ISSN 0917-2440 PROCEEDINGS THE SECOND INTERNATIONAL SYMPOSIUM ON SPUTTERING & PLASMA PROCESSES ~ ISSP'93 ~ ' SUBJECT: Fundamentals of Sputtering and its . Applications for Electronic Materials i May 27-28, 1993 | TOKYO, JAPAN i | 1 \ { ' ORGANIZED BY: ISSP'93 Committee SUPPORTED BY: ‘The Study Committee of Sputtering and Plasma Processes, Japan Technology Transfer Association WITH THE COOPERATION OF: The Japan Society of Applied Physics ‘The Vacuum Society of Japan ‘The Surface Science Socicty of Japan ‘THE SURFACE FINISHING SOCIETY OF JAPAN ‘The Ceramic Society of Japan ‘The Magnetics Society of Japan ‘The Materials Science Society of Japan The Institute of Electrical Engineering of Japan ‘THE INSTITUTE OF ELECTRONICS, INFORMATION AND COMMUNICATION ENGINEERSTHE ROLES OF ELECTRICALLY CHARGED PARTICLES AND ELECTRICAL FIELDS IN PLASMA POLYMERIZATION Georgy K. Vinogradov Department of Electrical Engineering and Electronics Nagoya University, Nagoya 464-01 Japant ANTRODUCTION Plasma-surface interactions in any kind of low pressure processing for film deposition, etching or modification are carried out through the bombardment of the surface with neutral and electrically charged particles. Namely these fluxes determine surface processes, but their formation occurs in a bulk plasma and in other areas (target in case of sputtering}. Traditionally PVD mechanisms are de- scribed as an “atomic billiard". Deposition and etching systems demonstrate re- sults far from that description due to much more complicated systems involving chemical reactions batween several initial components or their products both in a gas phage and on the surface. And one of the most complicated plasma chemical object may be represented by a plasma polymerization. Gas phase and surface pro- cesses ara strongly overwhelmed here, and beside this, organic films are very Sensitive for any kind of external influences in compare with inorganic materi- als. It makes investigations of the plasma polymerization very complex and some- time speculative, but it gives a principal possibility to find out such effects, which are below the level of sensitivity in case of inorganic materials, but still playing their role in a formation of film properties and fine structures. ‘The mechanism of film formation during the plasma polymerization involves both electrically charged and neutral particles bombarding the surface. There were many attempts to ascribe the key role in the process to one or another kind of particles, mainly to positive ions or free radicals, because there are two main traditional mechanisns of. chain polymerization well developed in a polyner chemistry. Numerous experimental data were derived suggesting for a participation of positive ions and free radicals in the process [1-4]. However, it appears to be the mechanism of plasea polymerization is very multifarious. It can not be treated from the stand point of a polymer chemistry. ‘Thermodynamic approaches also are absolutely invalid in case of non-equilibrium plasma. And at last, films formed under plasma conditions are not polymers, but rather high molecular weight randomly crosslinked materials. The mechanisns of piasma polymerization can not be derived from investigations of the structure of these highly integrated solid state products. And the only valid approach to disclose these phenomena seems to be the basic kinetic studies [5,6]. Naturally the mechanism of the process involves two general spheres of physical processes and chemical reactions: bulk plasma and surface. Here we would like to concentrate on surface heterogeneous processes, their diagnostics and general conclusions following mainly from the original experimental data. The approach and diagnostic tools, as well as the basic results proposed here, used to be relevant for various discharge systems and thin film processes. ELECTRIC KINETIG PROBES Systematic studies of heterogeneous stages of plasma polymerization have been carried out to reveal the role of electrically charged particles in film formation. It appears to be possible due to the development of a set of original methods of electrical probes which allow us to disrupt a self-consistency of pla~ sma chemical object to change independently charged particles fluxes on to the surface without essential variations of a surrounding plasma and neutral fluxes to reveal by this way their effect on surface phenomena. In other words, we wouldlike to establish and vary only a weak interaction of the object with a probe surface, but not to change the object itself. Intrinsic discharge parameters are essentially self-consistent including an interacting surface. There is no way to change one of the parameters without corresponding variations of others. Hence there is no way to reveal and prove mechanisms of plasma-surface interactions through an investigation of correlati- ons between external discharge parameters and surface phenomena. The recent know- Jeage of plasma chemistry.and physics is not adequate to describe variations of internal plasma parameters depending on the external with necessary degree of Precision. Langnuir probes are the most powerful unique tools for a local plasma diagnostics. However, they are also very sensitive for any sucface contaminations as Well. It was easy to detect less than one monolayer of a silicon dioxide sput- tered onto the thin probe in a discharge [7] or thin plasma polymerized layers [8). A small size of Langmuir probes makes them enable to assign I-V characteris- tics or measured particles fluxes bombarding the surface of the probe to the ele- ctron energy distribution function in a bulk plasma and some characteristics of positive ions. From another standpoint definite information concerning the fluxes of charged particles bombarding the probe surface may be assigned immediately to characterize the surface processes. Hence it is possible to atudy correlations between the parameters of charged particles bombarding the surface and film growth, etching or modification kinetics in that case when the kinetics of film Processing would be controlled on the surface of small electric probes. The principal point consist in that, that any substrate may be considered as a probe interacting with plasma. The only one thing we have to take care is the degree of perturbation of plasma parameters. * Thin probe enables us to change in a great extent an electrical potential of the surface and parameters of charged particles bonbarding the surface without appreciable variations of internal plasma parameters and fluxes of neutral particles. Thus the direct correlations between charged particles fluxes bombard- ing the surface and surface kinetics can be experimentally found to solve essential problems of mechanisms of the plasma-surface interaction and various kinds of plasma-surface processing. Also, non-Langmuir small flat substrates can be used for the kinetic probing as well because of a low degree of perturbations of a bulk plasma, In such case the neutral plasma composition would not be changed too much. The set of in situ methods was developed on the basis of electrical probes sensitive for the formation of surface layers. ‘The basic idea of kinetic probes consist of the use of a bias electric current supplied from a high impedance source instead of usually used bias voltage. It makes exceptional advantages in operations with such probes. In case of dielectric film formation on the surface of the probe its I-V characteristics will be dramatically changing permanently. It is easy to show, that the cross section of the family of I-V curves obtained in different moments of the film growth by the straight line i = const, gives the variation of the voltage drop across the film or the resistivity of the growing film on time. And the only condition must be satisfied, that the probe current is a function of potential difference between the surface and plasma: i = consteF(V-iR) . If V-iR = const, then V,= V-iR= const. Here { - probe current, V ~ probe potential in respect to plasma, R- film resistance, V, - electrical potential of the film surface in respect to plasma. It is easy to see, that keeping the probe potential constant during the dielectric film formation, the surface electric potential will be asymptotically shifting to the floating potential. It means that the kinetics of film formation under a iong enough period of time will show the same conditions of floating electric potential of the surface facing to plasma independently on the initial