Atomic insights into the oxygen incorporation in atomic layer deposited conductive nitrides and its mitigation by energetic ions

Oxygen is often detected as impurity in metal and metal nitride films prepared by atomic layer deposition (ALD) and its presence has profound and adverse effects on the material properties. In this work, we present the case study of HfNx films prepared by plasma-assisted ALD by alternating exposures of CpHf(NMe2)3 and H2 plasma. First, we identify the primary source of O contamination in the film. Specifically, we find that the extent of O incorporation in HfNx films is determined by the flux of background H2O/O2 residual gases reaching the HfNx surface during the ALD process and leads to the formation of Hf–O bonds. Then, we report on the decrease in the concentration of Hf–O bonds in the film upon application of an external radiofrequency (rf) substrate bias during the H2 plasma step. The experimental work is accompanied by first principles calculations to gain insights into the O incorporation and its mitigation upon the impingement of energetic ions on the surface. Specifically, we find that the dissociative binding of H2O on a bare HfN surface is highly favored, resulting in surface Hf–OH groups and concomitant increase in the oxidation state of Hf. We also show that energetic cations (H+, H2+ and H3+) lead to the dissociation of surface Hf–OH bonds, H2O formation, and its subsequent desorption from the surface. The latter is followed by reduction of the Hf oxidation state, presumably by H˙ radicals. The atomic-level understanding obtained in this work on O incorporation and its abstraction are expected to be crucial to prevent O impurities in the HfNx films and contribute to the fabrication of other technologically relevant low resistivity ALD-grown transition metal nitride films

Electrical control of uniformity in quantum dot devices

Highly uniform quantum systems are essential for the practical implementation of scalable quantum processors. While quantum dot spin qubits based on semiconductor technology are a promising platform for large-scale quantum computing, their small size makes them particularly sensitive to their local environment. Here, we present a method to electrically obtain a high degree of uniformity in the intrinsic potential landscape using hysteretic shifts of the gate voltage characteristics. We demonstrate the tuning of pinch-off voltages in quantum dot devices over hundreds of millivolts that then remain stable at least for hours. Applying our method, we homogenize the pinch-off voltages of the plunger gates in a linear array for four quantum dots reducing the spread in pinch-off voltage by one order of magnitude. This work provides a new tool for the tuning of quantum dot devices and offers new perspectives for the implementation of scalable spin qubit arrays

Low disorder and high valley splitting in silicon

The electrical characterisation of classical and quantum devices is a critical step in the development cycle of heterogeneous material stacks for semiconductor spin qubits. In the case of silicon, properties such as disorder and energy separation of conduction band valleys are commonly investigated individually upon modifications in selected parameters of the material stack. However, this reductionist approach fails to consider the interdependence between different structural and electronic properties at the danger of optimising one metric at the expense of the others. Here, we achieve a significant improvement in both disorder and valley splitting by taking a co-design approach to the material stack. We demonstrate isotopically-purified, strained quantum wells with high mobility of 3.14(8)$\times$10$^5$ cm$^2$/Vs and low percolation density of 6.9(1)$\times$10$^{10}$ cm$^{-2}$. These low disorder quantum wells support quantum dots with low charge noise of 0.9(3) $\mu$eV/Hz$^{1/2}$ and large mean valley splitting energy of 0.24(7) meV, measured in qubit devices. By striking the delicate balance between disorder, charge noise, and valley splitting, these findings provide a benchmark for silicon as a host semiconductor for quantum dot qubits. We foresee the application of these heterostructures in larger, high-performance quantum processors

Plasma-Assisted ALD of Highly Conductive HfNx: On the Effect of Energetic Ions on Film Microstructure

In this work, we report on the atomic layer deposition (ALD) of HfN x thin films by employing CpHf(NMe 2) 3 as the Hf(IV) precursor and Ar–H 2 plasma in combination with external RF substrate biasing as the co-reactant. Following up on our previous results based on an H 2 plasma and external RF substrate biasing, here we address the effect of ions with a larger mass and higher energy impinging on HfN x film surface during growth. We show that an increase in the average ion energy up to 304 eV leads to a very low electrical resistivity of 4.1 × 10 –4 Ωcm. This resistivity value is achieved for films as thin as ~ 35 nm, and it is an order of magnitude lower than the resistivity reported in literature for HfN x films grown by either CVD or ALD, while being comparable to the resistivity of PVD-grown HfN x films. From the extensive thin film characterization, we conclude that the impinging ions during the film growth lead to the very low electrical resistivity of HfN x films by suppressing the oxygen incorporation and in-grain nano-porosity in the films

Tuning material properties of oxides and nitrides by substrate biasing during plasma-enhanced atomic layer deposition on planar and 3D substrate topographies

Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiOx and HfOx and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiNx and HfNx films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiOx were slightly improved whereas those of SiNx were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed

Tailoring nanopore formation in atomic layer deposited ultrathin films

Selectivity is a critical attribute of catalysts used in manufacturing of essential and fine chemicals. An excellent way to induce selectivity in catalysts is by using ultrathin films with tailored nanoporosity. For instance, nanopores can be created in atomic layer deposition (ALD) ultrathin over-coatings on supported metal nanoparticles by subjecting the coatings to high temperature annealing. These nanopores expose the active surface of the underlying metal nanoparticles. The dimensions of these nanopores can be tuned to impart shape selectivity: only reactants or products with a specific size or shape can fit inside the pore. In this work, the authors explore the underlying mechanism driving nanopore formation in ALD films. Ultrathin films of ALD TiO2 (∼2.5 nm thick) and ALD Al2O3 (∼4.9 nm thick) were deposited on nonporous γ-Al2O3 nanoparticles. The pore formation and evolution were monitored in situ during thermal annealing using small-angle x-ray scattering (SAXS), and the crystallinity was monitored by in situ x-ray diffraction. A correlation between the nanopore formation and amorphous to crystalline phase transitions in the ALD layers was observed. The authors hypothesize that the pores form through the relaxation of stress induced by densification of the ALD films during the phase transitions. The authors developed a mathematical model to evaluate this hypothesis and found remarkable agreement between the model and the SAXS measurements