The spontaneous self-assembly of block copolymers into a variety of nanoscale morphologies makes these systems ideal candidates for next-generation lithography applications. However, industrial application requires long-range control over the domain order and orientation. Extensive work has been done to achieve linearity in nanopatterns on wafer size scales, but there is also a need to control the formation of point defects to generate, for example, T-junctions, jogs, and bends for semiconductor templating applications. As such, a fundamental understanding of block copolymer nanopattern formation and how structural defects contribute to instability in the films is crucial to achieve the perfection required to utilize these thin films as lithographic templates for nanotechnologies. Here, I present recent work on poly(styrene-block-methyl methacrylate) (PS-b-PMMA) thin films with environmentally controlled high-speed atomic force microscopy (AFM). By imaging films with minor variations in thickness above the glass transition temperature, we capture the early formation of hole, island, and continuous relief structures during thermal annealing. Additionally, we see how the striped nanoscale pattern develops in tandem with the changing mesoscale features. Confining the PS-b-PMMA in lithographic templates that are tapered in width, or wedge-shaped, generates dislocations at precise intervals locations in otherwise linearly aligned polymer domains. Examining polymer confined in these films reveals the pathways by which dislocations evolve and annihilate during thermal annealing, and how point defects in nanopatterns influence interfacial fluctuations in the surrounding polymer domains. Together, these studies contribute to the fundamental understanding of the dynamics and ordering of block copolymer thin films and reveal how topography - both native and imposed by lithography – impacts the nanoscale structure.

Plasma-enhanced atomic layer deposition (PEALD) enables the epitaxial growth of ultrathin indium nitride (InN) films at significantly reduced temperatures and with atomic-level control of layer thickness. These advantages are challenged by the inherent complexity of the growth process due to the reliance on plasma surface interactions [1], which necessitates a detailed understanding of the relationship between the plasma and the growth kinetics. To this end, synchrotron hard x-ray scattering techniques are well-suited to the in situ study of PEALD processes, as they are capable of operating in harsh environments during chemical reactions and can provide real-time information about the structural properties of the film. One such technique, grazing incidence small-angle x-ray scattering (GISAXS), probes nanoscale fluctuations in electron density averaged across the sample, which can provide an in-depth description of surface topography [2]. Initial studies of epitaxial InN growth under fixed plasma conditions demonstrated the utility of GISAXS for understanding the kinetics of PEALD processes, and showed that the growth proceeded in a Stranski-Krastanov mode where the critical thickness for island formation and the coarsening behavior were strongly influenced by temperature [3].

In this work, we utilize in situ GISAXS to investigate the early-stage PEALD growth kinetics of epitaxial InN within three different plasma regimes. The GISAXS data are supported by diagnostic studies of the plasma species generation in the inductively coupled plasma source as a function of the relative concentrations of the nitrogen/argon gas mixture used in the growth process. The growth mode is found to be correlated to the production of nitrogen species in the plasma, with high concentrations of atomic N species promoting Volmer-Weber growth and low concentrations promoting Stranski-Krastanov growth. Under conditions of high atomic N production, both the island radius and critical thickness for island formation are found to increase with ion flux. Furthermore, the InN island distance and areal density are found to change only during plasma exposure, and to continue changing with exposure even after the methylindium adlayer is believed to have fully reacted with the plasma. Our results demonstrate the potential to control the growth kinetics during PEALD of epitaxial films by intentionally accessing specific regimes of plasma species generation.

References

[1] D.R. Boris et al., J. Vac. Sci. Technol. A 38, 040801 (2020)
[2] G. Renaud, R. Lazzari, and F. Leroy, Surf. Sci. Rep. 64, 255 (2009)
[3] J.M. Woodward et al., J. Vac. Sci. Technol. A 37, 030901 (2019)

Low-temperature (<400 °C) deposition of transition metal dichalcogenide (TMD) films has been proposed as a potential route for fabricating diffusion barrier structures in field effect transistors and other electronic devices. Atomic layer deposition (ALD) is well-suited to this application due to its low thermal budget and high conformality, enabling its integration into back-end of line processing. Several publications have described the deposition of layered MoS₂ films by ALD, most commonly using MoCl₅ and H₂S as precursors^1–4. Inorganic precursors may be desirable for their high thermal stability and the lack of organic ligands, which often are a source of impurities in deposited films. However, MoCl₅ is a low-volatility solid under typical delivery conditions and can readily form oxychlorides upon exposure to moisture. Delivery challenges associated with MoCl₅ are reflected in the large variety of delivery methods and conditions reported in the literature, for instance a vessel temperature range of 70 °C to 210 °C. Deposition studies using MoCl₅ and H₂S also show inconsistent results with respect to MoS₂ morphology, grain size, and composition, with no deposition reported under some conditions⁵. This lack of reproducibility could stem from variations in MoCl₅ flux observed under different delivery configurations. To address this possibility, we monitored the flow of MoCl₅ and H₂S as a function of delivery conditions using direct absorbance measurements. We measured vapor phase spectra of neat MoCl₅ and its common oxychlorides using an ultraviolet-visible (UV-vis) spectrometer under static conditions. To evaluate precursor delivery under flow, we implemented in-line gas analyzers each consisting of a broadband source, a filter for wavelength selection, and an avalanche photodiode. We evaluated the delivery rates of MoCl₅ and H₂S injected from vapor draw and direct draw vessels, respectively. In addition to vapor phase measurements, we used real-time spectroscopic ellipsometry to characterize precursor adsorption under varying delivery conditions. Using results from these measurements, we will discuss the reproducibility of MoCl₅ and H₂S delivery rates and potential implications for MoS₂ deposition.

¹ R. Browning et al., Mater. Res. Express 2, 035006 (2015).

² A. Valdivia et al. Vac. Sci. Technol. Vac. Surf. Films 34, 021515 (2016).

³ L. Liu et al., Nanotechnology 28, 195605 (2017).

⁴ W. Ahn et al., Phys. Status Solidi RRL – Rapid Res. Lett. 15, 2000533 (2021).

⁵ M. Mattinen et al., Adv. Mater. Interfaces 4, 1700123 (2017).

Area-selective atomic layer deposition (AS-ALD) is a bottom-up fabrication technique that can address challenges related to conventional lithography in the fabrication of integrated circuits. Cu is the predominant interconnect metal while SiO₂ is used as the dielectric. In this work, we explore the growth of a dielectric on SiO₂, with Cu as the nongrowth surface. Using in situ reflection-absorption infrared spectroscopy (RAIRS) we previously showed that thiols are effective inhibitors for Cu, and readily adsorb onto the surface by reducing the native CuO_x layer. However, thiols have a low vapor pressure and thermal stability on Cu. With these inhibitors, the Cu surface can be re-dosed between ALD cycles, which is essential in plasma-assisted ALD processes. Moreover, the inhibitor readily desorbs from the non-growth surface after AS-ALD, which eliminates surface cleaning steps that are normally required with self-assembled monolayers. Recently, several small molecule inhibitors for Cu have been reported in the AS-ALD literature including alkynes, aniline, and pyridine.

For alkynes, we show that a H₂ plasma cleaning step is required to reduce the native CuO_x layer on the Cu surface. When Cu wafers left in atmospheric conditions are exposed to an H₂ plasma, RAIRS shows that surface carbonates are removed, which indirectly confirms the presence of surface CuO_x. Specifically, we show that after we optimized the H₂ plasma cleaning duration at 200 °C, 5-decyne adsorbs on the Cu surface. The adsorption of 5-decyne is apparent from the appearance of –C=C– and –C≡C– stretching vibrations in the ~1600 and ~2200 cm^–1 regions, respectively. In addition, we also observed the CH_x stretching and bending modes in the ~2900 and ~1400 cm^–1 regions, respectively. Adsorption of 5-decyne on PVD and CMP Cu was observed over the temperature range of 28 to 150 °C. As the substrate temperature increased for the PVD Cu surface, the intensity of the –C=C– mode decreased while the –C≡C– mode increased, indicating that chemisorption is favored at lower temperatures while strong physisorption is favored at higher temperatures. At higher temperatures, the CH_x stretching and bending mode intensities decreased, indicating lower 5-decyne adsorption. ALD of Al₂O₃ on Cu with 5-decyne as an inhibitor was tested with dimethyl aluminum isopropoxide (DMAI) and H₂O. Even at sub saturation doses of DMAI, AS-ALD was not observed. We will also compare 5-decyne as an inhibitor with aniline and pyridine, which have been demonstrated as more promising candidates.