Recently, a novel approach of depositing metallic films with chemical vapor deposition (CVD), using plasma electrons as reducing agents, has been presented and is herein referred to as e-CVD. By applying a positive substrate bias to the substrate holder, plasma electrons are drawn to the surface of the substrate, where the film growth occurs. In this work, we have characterized the electron flux at the substrate position in terms of energy and number density as well as the plasma potential and floating potential when maintaining an unbiased and a positively biased substrate. The measurements were performed using a modified radio frequency Sobolewski probe to overcome issues due to the coating of conventional electrostatic probes. The plasma was generated using a DC hollow cathode plasma discharge at various discharge powers and operated with and without precursor gas. The results show that the electron density is typically around 10(16) m(-3) and increases with plasma power. With a precursor, an increase in the substrate bias shows a trend of increasing electron density. The electron temperature does not change much without precursor gas and is found in the range of 0.3-1.1 eV. Introducing a precursor gas to the vacuum chamber shows an increase in the electron temperature to a range of 1-5 eV and with a trend of decreasing electron temperature as a function of discharge power. From the values of the plasma potential and the substrate bias potential, we were able to calculate the potential difference between the plasma and the substrate, giving us insight into what charge carriers are expected at the substrate under different process conditions.

Aluminum nitride (AlN) is a semiconductor with a very wide band gap and a potential dielectric material. Deposition of thin AlN films is routinely done by several techniques, including atomic layer deposition (ALD). In this study, we deposited AlN using ALD with trimethylaluminum (TMA) as the Al precursor and ammonia (NH3) with and without plasma activation as the N precursor in the temperature range from 100 to 400 degrees C while monitoring the surface reactions using mass spectrometry. Our results, combined with recent quantum chemical modelling, suggest that the surface chemistry of the deposition process is chemisorption of TMA followed by reductive elimination of the methyl groups to render mono methyl aluminum species. The NH3 chemisorption is done by ligand exchange to form CH4 and an -NH2 terminated surface.

A recently presented chemical vapor deposition (CVD) method involves using plasma electrons as reducing agents for deposition of metals. The plasma electrons are attracted to the substrate surface by a positive substrate bias. Here, we present how a standard quartz crystal microbalance (QCM) system can be modified to allow applying a DC bias to the QCM sensor to attract plasma electrons to it and thereby also enable in situ growth monitoring during the electron-assisted CVD method. We show initial results from mass gain evolution over time during deposition of iron films using the biased QCM and how the biased QCM can be used for process development and provide insight into the surface chemistry by time-resolving the CVD method. Post-deposition analyses of the QCM crystals by cross-section electron microscopy and high-resolution x-ray photoelectron spectroscopy show that the QCM crystals are coated by an iron-containing film and thus function as substrates in the CVD process. A comparison of the areal mass density given by the QCM crystal and the areal mass density from elastic recoil detection analysis and Rutherford backscattering spectrometry was done to verify the function of the QCM setup. Time-resolved CVD experiments show that this biased QCM method holds great promise as one of the tools for understanding the surface chemistry of the newly developed CVD method.

Group 11 thin films are desirable as interconnects in microelectronics. Although many M-N-bonded Cu precursors have been explored for vapor deposition, there is currently a lack of suitable Ag and Au derivatives. Herein, we present monovalent Cu, Ag, and Au 1,3-di-tert-butyltriazenides that have potential for use in vapor deposition. Their thermal stability and volatility rival that of current state-of-the-art group 11 precursors with bidentate M-N-bonded ligands. Solution-state thermolysis of these triazenides yielded polycrystalline films of elemental Cu, Ag, and Au. The compounds are therefore highly promising as single-source precursors for vapor deposition of coinage metal films.