The deposition of highly ordered, thin, organic films is of great importance to a variety of fields. The development of biological sensors, organic solar cells, and optical devices relies on the ability to grow thin layers of organic material with various thicknesses, compositions, functionalities, and levels of crystallinity. One promising method of creating such films is molecular layer deposition (MLD), which uses an alternating sequence of self-saturating reactions by vapor-phase organic precursors at the substrate to grow films in a layer-by-layer fashion. This technique has been demonstrated with a variety of precursor chemistries and has been shown capable of growing films on high aspect ratio features with low surface roughness and high conformality. But despite the growing use of MLD, many questions still remain as to the orientation of the molecular chains within the deposited films and the packing of these chains. Many different factors may contribute to varying degrees of crystallinity during growth, such as chain-chain steric repulsion, Van der Waals forces, chain growth angle, and inter-chain hydrogen bonding. Here, we demonstrate that some MLD chemistries can form nanoscale organic films that exhibit well-ordered packing. Polyurea MLD films with different thicknesses and backbone chemistries were grown in an MLD reactor and then examined with x-ray diffraction (XRD) using synchrotron radiation at the Stanford Synchrotron Radiation Lightsource (SSRL). Spectroscopic ellipsometry was used to observe film thickness, while x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy monitored for film degradation. XRD results for the polyurea MLD films show peaks at q-values of 1.5/Å, corresponding to a d-spacing around 4.2 Å. Changing the precursor from a more rigid to a more flexible backbone leads to variations in d-spacing and diffraction intensity. Growth on substrates with different surface chemistries and roughness, as well as the effect of heating and re-cooling the films, is also explored. These results suggest that thin organic films with varying levels of packing order can be grown using MLD by tuning the precursor chemistry.

The use of high-κ dielectrics on III-V semiconductors in place of Si/SiO₂ structures in metal oxide semiconductor devices has been perpetually hindered by poor quality native oxides at the substrate/film interface. A promising solution for the removal of these oxides is the atomic layer deposition (ALD) growth technique which has shown the ability to remove native oxides during deposition without additional processing for certain chemistries.^1–4

In this work, Ta₂O₅ thin films were deposited on InAs(100) by ALD using pentakis dimethyl amino tantalum (PDMAT) and H₂O to study the effects of film deposition on the native oxides. 3 and 7 nm films were grown at 150-300 °C on InAs substrates covered with native oxides and substrates chemically etched in NH₄OH. Analysis of the film deposited on native oxide covered substrates by x-ray photoelectron spectroscopy (XPS) shows arsenic and indium oxides are readily removed during deposition of 3 nm Ta₂O₅ at 250 and 300 °C, temperatures very close to the optimal ALD temperature for the specific chemistry. At lower temperatures both oxides persist with indium oxides generally being harder to remove.

Depth profiling by argon-ion sputtering data of 7 nm films shows that indium oxides have diffused into the Ta₂O₅ film. The sharp decrease in oxide signal after the first sputter cycle indicates that the majority of the indium oxide is located near the surface suggesting the migration of indium oxides to the film surface during deposition. Arsenic oxides, however, are detected in smaller amounts and generally speaking remain at the interface. For depositions on etched InAs no arsenic oxides were detected but a small amount of indium oxides remain even at the optimal deposition temperatures. Films grown on etched substrates always contain less indium and arsenic oxides than their equivalents deposited on native oxide surfaces. Mixing of indium oxide in the films may have a significant negative effect on their insulating properties negating any gain from a sharper interface.

¹ P.D. Ye, G.D. Wilk, B. Yang, J. Kwo, S.N.G. Chu, S. Nakahara, H.-J.L. Gossmann, J.P. Mannaerts, M. Hong, K.K. Ng, and J. Bude, Appl. Phys. Lett. 83, 180 (2003).

² M.M. Frank, G.D. Wilk, D. Starodub, T. Gustafsson, E. Garfunkel, Y.J. Chabal, J. Grazul, and D.A. Muller, Appl. Phys. Lett. 86, 152904 (2005).

³ M.L. Huang, Y.C. Chang, C.H. Chang, Y.J. Lee, P. Chang, J. Kwo, T.B. Wu, and M. Hong, Appl. Phys. Lett. 87, 252104 (2005).

⁴ C.-H. Chang, Y.-K. Chiou, Y.-C. Chang, K.-Y. Lee, T.-D. Lin, T.-B. Wu, M. Hong, and J. Kwo, Appl. Phys. Lett. 89, 242911 (2006).

A first experimental approach was based on the use of macroscopic, trench-like structures in combination with low precursor pressures. In this way, the transport of the precursor molecules in the test structures was governed by molecular flow, as in microscopic trenches under standard ALD conditions. This method allowed us to quantify the conformality of the trimethylaluminum (TMA)/H2O process as a function of the aspect ratio and the TMA exposure time. Our experimental data indicated that the sticking probability is a determining factor in the conformality of ALD [1]. A better understanding of the effect of this parameter on the conformality was obtained via kinetic modeling and Monte Carlo modeling.

As a second substrate, porous titania thin films with pore sizes in the low mesoporous regime (< 10 nm) were considered in order to get insights on the minimum pore diameter that can be achieved by ALD. Novel in situ characterization techniques were developed to monitor the pore filling by ALD. Synchrotron-based x-ray fluorescence and scattering techniques provided cycle-per-cycle information on the material uptake and densification of the porous film, while ellipsometric porosimetry was used to quantify the pore size reduction. This study nicely demonstrated the ability of ALD to tune the diameter of nanopores down to the molecular level [2].

Finally, we performed ALD of TiO2 into a 3D ordered silica powder with two types of mesopores [3]. By varying the Ti-precursor exposure time, we investigated the introduction of TiO2 into the differently sized mesopores. A TEM study revealed the diffusion limited nature of the TiO2 ALD process, leading to anisotropic penetration profiles in this specific pore structure. We observed a systematic deeper penetration of the deposition front along the main channels compared to the narrower mesopores. These results were corroborated by modeling work.

[1] J. Dendooven et al., J. Electrochem. Soc. 156, P63, 2009. [2] J. Dendooven et al., Chem. Mater. 24, 1992, 2012. [3] S. P. Sree et al., Chem. Mater. 24, 2775, 2012.

Atomic layer deposition (ALD) is commonly used to coat high aspect ratio structures, including vertically aligned carbon nanotube arrays (VACNTs). Previous studies, however, have demonstrated precursor diffusion depths of only 60 µm for long exposure times, leading to a “canopy effect” where preferential coating takes place at the top of arrays. In this research we report the first example of conformal Al₂O₃ ALD on 1.5 mm tall VACNTs with uniform coating distribution from CNT base to tip. Large-scale CNT arrays with free volume aspect ratios ~15,000 were able to be uniformly coated by manipulating sample orientation and mounting techniques, as confirmed by cross-sectional energy dispersive x-ray spectroscopy. Conformal coating was achieved through modification of CNT surface chemistry via vapor phase techniques including pyrolytic carbon deposition and atmospheric pressure oxygen plasma functionalization. Thermogravimetric analysis revealed that arrays which were functionalized prior to ALD coating were more stable to thermal degradation compared to untreated, ALD coated arrays. Interestingly, CNTs could be easily removed during thermal oxidation to yield arrays of continuous, high surface area, vertically aligned Al₂O₃ nanotubes. Additionally, functionalized and ALD coated arrays exhibited compressive moduli two times greater than pristine arrays coated for the same number of cycles. Al₂O₃ coated arrays exhibited hydrophilic wetting behavior as well as foam-like recovery following compressive strain. These processing techniques have been successfully applied to other ALD precursors to yield CNT arrays uniformly coated with ZnO and TiO₂ as well.