Atomic Layer Deposition Al2O3 Research Articles

Electrochemical characterization of localized corrosion mechanism of ALD Al2O3-coated copper for microelectronic application

To achieve performance and reliability in microelectronics devices, copper interconnections must be protected from aggressive environment during the manufacturing process and throughout the life of the devices. Atomic Layer Deposition Al2O3 thin films has been used as a compatible layer with key integration process steps, as well as being corrosion-resistant in neutral media. However, electrochemical tests in aggressive environment have revealed that the alumina prematurely failed to protect copper from localized corrosion. In this study, local and global electrochemical techniques have been employed to evaluate the reactivity of copper at multiple scales and to elucidate the underlying corrosion mechanisms.

Impact of channel thickness on device scaling in vertical InGaZnO channel charge-trap memory transistors with ALD Al2O3 tunneling layer

This study investigates the impact of channel thickness (TCH) variation on memory performance and its physical origins in vertical channel charge trap memory (V-CTM) using InGaZnO (IGZO) channels for X–Y scaling. When the TCH decreased, the subthreshold slope (SS) increased from 0.21 to 0.30 V/dec, while the minimum program voltage decreased from 12 to 8 V, indicating a performance trade-off. The analysis of bulk trap density extracted by SS, density of states distribution, and x-ray photoelectron spectroscopy confirmed an increase in the number of trap states and hydrogen-related defects in the IGZO channel when a thin TCH is employed. As a result, it was expected that the barrier height at the active layer/TL would be lowered during program operations at relatively thin channel. However, the SS would also be degraded due to an increase in sub-gap states, such as OH- and VOH, induced by hydrogen incorporation. The V-CTM with an optimal TCH of 7 nm had a maximum memory window of 5.7 V. The program/erase states were maintained for 106 s before experiencing a 50 % charge loss, and 5-level memory states were verified to be available within a memory window of 3.2 V for 108 s with little degradation. It was noteworthy that the long-term reliability and multilevel implementation could be secured for the V-CTM with a TCH as thin as 7 nm, demonstrating the sound feasibility of its X–Y scaling. This work presents new key parameters and understanding of device integration issues for future 3D structured memory transistors, and aims to contribute to the advancement of memory technologies using oxide semiconductor channels.

Optimizing the quality factor of InP nanobeam cavities using atomic layer deposition

Photonic crystal nanobeam cavities are valued for their small mode volume, CMOS compatibility, and high coupling efficiency-crucial features for various low-power photonic applications and quantum information processing. However, despite their potential, nanobeam cavities often suffer from low quality factors due to fabrication imperfections that create surface states and optical absorption. In this work, we demonstrate InP nanobeam cavities with up to 140% higher quality factors by applying a coating of Al2O3 via atomic layer deposition to terminate dangling bonds and reduce surface absorption. Additionally, changing the deposition thickness allows precise tuning of the cavity mode wavelength without compromising the quality factor. This Al2O3 atomic layer deposition approach holds great promise for optimizing nanobeam cavities that are well-suited for integration with a wide range of photonic applications.

Low‐Temperature Dual‐Material Area‐Selective Deposition: Molybdenum Hexafluoride‐Mediated SiO2 Fluorination/Passivation for Self‐Aligned Molybdenum/Metal Oxide Nanoribbons

AbstractArea‐selective deposition (ASD) is a forefront nanopatterning technique gaining substantial attention in the semiconductor industry. While current research primarily addresses single‐material ASD, exploring multi‐material ASD is essential for mitigating complexity in advanced nanopatterning. This study describes molybdenum hexafluoride (MoF6)‐mediated fluorination/passivation of the hydroxylated SiO2 (SiO2‒OH) at 250 °C as a new method to pacify nucleation during subsequent ZnO and TiO2 atomic layer deposition (ALD). In contrast, Al2O3 ALD is not passivated on the fluorinated SiO2 (SiO2‒F). The study further shows that Mo ALD using MoF6 and silane (1 wt% SiH4 in Ar) selectively proceeds on hydrogen‐terminated Si (Si‒H), whereas SiO2‒OH becomes fluorine‐passivated without observable Mo deposition. This enables subsequent ZnO and TiO2 ASD on Mo versus SiO2‒F, as confirmed by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). Proposed growth and inhibition mechanisms highlight the importance of the metal oxide precursor in achieving selectivity. Taken together, self‐aligned Mo/ZnO and Mo/TiO2 nanoribbons are demonstrated on coplanar nanoscale Si‒H/SiO2‒OH patterns by sequentially integrating two individual ASD processes: 1) Mo ASD on Si‒H versus SiO2‒OH; and 2) ZnO or TiO2 ASD on Mo versus SiO2‒F. This work highlights the potential for this approach in new ASD systems.

Enhanced cyclability of lithium-ion batteries resulting from atomic layer deposition of Al2O3 on LiFePO4 electrodes

Enhanced cyclability of lithium-ion batteries resulting from atomic layer deposition of Al2O3 on LiFePO4 electrodes

Effect of the number and distribution of Al2O3 atomic layer deposition cycles within HfO2 layer on ferroelectric characteristics

We comprehensively analyze the effects of the number and distribution of Al2O3 atomic layer deposition (ALD) cycles into a 10-nm-thick HfO2 matrix on the ferroelectric switching behavior. An ALD cycle containing one pulse for Hf (or Al) precursor and one pulse of water as reactant is repeated 150 times for the given thickness of 10 nm. Spontaneous remnant polarization (Pr) is enabled through the formation of crystalline Al-doped HfO2 (Al:HfO2) by incorporating at least two Al2O3 ALD cycles evenly into the HfO2 film under annealing at 600 °C for 3 min following W top electrode (TE) deposition. When more than four Al2O3 cycles are used, the Al elements function as leakage sources rather than stressors, resulting in an open hysteresis loop and a weak endurance of 105 cycles. Notably, an improved 2 Pr of ∼9 μC/cm2 is achieved when the Al2O3 layers are concentrated near the lower region of the HfO2. On the other hand, as the Al2O3 layers are intensively located in the upper region of the HfO2, a dielectric response is observed in the polarization–voltage and current–voltage measurements. Our results indicate that the two mechanical stresses induced by the Al dopant with a size smaller than Hf and the difference in the thermal expansion coefficient between TE and Al:HfO2 effectively activate both the lower and upper sites. Therefore, many dipoles are observed to participate in the polarization owing to the stresses that are applied evenly throughout the Al:HfO2 layer to form the orthorhombic phase.

Grain boundary complexion modification for interface stability in garnet based solid-state Li batteries

The garnet type solid-state electrolyte (SSE) encounters challenges related to poor interfacial contact with Li metal and dendrite penetration problem. This study addresses these issues by manipulating the surface property of garnet-based LLZTO (Li6.5La3Zr1.6Ta0.4O12) SSE. The manipulation is achieved by varying thickness of Al2O3 atomic layer deposition (ALD), followed by sintering. Research results show that the relative density, ionic conductivity, and hardness of LLZTO are improved while electronic conductivity is reduced due to the formation of multiple complexions at grain boundary (GB). The SSE pellets also demonstrate improved wettability with Li metal, leading to stable galvanostatic Li plating/stripping cycling with low polarization, which allows for batter battery performance than pristine one. The concept of modifying SSE through the grain boundary complexion modification by thin ALD coating for enhancing the dendrite tolerance with better electrochemical properties of SSE may open a new direction for solid state battery research.

Reducing contact resistance of MoS2-based field effect transistors through uniform interlayer insertion via atomic layer deposition.

Molybdenum disulfide (MoS2), a semiconducting two-dimensional layered transition metal dichalcogenide (2D TMDC), with attractive properties enables the opening of a new electronics era beyond Si. However, the notoriously high contact resistance (RC) regardless of the electrode metal has been a major challenge in the practical applications of MoS2-based electronics. Moreover, it is difficult to lower RC because the conventional doping technique is unsuitable for MoS2 due to its ultrathin nature. Therefore, the metal-insulator-semiconductor (MIS) architecture has been proposed as a method to fabricate a reliable and stable contact with low RC. Herein, we introduce a strategy to fabricate MIS contact based on atomic layer deposition (ALD) to dramatically reduce the RC of single-layer MoS2 field effect transistors (FETs). We utilize ALD Al2O3 as an interlayer for the MIS contact of bottom-gated MoS2 FETs. Based on the Langmuir isotherm, the uniformity of ALD Al2O3 films on MoS2 can be increased by modulating the precursor injection pressures even at low temperatures of 150 °C. We discovered, for the first time, that film uniformity critically affects RC without altering the film thickness. Additionally, we can add functionality to the uniform interlayer by adopting isopropyl alcohol (IPA) as an oxidant. Tunneling resistance across the MIS contact is lowered by n-type doping of MoS2 induced by IPA as the oxidant in the ALD process. Through a highly uniform interlayer combined with strong doping, the contact resistance is improved by more than two orders of magnitude compared to that of other MoS2 FETs fabricated in this study.

Formation of oxygen vacancy at surfaces of ZnO by trimethylaluminum

The two-dimensional electron gas (2DEG) is a group of electrons that can move freely in horizontal dimensions but are confined in the third direction. It has been reported that atomic layer deposition (ALD) of Al2O3 on various reducible n-type oxides can lead to the formation of 2DEG at the heterojunction interfaces, among which ZnO is known to provide promising properties. In this study, we have performed a theoretical analysis using density functional theory calculations combined with experimental investigations to elucidate the surface reactions of Al2O3 ALD on low-index nonpolar ZnO surfaces, specifically focusing on the formation of oxygen vacancies (VO). The trimethylaluminum precursor was observed to undergo sequential dissociation of CH3 ligands, leading to the removal of surface oxygen of ZnO in the form of dimethyl ether. In addition, by examining the electronic structure after the removal of oxygen, the localization of the charge density at the surface was confirmed. Experimentally, the carrier density of the 2DEG at the Al2O3/ZnO interface showed a strong dependence on the ALD process temperature of Al2O3, confirming the endothermic nature of the formation of the 2DEG. By examining the characteristics of the 2DEG induced by VO, insights into the fundamental comprehension of oxide-based 2DEG systems are provided.

Effect of hydrogen on the chemical state, stoichiometry and density of amorphous Al2O3 films grown by thermal atomic layer deposition

Amorphous oxide thin films grown by thermal atomic layer deposition (ALD) typically contain high impurity concentrations of hydrogen, which affects both chemistry and structure and thereby the functional properties, such as the barrier properties in, for example, microelectronic and photovoltaic devices. This study discloses the effect of H incorporation in amorphous Al2O3 ALD oxide films on the local chemical binding states of Al, O and H, as well as the oxide density and stoichiometry, by a combined analytical approach using elastic recoil detection analysis, Rutherford backscattering spectroscopy and full chemical state analysis by dual‐source X‐ray photoelectron spectroscopy (XPS)/hard X‐ray photoelectron spectroscopy (HAXPES). The experimental findings are compared with crystalline anhydrous α‐Al2O3 and hydroxide α‐Al (OH)3 reference phases and further supported by molecular dynamic simulations. It is shown that H preferably forms covalent –OH hydroxyl bonds with O in the nearest‐neighbour coordination spheres of interstitial Al cations, which affects both the ligand electronic polarizability and the bond length of the randomly interconnected [AlOn] polyhedral building blocks in the amorphous ALD oxide films.

Prolonging the Cycle Stability of Anion Redox P3-Type Na0.6Li0.2Mn0.8O2 through Al2O3 Atomic Layer Deposition Surface Modification.

Sodium-ion batteries (SIBs) are becoming an alternative option for large-scale energy storage systems owing to their low cost and abundance. The lattice oxygen redox (LOR), which has the potential to increase the reversible capacity of materials, has promoted the development of high-energy cathode materials in SIBs. However, the utilization of oxygen anion redox reactions usually results in harmful lattice oxygen release, which hastens structural deformation and declines electrochemical performance, severely hindering their practical application. Herein, a ribbon-ordered superstructured P3-type Na0.6Li0.2Mn0.8O2 (NLMO) cathode with a uniform Al2O3 coating through atomic layer deposition (ALD) was synthesized. The cycling stability and rate capability of the materials were improved by a proper thickness of the Al2O3 layer. Differential electrochemical mass spectrometry (DEMS) results clearly suggest that the Al2O3 coating can inhibit the CO2 release caused by the highly active surface of the NLMO material. Moreover, the results of transmission electron microscopy (TEM) and etching X-ray photoelectron spectroscopy (XPS) show that the Al2O3 coating can effectively prevent electrolyte and electrode side reactions and the dissolution of Mn. This surface engineering strategy sheds light on the way to prolong the cycling stability of anionic redox cathode materials.

Influence of Al2O3 atomic-layer deposition temperature on positive-bias instability of metal/Al2O3/β-Ga2O3 capacitors

The influence of Al2O3 atomic-layer deposition (ALD) temperature on the electric characteristics of Al/Al2O3/(2¯01) β-Ga2O3 capacitors was investigated focusing on the positive-bias instability (PBI) of the capacitors. The current in the capacitors increased with ALD temperature, mostly because of the reduced energy barrier height for the electron field emission from the substrate and less negative Al2O3 charge, as revealed by the analysis conducted assuming a space-charge-controlled field emission process. The PBI tests were conducted for cumulative voltage stressing times vastly ranging from 3 × 10−6 to 4 × 105 s. The capacitance–voltage (C–V) characteristics of the capacitors for an ALD temperature of 100 °C displayed negative shifts in the middle of voltage stressing, unlike those for the other ALD temperatures. The bias stability of the capacitors was found to be considerably improved by high-temperature (450 °C) ALD. Additionally, the C–V characteristic shifts caused by the voltage stressing were theoretically reproduced quite accurately, assuming a model proposed in this study. In the simulations, the trap distributions in the Al2O3 films were assumed to be uniform both spatially and energetically. Importantly, the experimental results for various stressing voltages were excellently fitted by the simulations that assumed the same trap distribution. The trap densities in the Al2O3 films thus estimated reduced from 1.2 × 1020 to 2.2 × 1019 cm−3 eV−1 for ALD temperatures of 100–450 °C. This reduction in the trap densities was a major cause of the bias stability enhancement for high-temperature ALD. Moreover, the trap density as a function of ALD temperature qualitatively agreed with the aforementioned Al2O3 charge generated by the current measurements. This agreement provides a strong basis for the validity of the PBI model proposed in this study.

(Invited) Small Molecule Inhibitor-Based Approaches for Area-Selective Deposition from First Principles

Atomic layer deposition tackles ever new research questions. Area-selective deposition is one of these recent challenges. Several approaches have been developed to achieve selectivity. One of the most promising is using comparatively small molecules to block the non-growth surface while leaving the growth surface uncovered for the ALD process.This approach requires in-depth knowledge of the surface chemistry of both surfaces involved. In addition, the decomposition pathways of SMI-covered surfaces need to be uncovered to enable stable ALD growth over a maximum number of cycles.These questions are very challenging for lab-based investigations. We present recent progress in the ab initio description of key questions regarding SMI-based ALD processes. At the example of silanol-based SMIs, surface chemistry for Al2O3 growth on Cu while blocking SiO2 will be discussed and compared to experimental findings.[1] Furthermore, the importance of choosing the appropriate surface model will be highlighted. Especially for the challenging question of SMI-layer decomposition.[1 J. Yarbrough, F. Pieck, D. Grigjanis, I.-K. Oh, P. Maue, R. Tonner-Zech, S. F. Bent, "Tuning Molecular Inhibitors and Aluminum Precursors for the Area-Selective Atomic Layer Deposition of Al2O3", Chem. Mater. 2022, 34, 4646-4659.We gratefully acknowledge funding from a Merck KGaA, Darmstadt, Germany 350th Anniversary Research Award. Computations were performed on the CSC Frankfurt, HLR Stuttgart, ZIH Dresden and HPC Regensburg.Figure 1 General structure (a) of the studied SMIs with different reactive and blocking groups (b). Schematic structures of the calculated condensation reactions of the SMIs with OH groups of the SiO2 surface (c). Color code: Si (blue), O (red), and H (white). Figure 1

Atomic Layer Deposition of HfAlOx for High-k Gate Dielectrics

Nowadays, the downscaling of CMOS devices requires continued effort to propose high performance components with extremely compact size. Surely, this trend is not achievable without extremely enhanced High-k gate stack materials, inter alia. For years, HfO2-based dielectrics deposited using ALD (Atomic Layer Deposition) technique are perfect dielectrics of choice for various devices and applications (Memristor, resistive random access memory, ferroelectric random access memory, antiferrolectric capacitances, ferroelectric FET...).As such, HfAlOx films present a good compromise between HfO2 and Al2O3 in term of coupling properties and insulating capabilities in comparison with both single HfO2 and Al2O3 films. The purpose of this work is to evaluate binary high-k HfAlOx dielectrics deposited by ALD technique. ALD is well suited for deposition of ultrathin films with exceptional capabilities enabling precise thickness, stoichiometry control and conformal growth at atomic scale. In this work, we focused on Al2O3/HfO2 films fabricated using two approaches: (i) repeatedly alternating the deposition of two different and separate extremely thin oxides (Al2O3 and HfO2; particular focus on HfO2/Al2O3/HfO2/Al2O3/HfO2 multilayer stack with equivalent Al fraction around 30%); (ii) combination of ALD super cycles allowing the formation HfAlOx layers. We analyze the general performance and the behavior of the binary high-k HfAlOx dielectrics (10 nm thin layers deposited at 300°C using TiCl4-TMA-H2O precursors) using physico-chemical (X-ray photoelectron spectroscopy XPS, X-ray reflectometry XRR, wavelength dispersive X-ray fluorescence WDXRF) and electrical measurements (Hg probe measurements, MIM capacitance).The incorporation of Al2O3 in the composition of the HfO2 gate dielectrics allows a perfect monitoring of physico-chemical properties varying from HfO2 layers to Al2O3 layers by controlling the number of Al2O3 and HfO2 ALD cycles. In this respect, we were able to monitor the Al fraction in the range of 5% to ~86% in the mixed binary dielectrics (Figure 1: XRR density of mixed binary layers vs Al/[Al+Hf] ratio, Figure 2: Al and Hf fractions in the mixed layer determined by WDXRF and XPS analysis).The electrical characteristics of the HfAlOx dielectrics confirm the influence of the Al fraction in the HfO2 layer. The leakage currents of the mixed layers decreases with increasing the Al fraction (Figure 3: J/E characteristics of mixed and stacked HfAlOx layers). The breakdown voltages for all mixed HfAlOx layers are greater than that of reference HfO2 layer. On the other hand, the shown multilayer presents an intermediate leakage currents profiles between the two mixed HfAlOx (25%Al and 40%Al). Thus, the incorporation of Al in the construction of HfAlOx system is likely to decrease the number of defects. Furthermore, the fully integrated MIM structures exhibit areal capacitance in the range 10-15 nF/mm2 of ALD-based high-k HfAlOx (10 to 12 nm) depending on the Al fraction. Thus, ALD-HfAlOx with various composition highlight the potential tremendous for high-κ capacitances stack for CMOS semiconductor devices. Figure 1

New ALD ZnO Precursors and Processes for Protective Coatings on Lithium-Ion Battery Cathodes

The ever-increasing demand for Li-ion batteries commands their performance to increase while at the same time size and mass to decrease. One promising cathode material to achieve this is the Ni-rich LiNi0.8Mn0.1Co0.1, (NMC811), a high-capacity layered oxide cathode material. However, NMC811 suffers from capacity fading during electrochemical cycling of the cells. This phenomenon is connected to the dissolution of the active transition metal ions in the cathodes, phase changes and to side reactions happening at the interface of the cathode and the electrolyte or with formed HF but remains poorly understood.[1] To mitigate these problems, many different coating processes have been employed. In the realm of atomic layer deposition (ALD), the predominant coating material is the very stable insulating Al2O3 prepared from trimethyl aluminum and H2O. However, ZnO is an alternative transition metal oxide coating that shows promise since it is an amphoteric conductor. Recently, amorphous ZnO coatings prepared by sol-gel methods were shown to significantly boost the capacity retention of NMC cathodes.[2] Taking inspiration from a recent study that compared different ALD Al2O3 precursors and their ability to precisely tune the protective coating, we set out to investigate the suitability of ZnO ALD films as protective coatings and the influence of different precursors used for that purpose.[3] We selected four Zn precursors for cathode surface treatments in this study with different coordination motifs, metal-to-ligand bonds and reactivities, (Fig. 1). The ZnO ALD processes for these precursors were established by in-situ spectroscopic ellipsometry, and the resulting films were subjected to compositional analysis by XPS and RBS/NRA proving high purity ZnO. Further, UV-VIS measurements were conducted to investigate the band gaps of the materials which showed interesting precursor dependent differences. To analyze the growth behavior of the different precursors, in-situ FTIR studies were conducted hinting at distinct decomposition/deposition behavior of each precursor, as shown by the FTIR difference spectra for ZnEt(HMDS) in Fig. 2. The in-situFTIR studies also revealed different nucleation behaviors for the ALD ZnO precursors on the NMC811 cathode surface. Next, we coated NMC811 powder with 1 and 5 ZnO ALD cycles and performed XPS to verify successful ZnO ALD, analyze the surface species, and probe for potential oxidation state changes caused by the applied precursors. Whereas the observed changes in the oxidation states were small, a reproducible reduction was seen for the Ni, Co, and Mn transition metals in the cathode material, see exemplarily the ratio of Co 2+ and 3+ species in Fig. 3. Coin cell cycling tests of cathodes fabricated from the ALD ZnO-coated NMC811 powders prepared using the different Zn precursors are ongoing. These results will be especially noteworthy and showcase how the choice of ALD precursor influences the properties of a battery protective coating and allows fine tuning of the cathode surface properties.[1] Z. Ruff, C. Xu, C. P. Grey, J. Electrochem. Soc. 2021, 168, 060518.[2] Y. Li, X. Li, J. Hu, W. Liu, H. Maleki Kheimeh Sari, D. Li, Q. Sun, L. Kou, Z. Tian, L. Shao, C. Zhang, J. Zhang, X. Sun, Energy Environ. Mater. 2020, 3, 522–528.[3] D. Kang, R. E. Warburton, A. U. Mane, J. Greeley, J. W. Elam, Applied Surface Science 2022, 599, 153329. Figure 1

Analyzing the Li-Al-O Interphase of Atomic Layer-Deposited Al2O3 Films on Layered Oxide Cathodes Using Atomistic Simulations.

Alumina surface coatings are commonly applied to layered oxide cathode particles for lithium-ion battery applications. Atomic layer deposition (ALD) is one such surface coating technique, and ultrathin alumina ALD films (<2 nm) are shown to improve the electrochemical performance of LiNixMnyCo1-x-yO2 materials, with groups hypothesizing that a beneficial Li-Al-O product is being formed during the alumina ALD process. However, the atomic structure of these films is still not well understood, and quantifying the interface of ultrathin (∼1 nm) ALD films is an arduous experimental task. Here, we perform molecular dynamics simulations of amorphous alumina films of varying thickness in contact with the (0001) LiCoO2 (LCO) surface to quantify the film nanostructure. We calculate elemental mass density profiles through the films and observe that the Li-Al-O interphase extends ∼2 nm from the LCO surface. Additionally, we observe layering of Al and O atoms at the LCO-film interface that extends for ∼1.5 nm. To access the short-range order of the amorphous film, we calculated the Al coordination numbers through the film. We find that while [4]Al is the prevailing coordination environment, significant amounts of [6]Al exist at the interface between the LiCoO2 surface and the film. Taken together, these principal findings point to a pseudomorphic Li-Al-O overlayer that approximates the underlying layered LiCoO2 lattice but does not exactly replicate it. Additionally, with sufficient thickness, the Li-Al-O film transitions to an amorphous alumina structure. We anticipate that our findings on the ALD-like, Li-Al-O film nanostructure can be applied to other layered LiNixMnyCo1-x-yO2 materials because of their shared crystal structure with LiCoO2. This work provides insight into the nanostructure of amorphous ALD alumina films to help inform their use as protective coatings for Li-ion battery cathode active materials.

Impact of Al2O3 spacers on the improvement in short-channel effects for the mesa-shaped vertical-channel In-Ga-Zn-O thin-film transistors with a channel length below 100 nm

To achieve a channel length scaling and an improvement in short-channel effect (SCE) for the mesa-shaped vertical thin-film transistors (VTFTs) using In-Ga-Zn-O (IGZO) channels prepared by atomic layer deposition (ALD), the impacts of two strategic approaches were investigated: the introduction of an ALD Al2O3 spacer and the modulation of ALD oxidants. The Al2O3 spacers were patterned with sound profiles by means of a hybrid-etching technique combining a wet- and plasma dry-etching processes to form vertical sidewalls corresponding to a channel length. For the cases when the Al2O3 spacers were prepared with H2O oxidant, the IGZO VTFT with an In/Ga ratio of 1.7 showed the degradations in device characteristics including a turn-on voltage (VON) of −8.0 V and a subthreshold swing (SS) of 1.50 V/dec. When the In/Ga ratio was increased to 2.9, the device failed to be operated with conductive properties. The excess hydrogen contained within the Al2O3 spacer was suggested to be thermally diffused into the IGZO from the back-channel interface, leading to marked increase in the number of conduction carriers within the channel. To suppress the doping effect of hydrogen from the spacer, the ALD oxidant was strategically modulated to O3. As results, the VON and SS of the IGZO VTFT were markedly improved to be −2.0 V and 0.483 V/dec, respectively. Additionally, the drain induced barrier lowering coefficient was also significantly enhanced from 2.9 to 0.13 V/V, demonstrating the excellent immunity against the SCE for the IGZO VTFTs with nanoscale channel lengths. It was concluded from these findings that the spacer engineering can be one of the most important guides for the implementation of IGZO VTFTs with channel lengths below 100 nm.

&lt;i&gt;In Situ&lt;/i&gt; ALD-TEM System to Study Atomic Nucleation Phenomena - Enabled by Ultrathin Large Aspect Ratio Free-Standing Shell Structures

Today, Atomic Layer Deposition (ALD) sets the limits for achieving nanometer precision of thin, yet almost dense films. However, the initial growth process, determining possible film thinness, is poorly understood. A better understanding can be obtained with the help of in-situ characterization during film growth with high spatial and chemical resolution. Transmission Electron microscopy (TEM) would be a suitable and widely available technique to accomplish this objective. However, standard instruments have differing vacuum requirements than those necessary for ALD. During ALD, TEM detectors could be damaged as they are being exposed to corrosive volatile chemical compounds. Here we present a dedicated TEM holder design, where ALD deposition occurs inside a microchip containing a large area cavity surrounded by thin film Al2O3 membranes. These membranes act as windows for TEM characterization while decoupling the ALD process from the TEM environment. The microchip consists of longitudinal large overhang shell structures, themselves made by ALD and etched in an HF vapor etch processes. The set-up, which includes controlled heating, was tailored to ALD requirements, and passed a vacuum-pressure test. Post-mortem inspection of film growth on a silicon sample chip demonstrates the successful formation of an ALD Al2O3 film with 40 nm thickness inside the cavity. These results demonstrate the potential of the system to enable a range of experiments on growth phenomena that may lead to even thinner films and better control of interfaces than previously possible.

Stability of industrial gallium-doped Czochralski silicon PERC cells and wafers

The carrier lifetime stability of gallium-doped silicon wafers and performance stability of industrial PERC solar cells produced from sister wafers were investigated under four different illumination conditions and temperatures. The seven investigated materials feature a resistivity variation of 0.4–1.0 Ωcm and lifetime samples were processed to create high hydrogen content (with PECVD SiNx) or low hydrogen content (with ALD Al2O3 or HfO2). Our results confirm that the material itself is prone to light and elevated temperature induced degradation (LeTID), however experiments on PERC cells produced utilising the same silicon material indicate that the production process can successfully suppress LeTID. In contrast to earlier studies, we observe only small levels of degradation at the cell level, with some showing an improvement in cell parameters under LeTID testing conditions. Our results indicate that LeTID is not necessarily a major issue for the performance of modern passivated emitter and rear cells made from gallium-doped silicon substrates.

Al2O3 atomic layer deposition on a porous matrix of carbon fibers (FiberForm) for oxidation resistance

Atomic layer deposition (ALD) was used to coat a porous matrix of carbon fibers known as FiberForm with Al2O3 to improve oxidation resistance. Static trimethylaluminum (TMA) and H2O exposures for Al2O3 ALD were used to obtain the uniform coating of this high porosity material. The carbon surfaces were initially functionalized for Al2O3 ALD by exposure to sequential exposures of nitrogen dioxide and TMA. A gravimetric model was developed to predict the mass gain per cycle under conditions when the ALD reactions reached saturation during each reactant exposure. The uniformity of the Al2O3 ALD coating on FiberForm was confirmed by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) analysis. The SEM, EDS, and gravimetric models were all consistent with a uniform Al2O3 ALD coating on the porous carbon fiber network when the ALD reactions reached saturation on the entire surface area. In contrast, the profile of the Al2O3 ALD coating on the FiberForm was also characterized using undersaturation conditions when the ALD reactions did not reach saturation throughout the FiberForm sample. Based on comparisons with results from models for ALD in porous substrates, these Al2O3 coverage profiles were consistent with diffusion-limited Al2O3 ALD. Oxidation of the FiberForm and the Al2O3 ALD-coated FiberForm was also investigated by thermogravimetric analysis (TGA). TGA revealed that a 50 nm thick Al2O3 coating deposited using 400 Al2O3 ALD cycles enhanced the oxidation resistance. The Al2O3 ALD coating increased the oxidation onset temperature by ∼200 °C from 500 to 700 °C. The oxidation of the FiberForm removed carbon and left the Al2O3 ALD coating behind as a white “skeleton” that preserved the shape of the original FiberForm sample. The Al2O3 ALD coating also decreased the oxidation rate of the FiberForm by ∼30%. The oxidation rate of the Al2O3 ALD-coated FiberForm samples was constant and independent of the thickness of the Al2O3 ALD coating. This behavior suggested that the oxidation is dependent on the competing O2 diffusion into the FiberForm and CO2 diffusion out of the FiberForm.