VO₂ films are known to undergo a metal-insulator phase transition (MIT) at a critical temperature (T_c = 68°C) near room temperature which results in significant changes in thermal emittance, optical transmittance and reflectance, and intrinsic electrical properties; thus attracting interest in a variety of new electronic, optoelectronic, and photonic applications. Atomic layer deposition (ALD) provides a way to obtain large area film uniformity, abrupt interfaces and angstrom-scale control of thickness conformally across planar, as well as three-dimensional, high surface area nanostructures, which could be used to integrate VO₂ films into complex electronic and optical devices for additional functionality. In this work, VO₂ electrical devices and VO₂ coated SiC-based nanoresonantors are used to investigate the impact of film thickness on electrical and optical properties.

The influence of VO₂ thickness on electrical performance was investigated using a simple two-terminal device structure. Sheet resistance measurements as a function of temperature revealed that the R_off/R_on ratio increased with increasing VO₂ thickness, up to R_off/R_on of ~7000 for a 92 nm film. Similarly, the T_c increased slightly with increasing thickness (T_c = 66^oC for 35nm, 73^oC for 92nm), while all films show relatively low hysteresis (ΔT<8^oC). Initial small-signal rf measurements using the 92 nm ALD VO₂ film demonstrated a cut-off frequency of greater than 1 THz, indicating the potential for rf-switch applications into millimeter wavelength frequencies using these ultra-thin ALD films, and the potential of these films to be conformally integrated into complex circuits with an ALD process.

For applications in the infrared, surface phonon-polariton-based SiC nanoresonators exhibiting strong, narrowband absorption features within the 10-12.5 μm range were coated with different thickness ALD VO₂ films. Since these films are transparent to infrared light below the Tc and reflective above the Tc, conformally coating these SiC nanostructures provides a way to add functionality to these structures by modulating the amplitude of the resonances with temperature. Initial results show that the magnitude of the resonance suppression increases with increasing VO₂ thickness and a VO₂ film thickness greater than 16nm is required to fully inhibit the signal. It was also determined that the SiC resonances become increasingly shifted and broadened with increasing thickness of the VO₂ coating. These results suggest that VO₂ can add active tunability and integrated switching to optical structures.

Graphene has emerged as one of the promising candidates for post-Si electronics, both for channel (Logic, RF, sensors) and interconnect applications. Further, other two-dimensional (2D) materials such as transition metal dichalcogenides (MX2, with M a transition metal of group 4–7 and X a chalcogen) have versatile properties that complement or even supersede those of graphene. Both categories however share similar problems, related to the absence of good quality synthesis processes, subsequent layer transfer processes and doping and contacting challenges. To tackle the first challenge – growth – chemical vapor deposition (CVD) is widely considered to be the most economically viable method to produce both graphene and MX2 materials for high-end applications. However, in most cases, this deposition technique typically yields undesired grain boundaries in the 2D crystals, which drastically increases the sheet resistance of the layer. Strategies w.r.t. template and process development will be presented. Further, given growth temperature and template, direct growth on devices is often unfeasible, thus a second challenge relates to the requirement for a transfer process. For graphene, several transfer process possibilities have been evaluated, but up to now, the graphene transfer suffers from contamination often coming from the temporary support layer and/or etching products, wrinkle formation during bonding, crack formation during graphene handling, ... Moreover, with improvement in 2D quality the release from the growth template is hindered due to increased adhesion forces. At least for MX2 materials, the transfer challenge can be avoided through area selective growth. A process based on a reductive two step CVD process will be presented, whereby in a first step the metal precursor (WF6) is reduced to a lower oxidation state through sacrificial reaction with Si. Subsequently, the metallic film is allowed to react with a sulphur precursor (H2S). Challenges are again related to the (poly)crystallinity of the films and the control of lateral 2D versus crystal 3D growth. Last but not least, a third challenge related to 2D materials resides in the contacting and doping of these materials. Different strategies have been proposed to achieve doping, but in this presentation we will demonstrate the self-assembly of organic molecules physisorbed on top bulk and thin 2D layers as a means to achieve controlled doping.

Transition metal disilicides are of great interest in Metal-Oxide-Semiconductor Field Effect Transistors (MOSFETs) due to their ability to tune the work function at the metal contact in the source/drain regions. Various kinds of transition metal silicides such as TiSi₂, NiSi₂ and WSi₂ have been studied in previous decades, however, nanoscale studies of TaSi₂ are relatively scarce. Previously, Lemonds et al. successfully demonstrated atomic layer deposition (ALD) of tantalum silicide (TaSi_x) on SiO₂ using TaF₅ and Si₂H₆. In this work, it is demonstrated that using similar reaction conditions TaSi₂ can be grown by ALD process on oxide-free clean Si(001). The growth rate of TaSi₂ on Si(001) was monitored in-situ using a Quartz Crystal Microbalance (QCM) during the deposition. This enabled optimization of the TaF₅ and Si₂H₆ dosing to avoid chemical vapor deposition (CVD) components. Scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), scanning tunneling spectroscopy (STS) and atomic force microscopy (AFM) have been used to investigate the atomic and electronic structure of Si(001) surface after TaSi₂ thin film deposition. HF cleaned Si(001) was used for the substrate. The chemical composition was determined by XPS after ALD to be that of a stoichiometric TaSi₂ film formed on the Si substrate. The key variables in forming stoichiometric TaSi₂ are the ratio of the precursors and the surface temperatures. In the ALD process, a 100x fold excess of Si₂H₆ is required to prevent formation of TaOx; in addition, the surface temperature must be above 240C. These requirements for excess Si₂H₆ and a high surface temperature are likely due to high activation barrier to break the residual Ta-F bonds on the surface after the TaF₄ half pulse since the Ta-F bonds are stronger than the Si-H bonds.

Different forms of carbon-doped Ge₂Sb₂Te₅ chalcogenide thin films have been evaluated for potential use in phase change memory and thermal sensor applications. This includes films sputter deposited from single, carbon-doped targets and refined multilayers made by sequential deposition of chalcogenideand C layers_. In both forms, the crystallization temperature (T_cryt) and the resistance change through crystallization vary with carbon content. Doped chalcogenide films sputter deposited from single targets exhibit increased T_cryt as the concentration of C is made larger. For example, films having ~7 at.% C exhibit a T_cryt that is approximately one hundred and fifteen degrees above that of undoped Ge₂Sb₂Te₅. Films with reduced C content, in the range 1-6 at.%, show intermediate crystallization temperatures. Multilayers fabricated by the sequential deposition of thin chalcogenideand C layers behave much like films grown from single targets, provided that multilayer periodicity is made small, < 3 nm. The crystallization temperature of multilayers also increases with C concentration and a prompt transition to a crystalline phase is observed when the carbon content is low. Interestingly, multilayers made with > 9 at.% C do not transition abruptly to a crystalline state. Instead, a transformation occurs over a broad range of elevated temperature. Each form of chalcogenide thin film exhibits a decreased resistivity upon crystallization. In most cases, resistivity is reduced by 5 decades upon transforming to a face centered cubic structure or a subsequent hexagonal close packed lattice at higher temperature. The changes to microstructure and thickness associated with phase change will also be described. These film properties are investigated by cross-section and plan view electron microscopy.

This work was supported by Sandia National Laboratories. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.

Porous SiCOH films are of great interest in semiconductor fabrication due to their low-k properties. Post-deposition treatments of SiCOH thin films are required to decompose labile pore generators (porogens) and to ensure optimum network formation to improve the electrical and mechanical properties of low-k dielectrics. The goal of this work is to optimize the vacuum-ultraviolet spectrum to identify those wavelengths that will have the most beneficial effect on improving dielectric properties and minimizing damage without the need for thermal heating of the dielectric. Vacuum ultraviolet (VUV) irradiation between 8.3-8.9 eV was found to increase the hardness and elastic modulus of low-k dielectrics at room temperature. Combined with UV exposure of 6.2 eV, it was found that this UV/VUV curing process compares favorably with current UV curing. The results also show that UV/VUV curing can overcome many of the drawbacks of UV curing and improve properties of dielectrics more efficiently without the need for high-temperature heating of the dielectric.

This work was supported by the Semiconductor Research Corporation under Contract 2012-KJ-2359

The effects of cesium (Cs) ion-implantation on uncured plasm a-enhanced chemical-vapor-deposited (PECVD) organosilicate low dielectric constant (low-k) (SiCOH) films have been investigated and compared with the effects of ultraviolet (UV) curing. The mechanical properties, including the elastic modulus and hardness, of the films were improved by up to 30% with Cs implantation, and further up to 52% after annealing at 400°C in a N2 ambient for one hour. These improvements in mechanical properties are either comparable with or better than the effects of UV-curing. These improvements are attributed to an enhancement of the Si-O-Si network structure. The k-value of the SiCOH films increased slightly after Cs implantation, and increased further after annealing. These increases are attributed to two carbon-loss mechanisms, i.e. the carbon loss due to Si-CH3 bond breakage from implanted Cs ions, and the carbon loss due to oxidation during the annealing. The time-zero dielectric breakdown strength was improved after the Cs implantation and the subsequent annealing, and were shown to be better compared with the UV-cured SiCOH films. Within the investigated range of implantation dose, an optimal dose can be found to achieve the best effects. These results indicate that Cs ion implantation has the potential to be a supplement to or a substitution for the incumbent UV curing method for processing SiCOH low-k films.

This work was supported by the Semiconductor Research Corporation under Contract 2012-KJ-2359.

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