W Wytze Keuning

Low Temperature Plasma-Enhanced Atomic Layer Deposition of Metal Oxide Thin Films

Many reported atomic layer deposition (ALD) processes are carried out at elevated temperatures (>150°C), which can be problematic for temperature-sensitive substrates. Plasma-enhanced ALD routes may provide a solution, as the ALD temperature window can, in theory, be extended to lower deposition temperatures due to the reactive nature of the plasma. As such, the plasma-enhanced ALD of Al 2 O 3 , TiO 2 , and Ta 2 O 5 has been investigated at 25-400°C using [Al(CH 3 ) 3 ], [Ti(O i Pr) 4 ], [Ti(Cp Me )(O i Pr) 3 ], [TiCp*(OMe) 3 ], and [Ta(NMe 2 ) 5 ] as precursors. An O 2 plasma was employed as the oxygen source in each case. We have demonstrated metal oxide thin-film deposition at temperatures as low as room temperature and compared the results with corresponding thermal ALD routes to the same materials. The composition of the films was determined by Rutherford backscattering spectroscopy. Analysis of the growth per cycle data and the metal atoms deposited per cycle revealed that the growth per cycle is strongly dependent on the film density at low deposition temperatures. Comparison of these data for Al 2 O 3 ALD processes in particular, showed that the number of Al atoms deposited per cycle was consistently high down to room temperature for the plasma-enhanced process but dropped for the thermal process at substrate temperatures lower than 250°C.

Cathode encapsulation of organic light emitting diodes by atomic layer deposited Al2O3 films and Al2O3/a-SiNx: H stacks

Al2O3 thin films synthesized by plasma-enhanced atomic layer deposition (ALD) at room temperature (25 °C) have been tested as water vapor permeation barriers for organic light emitting diode devices. Silicon nitride films (a-SiNx:H) deposited by plasma-enhanced chemical vapor deposition served as reference and were used to develop Al2O3/a-SiNx:H stacks. On the basis of Ca test measurements, a very low intrinsic water vapor transmission rate of ≤ 2 × 10−6 g m−2 day−1 and 4 × 10−6 g m−2 day−1 (20 oC/50% relative humidity) were found for 20–40 nm Al2O3 and 300 nm a-SiNx:H films, respectively. The cathode particle coverage was a factor of 4 better for the Al2O3 films compared to the a-SiNx:H films and an average of 0.12 defects per cm2 was obtained for a stack consisting of three barrier layers (Al2O3/a-SiNx:H/Al2O3).

Opportunities for plasma-assisted atomic layer deposition

Within the method of atomic layer deposition (ALD), additional reactivity can be delivered to the surface in the form of plasma-produced species. The application of such a low- temperature plasma in the ALD cycle can therefore open up a processing parameter space that is unattainable by the strictly thermally driven process. In this contribution several possible benefits of plasma-assisted ALD will be reviewed showing bright prospect for plasma-assisted ALD for a large variety of applications, also far beyond the typical use in semiconductor devices.

Thermal and Plasma Enhanced Atomic Layer Deposition of Al2O3 on GaAs Substrates

A good dielectric layer on the GaAs substrate is one of the critical issues to be solved for introducing GaAs as a candidate to replace Si in semiconductor processing. In literature, promising results have been shown for Al 2 O 3 on GaAs substrates. Therefore, atomic layer deposition (ALD) of Al 2 O 3 has been studied on GaAs substrates. We have been investigating the influence of the ALD process (thermal vs plasma-enhanced ALD) as well as the influence of the starting surface (no clean vs partial removal of the native oxide). Ellipsometry and total X-ray reflection fluorescence were applied to study the growth of the ALD layers. Angle-resolved X-ray photoelectron spectroscopy was used to determine the composition of the interlayer. Both processes were shown to be roughly independent of the starting surface with a minor dependence for the thermal ALD. Thermally deposited ALD layers exhibited better electrical characteristics based on capacitance measurements. This could be linked to the thinner interlayer observed for thermally deposited Al 2 O 3 . However, the Fermi level was not unpinned in all cases, suggesting that more work needs to be done for passivating the interface between GaAs and the high-k layer.

Controlling the resistivity gradient in aluminum-doped zinc oxide grown by plasma-enhanced chemical vapor deposition

Aluminum-doped ZnO (ZnO:Al) grown by chemical vapor deposition (CVD) generally exhibit a major drawback, i.e., a gradient in resistivity extending over a large range of film thickness. The present contribution addresses the plasma-enhanced CVD deposition of ZnO:Al layers by focusing on the control of the resistivity gradient and providing the solution towards thin (≤300 nm) ZnO:Al layers, exhibiting a resistivity value as low as 4 × 10−4 Ω cm. The approach chosen in this work is to enable the development of several ZnO:Al crystal orientations at the initial stages of the CVD-growth, which allow the formation of a densely packed structure exhibiting a grain size of 60–80 nm for a film thickness of 95 nm. By providing an insight into the growth of ZnO:Al layers, the present study allows exploring their application into several solar cell technologies.

A new concept for spatially divided Deep Reactive Ion Etching with ALD-based passivation

Conventional Deep Reactive Ion Etching (DRIE) is a plasma etch process with alternating half-cycles of 1) Si-etching with SF6 to form gaseous SiFx etch products, and 2) passivation with C4F8 that polymerizes as a protecting fluorocarbon deposit on the sidewalls and bottom of the etched features. In this work we report on a novel alternative and disruptive technology concept of Spatially-divided Deep Reactive Ion Etching, S-DRIE, where the process is converted from the time-divided into the spatially divided regime. The spatial division can be accomplished by inert gas bearing ‘curtains’ of heights down to ~20 um. These curtains confine the reactive gases to individual (often linear) injection slots constructed in a gas injector head. By horizontally moving the substrate back and forth under the head one can realize the alternate exposures to the overall cycle. A second improvement in the spatially divided approach is the replacement of the CVD-based C4F8 passivation steps by ALD-based oxide (e.g. SiO2) deposition cycles. The method can have industrial potential in cost-effective creation of advanced 3D interconnects (TSVs), MEMS manufacturing and advanced patterning, e.g., in nanoscale transistor line edge roughness using Atomic Layer Etching.

Atomic layer deposition of high-k dielectric layers on Ge and III-V MOS channels

Ge and III-V semiconductors are potential high performance channel materials for future CMOS devices. In this work, we have studied At. Layer Deposition (ALD) of high-k dielec. layers on Ge and GaAs substrates. We focus at the effect of the oxidant (H2O, O3, O2, O2 plasma) during gate stack formation. GeO2, obtained by Ge oxidn. in O2 or O3, is a promising passivation layer. The germanium oxide thickness can be scaled down below 1 nm, but such thin layers contain Ge in oxidn. states lower than 4+. Still, elec. results indicate that small amts. of Ge in oxidn. states lower than 4+ are not detrimental for device performance. Partial intermixing was obsd. for high-k dielec. and GeO2 or GaAsOx, suggesting possible correlations in the ALD growth mechanisms on Ge and GaAs substrates. [on SciFinder (R)]

Plasma-assisted atomic layer deposition of conformal Pt films in high aspect ratio trenches

To date, conventional thermal atomic layer deposition (ALD) has been the method of choice to deposit high-quality Pt thin films grown typically from (MeCp)PtMe3 vapor and O2 gas at 300 °C. Plasma-assisted ALD of Pt using O2 plasma can offer several advantages over thermal ALD, such as faster nucleation and deposition at lower temperatures. In this work, it is demonstrated that plasma-assisted ALD at 300 °C also allows for the deposition of highly conformal Pt films in trenches with high aspect ratio ranging from 3 to 34. Scanning electron microscopy inspection revealed that the conformality of the deposited Pt films was 100% in trenches with aspect ratio (AR) up to 34. These results were corroborated by high-precision layer thickness measurements by transmission electron microscopy for trenches with an aspect ratio of 22. The role of the surface recombination of O-radicals and the contribution of thermal ALD reactions is discussed.

PTFE treatment by remote atmospheric Ar/O2 plasmas : a simple reaction scheme model proposal

Polytetrafluoroethylene (PTFE) samples were treated by a remote atmospheric pressure microwave plasma torch and analyzed by water contact angle (WCA) and X-ray photoelectron spectroscopy (XPS). In the case of pure argon plasma a decrease of WCA is observed meanwhile an increase of hydrophobicity was observed when some oxygen was added to the discharge. The WCA results are correlated to XPS of reference samples and the change of WCA are attributed to changes in roughness of the samples. A simple kinetics scheme for the chemistry on the PTFE surface is proposed to explain the results.

Publisher's Note: “Controlling the resistivity gradient in aluminum-doped zinc oxide grown by plasma-enhanced chemical vapor deposition” [J. Appl. Phys. 112, 043708 (2012)]

Aluminum-doped ZnO (ZnO:Al) grown by chemical vapor deposition (CVD) generally exhibit a major drawback, i.e., a gradient in resistivity extending over a large range of film thickness. The present contribution addresses the plasma-enhanced CVD deposition of ZnO:Al layers by focusing on the control of the resistivity gradient and providing the solution towards thin (≤300 nm) ZnO:Al layers, exhibiting a resistivity value as low as 4 × 10−4 Ω cm. The approach chosen in this work is to enable the development of several ZnO:Al crystal orientations at the initial stages of the CVD-growth, which allow the formation of a densely packed structure exhibiting a grain size of 60–80 nm for a film thickness of 95 nm. By providing an insight into the growth of ZnO:Al layers, the present study allows exploring their application into several solar cell technologies.