Isotropic plasma-thermal atomic layer etching of superconducting TiN films using sequential exposures of molecular oxygen and SF6/_6/H2_2 plasma

Microwave loss in superconducting titanium nitride (TiN) films is attributed to two-level systems in various interfaces arising in part from oxidation and microfabrication-induced damage. Atomic layer etching (ALE) is an emerging subtractive fabrication method which is capable of etching with Angstrom-scale etch depth control and potentially less damage. However, while ALE processes for TiN have been reported, they either employ HF vapor, incurring practical complications; or the etch rate lacks the desired control. Further, the superconducting characteristics of the etched films have not been characterized. Here, we report an isotropic plasma-thermal TiN ALE process consisting of sequential exposures to molecular oxygen and an SF$_6$/H$_2$ plasma. For certain ratios of SF$_6$:H$_2$ flow rates, we observe selective etching of TiO$_2$ over TiN, enabling self-limiting etching within a cycle. Etch rates were measured to vary from 1.1 \r{A}/cycle at 150 $^\circ$C to 3.2 \r{A}/cycle at 350 $^\circ$C using ex-situ ellipsometry. We demonstrate that the superconducting critical temperature of the etched film does not decrease beyond that expected from the decrease in film thickness, highlighting the low-damage nature of the process. These findings have relevance for applications of TiN in microwave kinetic inductance detectors and superconducting qubits.Comment: 17 pages, 7 figure

Ultrathin superconducting TaCxN1−x films prepared by plasma-enhanced atomic layer deposition with ion-energy control

This work demonstrates that plasma-enhanced atomic layer deposition (PEALD) with substrate biasing enables the preparation of ultrathin superconducting TaCxN1−x films. By comparing with films grown without substrate biasing, the enhanced ion energies yield a hundredfold reduction in room-temperature resistivity: a comparably low value of 217 μΩ cm is obtained for a 40 nm film. The ion-energy control enables tuning of the composition, counteracts oxygen impurity incorporation, and promotes a larger grain size. Correspondingly, the critical temperature of superconductivity (Tc) displays clear ion-energy dependence. With optimized ion energies, a consistently high Tc around 7 K is measured down to 11 nm film thickness. These results demonstrate the high ultrathin-film quality achievable through PEALD combined with substrate biasing. This process is particularly promising for the fabrication of low-loss superconducting quantum devices

Innovative remote plasma source for atomic layer deposition for GaN devices

High-quality dielectric films could enable GaN normally off high-electron-mobility transistors (HEMTs). Plasma atomic layer deposition (ALD) is known to allow for controlled high-quality thin-film deposition, and in order to not exceed energy and flux levels leading to device damage, the plasma used should preferably be remote for many applications. This article outlines ion energy flux distribution functions and flux levels for a new remote plasma ALD system, Oxford Instruments Atomfab™, which includes an innovative, RF-driven, remote plasma source. The source design is optimized for ALD for GaN HEMTs for substrates up to 200 mm in diameter and allows for Al2O3 ALD cycles of less than 1 s. Modest ion energies of <50 eV and very low ion flux levels of <1013 cm−2 s−1 were found at low-damage conditions. The ion flux can be increased to the high 1014 cm−2 s−1 range if desired for other applications. Using low-damage conditions, fast ALD saturation behavior and good uniformity were demonstrated for Al2O3. For films of 20 nm thickness, a breakdown voltage value of 8.9 MV/cm was obtained and the Al2O3 films were demonstrated to be suitable for GaN HEMT devices where the combination with plasma pretreatment and postdeposition anneals resulted in the best device parameters

Plasma atomic layer deposition

Plasma atomic layer deposition (ALD) is optimized through modulation of the gas residence time during an excited species phase, wherein activated reactant is supplied such as from a plasma. Reduced residence time increases the quality of the deposited layer, such as reducing wet etch rates, increasing index of refraction and/or reducing impurities in the layer. For example, dielectric layers, particularly silicon nitride films, formed from such optimized plasma ALD processes have low levels of impurities remaining from the silicon precursor.</p

Plasma atomic layer deposition

Plasma atomic layer deposition (ALD) is optimized through modulation of the gas residence time during an excited species phase, wherein activated reactant is supplied such as from a plasma. Reduced residence time increases the quality of the deposited layer, such as reducing wet etch rates, increasing index of refraction and/or reducing impurities in the layer. For example, dielectric layers, particularly silicon nitride films, formed from such optimized plasma ALD processes have low levels of impurities remaining from the silicon precursor.</p

Electron Scattering and Doping Mechanisms in Solid-Phase-Crystallized In₂O₃:H Prepared by Atomic Layer Deposition

Hydrogen-doped indium oxide (In₂O₃:H) has recently emerged as an enabling transparent conductive oxide for solar cells, in particular for silicon heterojunction solar cells because its high electron mobility (>100 cm²/(V s)) allows for a simultaneously high electrical conductivity and optical transparency. Here, we report on high-quality In₂O₃:H prepared by a low-temperature atomic layer deposition (ALD) process and present insights into the doping mechanism and the electron scattering processes that limit the carrier mobility in such films. The process consists of ALD of amorphous In₂O₃:H at 100 °C and subsequent solid-phase crystallization at 150–200 °C to obtain large-grained polycrystalline In₂O₃:H films. The changes in optoelectronic properties upon crystallization have been monitored both electrically by Hall measurements and optically by analysis of the Drude response. After crystallization, an excellent carrier mobility of 128 ± 4 cm²/(V s) can be obtained at a carrier density of 1.8 × 10²⁰ cm^–3, irrespective of the annealing temperature. Temperature-dependent Hall measurements have revealed that electron scattering is dominated by unavoidable phonon and ionized impurity scattering from singly charged H-donors. Extrinsic defect scattering related to material quality such as grain boundary and neutral impurity scattering was found to be negligible in crystallized films indicating that the carrier mobility is maximized. Furthermore, by comparison of the absolute H-concentration and the carrier density in crystallized films, it is deduced that <4% of the incorporated H is an active dopant in crystallized films. Therefore, it can be concluded that inactive H atoms do not (significantly) contribute to defect scattering, which potentially explains why In₂O₃:H films are capable of achieving a much higher carrier mobility than conventional In₂O₃:Sn (ITO)

Atomic layer deposition of high-mobility hydrogen-doped zinc oxide

In this work, atomic layer deposition (ALD) has been employed to prepare high-mobility H-doped zinc oxide (ZnO:H) films. Hydrogen doping was achieved by interleaving the ZnO ALD cycles with H2 plasma treatments. It has been shown that doping with H2 plasma offers key advantages over traditional doping by Al and B, and enables a high mobility value up to 47 cm2/Vs and a resistivity of 1.8 mΩcm. By proper choice of a deposition regime where there is a strong competition between film growth and film etching by the H2 plasma treatment, a strongly enhanced grain size and hence increased carrier mobility with respect to undoped ZnO can be obtained. The successful incorporation of a significant amount of H from the H2 plasma has been demonstrated, and insights into the mobility-limiting scatter mechanisms have been obtained from temperature-dependent Hall measurements. A comparison with conventional TCOs has been made in terms of optoelectronic properties, and it has been shown that high-mobility ZnO:H has potential for use in various configurations of silicon heterojunction solar cells and silicon-perovskite tandem cells