru non-growth area at substrate temperatures above 250 °C. At these temperatures, a greatly improved selectivity is observed for area-selective TaN ALD using aniline as an inhibitor. The results suggest that catalytic surface reactions of the SMI play an important role in improving precursor blocking, likely through the formation of a more carbon-rich inhibitor layer. More prominently, catalytic surface reactions can provide a new strategy for forming inhibitor layers that are otherwise very challenging or impossible to form directly through vapor-phase application.

Nb Doping and Alloying of 2D WS2 by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

We utilize plasma-enhanced atomic layer deposition to synthesize two-dimensional Nb-doped WS2 and NbxW1-xSy alloys to expand the range of properties and improve the performance of 2D transition metal dichalcogenides for electronics and catalysis. Using a supercycle deposition process, films are prepared with compositions spanning the range from WS2 to NbS3. While the W-rich films form crystalline disulfides, the Nb-rich films form amorphous trisulfides. Through tuning the composition of the films, the electrical resistivity is reduced by 4 orders of magnitude compared to pure ALD-grown WS2. To produce Nb-doped WS2 films, we developed a separate ABC-type supercycle process in which a W precursor pulse precedes the Nb precursor pulse, thereby reducing the minimum Nb content of the film by a factor of 3 while maintaining a uniform distribution of the Nb dopant. Initial results are presented on the electrical and electrocatalytic performances of the films. Promisingly, the NbxW1-xSy films of 10 nm thickness and composition x ≈ 0.08 are p-type semiconductors and have a low contact resistivity of (8 ± 1) × 102 Ω cm to Pd/Au contacts, demonstrating their potential use in contact engineering of 2D TMD transistors.

Low Surface Recombination in Hexagonal SiGe Alloy Nanowires: Implications for SiGe-Based Nanolasers.

Monolithic integration of silicon-based electronics and photonics could open the door toward many opportunities including on-chip optical data communication and large-scale application of light-based sensing devices in healthcare and automotive; by some, it is considered the Holy Grail of silicon photonics. The monolithic integration is, however, severely hampered by the inability of Si to efficiently emit light. Recently, important progress has been made by the demonstration of efficient light emission from direct-bandgap hexagonal SiGe (hex-SiGe) alloy nanowires. For this promising material, realized by employing a nanowire structure, many challenges and open questions remain before a large-scale application can be realized. Considering that for other direct-bandgap materials like GaAs, surface recombination can be a true bottleneck, one of the open questions is the importance of surface recombination for the photoluminescence efficiency of this new material. In this work, temperature-dependent photoluminescence measurements were performed on both hex-Ge and hex-SiGe nanowires with and without surface passivation schemes that have been well documented and proven effective on cubic silicon and germanium to elucidate whether and to what extent the internal quantum efficiency (IQE) of the wires can be improved. Additionally, time-resolved photoluminescence (TRPL) measurements were performed on unpassivated hex-SiGe nanowires as a function of their diameter. The dependence of the surface recombination on the SiGe composition could, however, not be yet addressed given the sample-to-sample variations of the state-of-the-art hex-SiGe nanowires. With the aforementioned experiments, we demonstrate that at room temperature, under high excitation conditions (a few kW cm-2), the hex-(Si)Ge surface is most likely not a bottleneck for efficient radiative emission under relatively high excitation conditions. This is an important asset for future hex(Si)Ge optoelectronic devices, specifically for nanolasers.

ALD-grown two-dimensional TiSx metal contacts for MoS2 field-effect transistors.

Metal contacts to MoS2 field-effect transistors (FETs) play a determinant role in the device electrical characteristics and need to be chosen carefully. Because of the Schottky barrier (SB) and the Fermi level pinning (FLP) effects that occur at the contact/MoS2 interface, MoS2 FETs often suffer from high contact resistance (Rc). One way to overcome this issue is to replace the conventional 3D bulk metal contacts with 2D counterparts. Herein, we investigate 2D metallic TiSx (x ∼ 1.8) as top contacts for MoS2 FETs. We employ atomic layer deposition (ALD) for the synthesis of both the MoS2 channels as well as the TiSx contacts and assess the electrical performance of the fabricated devices. Various thicknesses of TiSx are grown on MoS2, and the resultant devices are electrically compared to the ones with the conventional Ti metal contacts. Our findings show that the replacement of 5 nm Ti bulk contacts with only ∼1.2 nm of 2D TiSx is beneficial in improving the overall device metrics. With such ultrathin TiSx contacts, the ON-state current (ION) triples and increases to ∼35 µA µm-1. Rc also reduces by a factor of four and reaches ∼5 MΩ µm. Such performance enhancements were observed despite the SB formed at the TiSx/MoS2 interface is believed to be higher than the SB formed at the Ti/MoS2 interface. These device metric improvements could therefore be mainly associated with an increased level of electrostatic doping in MoS2, as a result of using 2D TiSx for contacting the 2D MoS2. Our findings are also well supported by TCAD device simulations.

In Situ IR Spectroscopy Studies of Atomic Layer-Deposited SnO2 on Formamidinium-Based Lead Halide Perovskite.

Perovskite photovoltaics has achieved conversion efficiencies of 26.0% by optimizing the optoelectronic properties of the absorber and its interfaces with charge transport layers (CTLs). However, commonly adopted organic CTLs can lead to parasitic absorption and device instability. Therefore, metal oxides like atomic layer-deposited (ALD) SnO2 in combination with fullerene-based electron transport layers have been introduced to enhance mechanical and thermal stability. Instead, when ALD SnO2 is directly processed on the absorber, i.e., without the fullerene layer, chemical modifications of the inorganic fraction of the perovskite occur, compromising the device performance. This study focuses on the organic fraction, particularly the formamidinium cation (FA+), in a CsFAPb(I,Br)3 perovskite. By employing in situ infrared spectroscopy, we investigate the impact of ALD processing on the perovskite, such as vacuum level, temperature, and exposure to half and full ALD cycles using tetrakis(dimethylamido)-Sn(IV) (TDMA-Sn) and H2O. We observe that exposing the absorber to vacuum conditions or water half-cycles has a negligible effect on the chemistry of the perovskite. However, prolonged exposure at 100 °C for 90 min results in a loss of 0.7% of the total formamidinium-related vibrational features compared to the pristine perovskite. Supported by density functional theory calculations, we speculate that FA+ deprotonates and that formamidine desorbs from the perovskite surface. Furthermore, the interaction between TDMA-Sn and FA+ induces more decomposition of the perovskite surface compared to vacuum, temperature, or H2O exposure. During the exposure to 10 ALD half-cycles of TDMA-Sn, 4% of the total FA+-related infrared features are lost compared to the pristine perovskite. Additionally, IR spectroscopy suggests the formation and trapping of sym-triazine, i.e., a decomposition product of FA+. These studies enable to decouple the effects occurring during direct ALD processing on the perovskite and highlight the crucial role of the Sn precursor in affecting the perovskite surface chemistry and compromising the device performance.

Toolbox of Advanced Atomic Layer Deposition Processes for Tailoring Large-Area MoS2 Thin Films at 150 °C.

Two-dimensional MoS2 is a promising material for applications, including electronics and electrocatalysis. However, scalable methods capable of depositing MoS2 at low temperatures are scarce. Herein, we present a toolbox of advanced plasma-enhanced atomic layer deposition (ALD) processes, producing wafer-scale polycrystalline MoS2 films of accurately controlled thickness. Our ALD processes are based on two individually controlled plasma exposures, one optimized for deposition and the other for modification. In this way, film properties can be tailored toward different applications at a very low deposition temperature of 150 °C. For the modification step, either H2 or Ar plasma can be used to combat excess sulfur incorporation and crystallize the films. Using H2 plasma, a higher degree of crystallinity compared with other reported low-temperature processes is achieved. Applying H2 plasma steps periodically instead of every ALD cycle allows for control of the morphology and enables deposition of smooth, polycrystalline MoS2 films. Using an Ar plasma instead, more disordered MoS2 films are deposited, which show promise for the electrochemical hydrogen evolution reaction. For electronics, our processes enable control of the carrier density from 6 × 1016 to 2 × 1021 cm-3 with Hall mobilities up to 0.3 cm2 V-1 s-1. The process toolbox forms a basis for rational design of low-temperature transition metal dichalcogenide deposition processes compatible with a range of substrates and applications.

Optical Simulation-Aided Design and Engineering of Monolithic Perovskite/Silicon Tandem Solar Cells.

Monolithic perovskite/c-Si tandem solar cells have attracted enormous research attention and have achieved efficiencies above 30%. This work describes the development of monolithic tandem solar cells based on silicon heterojunction (SHJ) bottom- and perovskite top-cells and highlights light management techniques assisted by optical simulation. We first engineered (i)a-Si:H passivating layers for (100)-oriented flat c-Si surfaces and combined them with various (n)a-Si:H, (n)nc-Si:H, and (n)nc-SiOx:H interfacial layers for SHJ bottom-cells. In a symmetrical configuration, a long minority carrier lifetime of 16.9 ms was achieved when combining (i)a-Si:H bilayers with (n)nc-Si:H (extracted at the minority carrier density of 1015 cm-3). The perovskite sub-cell uses a photostable mixed-halide composition and surface passivation strategies to minimize energetic losses at charge-transport interfaces. This allows tandem efficiencies above 23% (a maximum of 24.6%) to be achieved using all three types of (n)-layers. Observations from experimentally prepared devices and optical simulations indicate that both (n)nc-SiOx:H and (n)nc-Si:H are promising for use in high-efficiency tandem solar cells. This is possible due to minimized reflection at the interfaces between the perovskite and SHJ sub-cells by optimized interference effects, demonstrating the applicability of such light management techniques to various tandem structures.

Surface Smoothing by Atomic Layer Deposition and Etching for the Fabrication of Nanodevices.

In many nano(opto)electronic devices, the roughness at surfaces and interfaces is of increasing importance, with roughness often contributing toward losses and defects, which can lead to device failure. Consequently, approaches that either limit roughness or smoothen surfaces are required to minimize surface roughness during fabrication. The atomic-scale processing techniques atomic layer deposition (ALD) and atomic layer etching (ALE) have experimentally been shown to smoothen surfaces, with the added benefit of offering uniform and conformal processing and precise thickness control. However, the mechanisms which drive smoothing during ALD and ALE have not been investigated in detail. In this work, smoothing of surfaces by ALD and ALE is studied using finite difference simulations that describe deposition/etching as a front propagating uniformly and perpendicular to the surface at every point. This uniform front propagation model was validated by performing ALD of amorphous Al2O3 using the TMA/O2 plasma. ALE from the TMA/SF6 plasma was also studied and resulted in faster smoothing than predicted by purely considering uniform front propagation. Correspondingly, it was found that for such an ALE process, a second mechanism contributes to the smoothing, hypothesized to be related to curvature-dependent surface fluorination. Individually, the atomic-scale processing techniques enable smoothing; however, ALD and ALE will need to be combined to achieve thin and smooth films, as is demonstrated and discussed in this work for multiple applications.

Atomic Layer Deposition of Large-Area Polycrystalline Transition Metal Dichalcogenides from 100 °C through Control of Plasma Chemistry.

Two-dimensional transition metal dichalcogenides, such as MoS2, are intensely studied for applications in electronics. However, the difficulty of depositing large-area films of sufficient quality under application-relevant conditions remains a major challenge. Herein, we demonstrate deposition of polycrystalline, wafer-scale MoS2, TiS2, and WS2 films of controlled thickness at record-low temperatures down to 100 °C using plasma-enhanced atomic layer deposition. We show that preventing excess sulfur incorporation from H2S-based plasma is the key to deposition of crystalline films, which can be achieved by adding H2 to the plasma feed gas. Film composition, crystallinity, growth, morphology, and electrical properties of MoS x films prepared within a broad range of deposition conditions have been systematically characterized. Film characteristics are correlated with results of field-effect transistors based on MoS2 films deposited at 100 °C. The capability to deposit MoS2 on poly(ethylene terephthalate) substrates showcases the potential of our process for flexible devices. Furthermore, the composition control achieved by tailoring plasma chemistry is relevant for all low-temperature plasma-enhanced deposition processes of metal chalcogenides.

Plasma-Enhanced Atomic Layer Deposition of HfO2 with Substrate Biasing: Thin Films for High-Reflective Mirrors.

Tuning ion energies in plasma-enhanced atomic layer deposition (PEALD) processes enables fine control over the material properties of functional coatings. The growth, structural, mechanical, and optical properties of HfO2 thin films are presented in detail toward photonic applications. The influence of the film thickness and bias value on the properties of HfO2 thin films deposited at 100 °C using tetrakis(dimethylamino)hafnium (TDMAH) and oxygen plasma using substrate biasing is systematically analyzed. The HfO2 films deposited without a substrate bias show an amorphous microstructure with a low density, low refractive index, high incorporation of residual hydroxyl (OH) content, and high residual tensile stress. The material properties of HfO2 films significantly improved at a low bias voltage due to the interaction with oxygen ions accelerated to the film. Such HfO2 films have a higher density, higher refractive index, and lower residual OH incorporation than films without bias. The mechanical stress becomes compressive depending on the bias values. Further increasing the ion energies by applying a larger substrate bias results in a decrease of the film density, refractive index, and a higher residual OH incorporation as well as crystalline inclusions. The comparable material properties of the HfO2 films have been reported using tris(dimethylamino)cyclopentadienyl hafnium (TDMACpH) in a different apparatus, indicating that this approach can be transferred to various systems and is highly versatile. Finally, the substrate biasing technique has been introduced to deposit stress-compensated, crack- and delamination-free high-reflective (HR) mirrors at 355 and 532 nm wavelengths using HfO2 and SiO2 as high and low refractive index materials, respectively. Such mirrors could not be obtained without the substrate biasing during the deposition because of the high tensile stress of HfO2, leading to cracks in thick multilayer systems. An HR mirror for 532 nm wavelength shows a high reflectance of 99.93%, a residual transmittance of ∼530 ppm, and a low absorption of ∼11 ppm, as well as low scattering losses of ∼4 ppm, high laser-induced damage threshold, low mechanical stress, and high environmental stability.

Relation between Reactive Surface Sites and Precursor Choice for Area-Selective Atomic Layer Deposition Using Small Molecule Inhibitors.

Implementation of vapor/phase dosing of small molecule inhibitors (SMIs) in advanced atomic layer deposition (ALD) cycles is currently being considered for bottom-up fabrication by area-selective ALD. When SMIs are used, it can be challenging to completely block precursor adsorption due to the inhibitor size and the relatively short vapor/phase exposures. Two strategies for precursor blocking are explored: (i) physically covering precursor adsorption sites, i.e., steric shielding, and (ii) eliminating precursor adsorption sites from the surface, i.e., chemical passivation. In this work, it is determined whether steric shielding is enough for effective precursor blocking during area-selective ALD or whether chemical passivation is required as well. At the same time, we address why some ALD precursors are more difficult to block than others. To this end, the blocking of the Al precursor molecules trimethylaluminum (TMA), dimethylaluminum isopropoxide (DMAI), and tris(dimethylamino)aluminum (TDMAA) was studied by using acetylacetone (Hacac) as inhibitor. It was found that DMAI and TDMAA are more easily blocked than TMA because they adsorb on the same surface sites as Hacac, while TMA is also reactive with other surface sites. This work shows that chemical passivation plays a crucial role for precursor blocking in concert with steric shielding. Moreover, the reactivity of the precursor with the surface groups on the non-growth area dictates the effectiveness of blocking precursor adsorption.

PO x /Al2O3 Stacks for c-Si Surface Passivation: Material and Interface Properties.

Phosphorus oxide (PO x ) capped by aluminum oxide (Al2O3) has recently been discovered to provide excellent surface passivation of crystalline silicon (c-Si). In this work, insights into the passivation mechanism of PO x /Al2O3 stacks are gained through a systematic study of the influence of deposition temperature (T dep = 100-300 °C) and annealing temperature (T ann = 200-500 °C) on the material and interface properties. It is found that employing lower deposition temperatures enables an improved passivation quality after annealing. Bulk composition, density, and optical properties vary only slightly with deposition temperature, but bonding configurations are found to be sensitive to temperature and correlated with the interface defect density (D it), which is reduced at lower deposition temperature. The fixed charge density (Q f) is in the range of + (3-9) × 1012 cm-2 and is not significantly altered by annealing, which indicates that the positively charged entities are generated during deposition. In contrast, D it decreases by 3 orders of magnitude (∼1013 to ∼1010 eV-1 cm-2) upon annealing. This excellent chemical passivation is found to be related to surface passivation provided by hydrogen, and mixing of aluminum into the PO x layer, leading to the formation of AlPO4 upon annealing.

On the Contact Optimization of ALD-Based MoS2 FETs: Correlation of Processing Conditions and Interface Chemistry with Device Electrical Performance.

Despite the extensive ongoing research on MoS2 field effect transistors (FETs), the key role of device processing conditions in the chemistry involved at the metal-to-MoS2 interface and their influence on the electrical performance are often overlooked. In addition, the majority of reports on MoS2 contacts are based on exfoliated MoS2, whereas synthetic films are even more susceptible to the changes made in device processing conditions. In this paper, working FETs with atomic layer deposition (ALD)-based MoS2 films and Ti/Au contacts are demonstrated, using current-voltage (I-V) characterization. In pursuit of optimizing the contacts, high-vacuum thermal annealing as well as O2/Ar plasma cleaning treatments are introduced, and their influence on the electrical performance is studied. The electrical findings are linked to the interface chemistry through X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM) analyses. XPS evaluation reveals that the concentration of organic residues on the MoS2 surface, as a result of resist usage during the device processing, is significant. Removal of these contaminations with O2/Ar plasma changes the MoS2 chemical state and enhances the MoS2 electrical properties. Based on the STEM analysis, the observed progress in the device electrical characteristics could also be associated with the formation of a continuous TiS x layer at the Ti-to-MoS2 interface. Scaling down the Ti interlayer thickness and replacing it with Cr is found to be beneficial as well, leading to further device performance advancements. Our findings are of value for attaining optimal contacts to synthetic MoS2 films.

Impact of Ions on Film Conformality and Crystallinity during Plasma-Assisted Atomic Layer Deposition of TiO2.

This work demonstrates that ions have a strong impact on the growth per cycle (GPC) and material properties during plasma-assisted atomic layer deposition (ALD) of TiO2 (titanium dioxide), even under mild plasma conditions with low-energy (<20 eV) ions. Using vertical trench nanostructures and microscopic cavity structures that locally block the flux of ions, it is observed that the impact of (low-energy) ions is an important factor for the TiO2 film conformality. Specifically, it is demonstrated that the GPC in terms of film thickness can increase by 20 to >200% under the influence of ions, which is correlated with an increase in film crystallinity and an associated strong reduction in the wet etch rate (in 30:1 buffered HF). The magnitude of the influence of ions is observed to depend on multiple parameters such as the deposition temperature, plasma exposure time, and ion energy, which may all be used to minimize or exploit this effect. For example, a relatively moderate influence of ions is observed at 200 °C when using short plasma steps and a grounded substrate, providing a low ion-energy dose of ∼1 eV nm-2 cycle-1, while a high effect is obtained when using extended plasma exposures or substrate biasing (∼100 eV nm-2 cycle-1). This work on TiO2 shows that detailed insight into the role of ions during plasma ALD is essential for precisely controlling the film conformality, material properties, and process reproducibility.

Oxygen Recombination Probability Data for Plasma-Assisted Atomic Layer Deposition of SiO2 and TiO2.

Atomic layer deposition (ALD) can provide nanometer-thin films with excellent conformality on demanding three-dimensional (3D) substrates. This also holds for plasma-assisted ALD, provided that the loss of reactive radicals through surface recombination is sufficiently low. In this work, we determine the surface recombination probability r of oxygen radicals during plasma ALD of SiO2 and TiO2 for substrate temperatures from 100 to ∼240 °C and plasma pressures from 12 to 130 mTorr (for SiO2). For both processes, the determined values of r are very low, i.e., ∼10-4 or lower, and decrease with temperature and pressure down to ∼10-5 within the studied ranges. Accordingly, deposition on trench structures with aspect ratios (ARs) of <200 is typically not significantly limited by recombination and obtaining excellent film conformality is relatively facile. For higher AR values, e.g., approaching 1000, the plasma time needed to reach saturation increases exponentially and becomes increasingly dependent on the process conditions and the corresponding value of r. Similar dependence on process conditions can be present for plasma ALD of other materials as well, where, in certain cases, film growth is already recombination-limited for AR values of ∼10. Radical recombination data and trends as provided by this work are valuable for optimizing plasma ALD throughput and feasibility for high-AR applications and can also serve as input for modeling of radical recombination mechanisms.

Atomic insights into the oxygen incorporation in atomic layer deposited conductive nitrides and its mitigation by energetic ions.

Oxygen is often detected as impurity in metal and metal nitride films prepared by atomic layer deposition (ALD) and its presence has profound and adverse effects on the material properties. In this work, we present the case study of HfNx films prepared by plasma-assisted ALD by alternating exposures of CpHf(NMe2)3 and H2 plasma. First, we identify the primary source of O contamination in the film. Specifically, we find that the extent of O incorporation in HfNx films is determined by the flux of background H2O/O2 residual gases reaching the HfNx surface during the ALD process and leads to the formation of Hf-O bonds. Then, we report on the decrease in the concentration of Hf-O bonds in the film upon application of an external radiofrequency (rf) substrate bias during the H2 plasma step. The experimental work is accompanied by first principles calculations to gain insights into the O incorporation and its mitigation upon the impingement of energetic ions on the surface. Specifically, we find that the dissociative binding of H2O on a bare HfN surface is highly favored, resulting in surface Hf-OH groups and concomitant increase in the oxidation state of Hf. We also show that energetic cations (H+, H2+ and H3+) lead to the dissociation of surface Hf-OH bonds, H2O formation, and its subsequent desorption from the surface. The latter is followed by reduction of the Hf oxidation state, presumably by H˙ radicals. The atomic-level understanding obtained in this work on O incorporation and its abstraction are expected to be crucial to prevent O impurities in the HfNx films and contribute to the fabrication of other technologically relevant low resistivity ALD-grown transition metal nitride films.

Electrochemical Activation of Atomic Layer-Deposited Cobalt Phosphate Electrocatalysts for Water Oxidation.

The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented. Atomic layer deposition (ALD) is adopted because it enables the synthesis of CoPi films with cobalt-to-phosphorous ratios between 1.4 and 1.9. It is shown that the pristine chemical composition of the CoPi film strongly influences its OER activity in the early stages of the activation process as well as after prolonged exposure to the electrolyte. The best performing CoPi catalyst, displaying a current density of 3.9 mA cm-2 at 1.8 V versus reversible hydrogen electrode and a Tafel slope of 155 mV/dec at pH 8.0, is selected for an in-depth study of the evolution of its electrochemical properties, chemical composition, and electrochemical active surface area (ECSA) during the activation process. Upon the increase of the number of CV cycles, the OER performance increases, in parallel with the development of a noncatalytic wave in the CV scan, which points out to the reversible oxidation of Co2+ species to Co3+ species. X-ray photoelectron spectroscopy and Rutherford backscattering measurements indicate that phosphorous progressively leaches out the CoPi film bulk upon prolonged exposure to the electrolyte. In parallel, the ECSA of the films increases by up to a factor of 40, depending on the initial stoichiometry. The ECSA of the activated CoPi films shows a universal linear correlation with the OER activity for the whole range of CoPi chemical composition. It can be concluded that the adoption of ALD in CoPi-based electrocatalysis enables, next to the well-established control over film growth and properties, to disclose the mechanisms behind the CoPi electrocatalyst activation.

Reaction Mechanisms during Atomic Layer Deposition of AlF3 Using Al(CH3)3 and SF6 Plasma.

Metal fluorides generally demonstrate a wide band gap and a low refractive index, and they are commonly employed in optics and optoelectronics. Recently, an SF6 plasma was introduced as a novel co-reactant for the atomic layer deposition (ALD) of metal fluorides. In this work, the reaction mechanisms underlying the ALD of fluorides using a fluorine-containing plasma are investigated, considering aluminum fluoride (AlF3) ALD from Al(CH3)3 and an SF6 plasma as a model system. Surface infrared spectroscopy studies indicated that Al(CH3)3 reacts with the surface in a ligand-exchange reaction by accepting F from the AlF3 film and forming CH3 surface groups. It was found that at low deposition temperatures Al(CH3)3 also reacts with HF surface species. These HF species are formed during the SF6 plasma exposure and were detected both at the surface and in the gas phase using infrared spectroscopy and quadrupole mass spectrometry (QMS), respectively. Furthermore, QMS and optical emission spectroscopy (OES) measurements showed that CH4 and CH y F4-y (y ≤ 3) species are the main reaction products during the SF6 plasma exposure. The CH4 release is explained by the reaction of CH3 ligands with HF, while CH y F4-y species originate from the interaction of the SF6 plasma with CH3 ligands. At high temperatures, a transition from AlF3 deposition to Al2O3 etching was observed using infrared spectroscopy. The obtained insights indicate a reaction pathway where F radicals from the SF6 plasma eliminate the CH3 ligands remaining after precursor dosing and where F radicals are simultaneously responsible for the fluorination reaction. The understanding of the reaction mechanisms during AlF3 growth can help in developing ALD processes for other metal fluorides using a fluorine-containing plasma as the co-reactant as well as atomic layer etching (ALE) processes involving surface fluorination.

Conformal Growth of Nanometer-Thick Transition Metal Dichalcogenide TiS x -NbS x Heterostructures over 3D Substrates by Atomic Layer Deposition: Implications for Device Fabrication.

The scalable and conformal synthesis of two-dimensional (2D) transition metal dichalcogenide (TMDC) heterostructures is a persisting challenge for their implementation in next-generation devices. In this work, we report the synthesis of nanometer-thick 2D TMDC heterostructures consisting of TiS x -NbS x on both planar and 3D structures using atomic layer deposition (ALD) at low temperatures (200-300 °C). To this end, a process was developed for the growth of 2D NbS x by thermal ALD using (tert-butylimido)-tris-(diethylamino)-niobium (TBTDEN) and H2S gas. This process complemented the TiS x thermal ALD process for the growth of 2D TiS x -NbS x heterostructures. Precise thickness control of the individual TMDC material layers was demonstrated by fabricating multilayer (5-layer) TiS x -NbS x heterostructures with independently varied layer thicknesses. The heterostructures were successfully deposited on large-area planar substrates as well as over a 3D nanowire array for demonstrating the scalability and conformality of the heterostructure growth process. The current study demonstrates the advantages of ALD for the scalable synthesis of 2D heterostructures conformally over a 3D substrate with precise thickness control of the individual material layers at low temperatures. This makes the application of 2D TMDC heterostructures for nanoelectronics promising in both BEOL and FEOL containing high-aspect-ratio 3D structures.

Nanoscale Encapsulation of Perovskite Nanocrystal Luminescent Films via Plasma-Enhanced SiO2 Atomic Layer Deposition.

Photoluminescence perovskite nanocrystals (NCs) have shown significant potential in optoelectronic applications in view of their narrow band emission with high photoluminescence quantum yields and color tunability. The main obstacle for practical applications is to obtain high durability against an external environment. In this work, a low temperature (50 °C) plasma-enhanced atomic layer deposition (PE-ALD) protection strategy was developed to stabilize CsPbBr3 NCs. Silica was employed as the encapsulation layer because of its excellent light transmission performance and water corrosion resistance. The growth mechanism of inorganic SiO2 via PE-ALD was investigated in detail. The Si precursor bis(diethylamino)silane (BDEAS) reacted with the hydroxyl groups (-OH) and thereby initiated the subsequent silica growth while having minimal influence to the organic ligands and did not cause PL quenching. Subsequently, O2 plasma with high reactivity was used to oxidize the amine ligands of the BDEAS precursor while did not etch the NCs. The obtained CsPbBr3 NCs/SiO2 film exhibited exceptional stability in water, light, and heat as compared to the pristine NC film. Based on this method, a white light-emitting diode with improved operational stability was successfully fabricated, which exhibited a wide color gamut (∼126% of the National Television Standard Committee). Our work successfully demonstrates an efficient protection scheme via the PE-ALD method, which extends the applied range of other materials for stabilization of perovskite NCs through this approach.