This paper reviews the low-pressure (<10 Pa), high-density plasma-assisted nitriding processes recently developed for metallurgical surface modification to improve wear, hardness and fatigue resistance of ferrous and non-ferrous materials. For that purpose, plasma generation is most frequently ensured by d.c. glow discharges at relatively high pressure (100–1000 Pa) with the underlying limitations associated with this technology. Nevertheless, more flexibility and control are required for plasma nitriding of promising non-ferrous materials such as titanium, aluminium and their alloys. These requirements are fulfilled by the recently developed enhanced or intensified plasma nitriding processes that operate at lower pressures (<10 Pa) such as: thermionically assisted d.c. triode arrangements (TAT), plasma immersion ion implantation (PIII) or plasma source ion implantation (PSII), electron cyclotron resonance (ECR) systems and thermionic arc discharges (TAD). The purpose of this paper is to review these new nitriding processes from both technological and fundamental points of view. Plasma parameters and plasma–surface interactions are considered for these processes.

Low-pressure, high-density plasma nitriding: mechanisms, technology and results

Distributed electron cyclotron resonance or DECR, a new plasma excitation technique well adapted to microwave multipolar plasmas, is described. The novel reactor concept is based upon the use of several microwave linear applicators working at the ECR mode along the multipolar confinement magnets. At a microwave frequency of 2.45 GHz, large volumes of highly homogeneous plasmas with an electron temperature of the order of 3 eV and ion densities better than 1011 cm−3 are currently being produced in DECR reactors.

Microwave multipolar plasmas excited by distributed electron cyclotron resonance: concept and performance

Recent developments in plasma assisted physical vapour deposition (PAPVD) processes are reviewed. A short section on milestones in advances in PAPVD covering the time period from 1938 when the first PAPVD system was patented to the end of the 1980s is followed by a more detailed discussion of some more recent advances, most of which have been related to increases in plasma density. It has been demonstrated that the state of the art PAPVD processes operate in a plasma density range of 1011 to 1013 cm-3. In this range a substantial fraction of the plasma consists of ionized film forming species. Hence, the energy of the condensing film forming species can be directly controlled, as opposed to utilizing indirect energy control with, for example, ionized inert gas bombardment. For a large variety of applications ranging from ceramic film synthesis at conditions far from thermodynamic equilibrium to state of the art metallization technology, such direct energy control of the condensing film forming species is of critical importance, and offers the possibility to engineer the coating microstructure and hence the coating properties.

https://iopscience.iop.org/article/10.1088/0022-3727/33/18/201/pdf

Recent developments in plasma assisted physical vapour deposition

Method and device for exciting a plasma using microwaves at the electronic cyclotronic resonance. The device for exciting a gaseous medium by microwaves comprises at least a co-axial structure for introducing the microwave power inside a multipolar confinement structure and at least one antenna coupled to said co-axial structure for the localized introduction of the microwave energy inside said multipolar magnetic confinement structure which comprises a set of permanent magnets creating a network of surfaces having a constant magnetic field and presenting locally an intensity which corresponds to the electronic cyclotronic resonance, and said antenna being positioned on said network of surfaces of constant magnetic field in an area of intensity corresponding to the electronic cyclotronic resonance. The invention finds an application in the creation of a homogenous, isotropic plasma of large volume and high density, which is free of fields in the area of use.

Method and device for exciting a plasma using microwaves at the electronic cyclotronic resonance

A parametric study of the etching of silicon has been performed in a Microwave Multipolar Plasma using an Electron Cyclotron Resonance excitation. The evolution of the anisotropy and etch rate is measured as a function of the SF6 pressure, ion energy (<100 eV) and ion current density collected on the silicon wafers. For a given ion current density and ion energy, perfect anisotropy is obtained below a critical SF6 pressure whereas the etch rate, independent of ion energy and current density, increases proportionally with the SF6 pressure in the domain investigated. These results, corroborated by the mass spectrometry analysis of the reaction products are explained through the diffusion model recently proposed for plasma etching.

A Parametric Study of the Etching of Silicon in SF6 Microwave Multipolar Plasmas: Interpretation of Etching Mechanisms

A plasma etching reactor is described which associates surface magnetic confinement, microwave discharge, and independently controlled substrate biasing. Preliminary measurements show that the reactor produces reactive plasmas allowing anisotropic fine line etching at low ion energy.

Plasma etching in magnetic multipole microwave discharge

Etching of SiO2 in SF6 plasmas: the role of ions and electrons in etching mechanisms

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Plasma etching in magnetic multipole microwave discharge

Etching of SiO2 in SF6 plasmas: the role of ions and electrons in etching mechanisms