Deposition technology is the backbone of thin film technology. It is based essentially on the history of improved adatom energetics, higher deposition rates, thickness uniformity, large area coverage, and of course, cost. This technology can be tracked from thermal evaporation and electrochemical deposition in the 1930’s (starting as early as the 1870’s ) to advanced processes such as atomic layer deposition (ALD) and high power impulse magnetron sputtering (HIPMS). Due to the low energy of evaporated atoms, quality, environmental stability and durability of thin films was initially a major problem. Additionally, since these are nonequilibrium processes, virtually and material composition is possible. Each process has made significant contributions to possible compositions, mechanical properties, electrical properties, optical properties, durability, environmental stability, manufacturability, and advanced applications. And evaporation technology is no exception. Additionally, a wide range of complex multilayer structures, substrate sizes and shapes, complex compositions, functionality, decorative coatings, microstructures and nanostructures is now possible.
Thermal evaporation is a physical vapor deposition (PVD) process that goes back as far as the 1850’s and was the first technology to facilitate numerous thin film applications [1,2]. The first evaporated thin films were probably prepared by Faraday in 1857 when he exploded metal wires in a vacuum . Deposition of thin metal films in vacuum by thermal heating was initiated in 1887 by Nahrwold and employed by Kundt in 1888 to measure refractive indices of these films [4,5]. As early as the 1920’s it was initially used to metallize auto parts, metallize mirrors (including large telescope mirrors), deposit antireflection coatings, and is still used today for a number of advanced applications . Production of fully dense coatings and self-supported shapes by high rate PVD processes started around 1961.
PVD processes, including thermal and electron beam evaporation involve atom-by-atom transfer of material from a source to a substrate. The three general steps in the formation of a deposit can be summarized as:
- Synthesis of the material to be deposited:
- Transition from a condensed phased (solid or liquid) to a vapor phase
- For compounds, a reaction between the components of the compound, some of which may be introduced into the chamber as a gas or vapor
- Transport of the vapors between source and substrate
- Condensation of vapors (and gases) followed by film nucleation and growth
In evaporation and other PVD processes, steps 1 and 3 can be independently controlled, giving the process a high degree of flexibility in controlling structure, properties and deposition rate.
Thermal evaporation (TE) involves resistive heating a solid material inside a high vacuum chamber, taking it to a temperature which vaporizes the material, while electron beam (e beam) evaporation uses an electron beam to heat the source (next Blog). In TE, metal material (in the form of wire, pellets, shot) is fed onto heated semimetal (ceramic) evaporation boats. A pool of melted metal forms in the boat cavity and evaporates into a cloud above the source. Alternatively the source material is placed in a crucible which is radiatively (radio frequency-RF) heated by a resistive filament or the source material may be hung from the filament itself (filament evaporation). MBE is an advanced form of thermal evaporation. Figure 1 shows a schematic of a thermal evaporation system and Figure 2 shows a thermal evaporation source.
This process requires a good vacuum (generally < 10-4 torr), however, even a relatively low vapor pressure is sufficient to raise a vapor cloud inside the chamber. This evaporated material now constitutes a vapor stream, which traverses the chamber and condenses on the substrate, forming a coating or film.
In most processes, source material is heated to its melting point and is liquid, and is usually located in the bottom of the chamber, often in some sort of upright crucible. The metal vapor then rises above this bottom source, and substrates are held inverted in appropriate fixtures at the top of the chamber. Multiple sources are used to deposit alloys, and care must be taken since each material evaporates at a different rate. Although many elements evaporate, a number of materials such as Cr, Cd, Mg, As and C sublime and elements such as Sb, Se and Ti are borderline between evaporation and sublimation . Sn, Al, Ga and Pb have low vapor pressures, just above their melting point while materials such as Cr have high vapor pressures. Although most elements vaporize as atoms, Sb, Sn, C and Se can vaporize in clusters of atoms .
Deposition rates for evaporated materials are generally very high, which minimizes incorporation of impurities into the film and can result in a very fine grain microstructure. Microstructure, durability and environmental stability of thin films to a large extent depends on the energy of the atoms arriving at the substrate. While deposition rates can be very high, thermally evaporated atoms arrive at the substrate with an energy of ~ tenths of eV. Adatom energetics are thus not impressive, which can result in a porous microstructure and poor film adhesion. As a result, high substrate temperatures or ion assist are often required to achieve fully dense and adherent films. Ion assist will be addressed in a future Blog.
- Historical Timeline of Vacuum Coating and Vacuum/Plasma Technology, Society of Vacuum Coaters: svc.org/history of vacuum coating/History-of-Vacuum-Coating.cfm*.
- Donald Mattox, Handbook of Physical Vapor Deposition, Noyes (1998).
- S Ismat et al., Chapter 4, Handbook of Deposition Technologies for Films and Coatings, Science, Applications and Technology, 3rd Ed., Peter M Martin Ed., Elsevier (2010).
- F Soddy, Proc R Soc Lond 78 (1967) 429.
- I Langmeir, J Am Chem Soc 35 (1913) 931.