Thin film

A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. Electronic semiconductor devices and optical coatings are the main applications benefiting from thin film construction.

A familiar application of thin films is the household mirror, which typically has a thin metal coating on the back of a sheet of glass to form a reflective interface. The process of silvering was once commonly used to produce mirrors. A very thin film coating (less than a nanometre thick) is used to produce two-way mirrors.

The performance of optical coatings (e.g. antireflective, or AR, coatings) are typically enhanced when the thin film coating consists of multiple layers having varying thicknesses and refractive indices. Similarly, a periodic structure of alternating thin films of different materials may collectively form a so-called superlattice which exploits the phenomenon of quantum confinement by restricting electronic phenomena to two-dimensions.

Work is being done with ferromagnetic and ferroelectric^[1] thin films for use as computer memory. It is also being applied to pharmaceuticals, via thin film drug delivery. Thin-films are used to produce thin-film batteries. Thin film application also be adopted on Dye-sensitized solar cell.

Ceramic thin films are in wide use. The relatively high hardness and inertness of ceramic materials make this type of thin coating of interest for protection of substrate materials against corrosion, oxidation and wear. In particular, the use of such coatings on cutting tools can extend the life of these items by several orders of magnitude.

Research is being done on a new class of thin film inorganic oxide materials, called amorphous heavy-metal cation multicomponent oxides, which could be used to make transparent transistors that are inexpensive, stable, and environmentally benign.^[2]

Deposition

The act of applying a thin film to a surface is thin-film deposition - any technique for depositing a thin film of material onto a substrate or onto previously deposited layers. "Thin" is a relative term, but most deposition techniques control layer thickness within a few tens of nanometres. Molecular beam epitaxy allows a single layer of atoms to be deposited at a time.

It is useful in the manufacture of optics (for reflective, anti-reflective coatings or self-cleaning glass, for instance), electronics (layers of insulators, semiconductors, and conductors form integrated circuits), packaging (i.e., aluminium-coated PET film), and in contemporary art (see the work of Larry Bell). Similar processes are sometimes used where thickness is not important: for instance, the purification of copper by electroplating, and the deposition of silicon and enriched uranium by a CVD-like process after gas-phase processing.

Deposition techniques fall into two broad categories, depending on whether the process is primarily chemical or physical.

Chemical deposition

Here, a fluid precursor undergoes a chemical change at a solid surface, leaving a solid layer. An everyday example is the formation of soot on a cool object when it is placed inside a flame. Since the fluid surrounds the solid object, deposition happens on every surface, with little regard to direction; thin films from chemical deposition techniques tend to be conformal, rather than directional.

Chemical deposition is further categorized by the phase of the precursor:

• Plating relies on liquid precursors, often a solution of water with a salt of the metal to be deposited. Some plating processes are driven entirely by reagents in the solution (usually for noble metals), but by far the most commercially important process is electroplating. It was not commonly used in semiconductor processing for many years, but has seen a resurgence with more widespread use of chemical-mechanical polishing techniques.

• Chemical solution deposition (CSD) uses a liquid precursor, usually a solution of organometallic powders dissolved in an organic solvent. This is a relatively inexpensive, simple thin film process that is able to produce stoichiometrically accurate crystalline phases. This technique is also known as the sol-gel method because the 'sol' (or solution) gradually evolves towards the formation of a gel-like diphasic system.

• Chemical vapor deposition (CVD) generally uses a gas-phase precursor, often a halide or hydride of the element to be deposited. In the case of MOCVD, an organometallic gas is used. Commercial techniques often use very low pressures of precursor gas.
  • Plasma enhanced CVD (PECVD) uses an ionized vapor, or plasma, as a precursor. Unlike the soot example above, commercial PECVD relies on electromagnetic means (electric current, microwave excitation), rather than a chemical reaction, to produce a plasma.

Physical deposition

Physical deposition uses mechanical, electromechanical or thermodynamic means to produce a thin film of solid. An everyday example is the formation of frost. Since most engineering materials are held together by relatively high energies, and chemical reactions are not used to store these energies, commercial physical deposition systems tend to require a low-pressure vapor environment to function properly; most can be classified as physical vapor deposition (PVD).

The material to be deposited is placed in an energetic, entropic environment, so that particles of material escape its surface. Facing this source is a cooler surface which draws energy from these particles as they arrive, allowing them to form a solid layer. The whole system is kept in a vacuum deposition chamber, to allow the particles to travel as freely as possible. Since particles tend to follow a straight path, films deposited by physical means are commonly directional, rather than conformal.

Examples of physical deposition include:

• A thermal evaporator uses an electric resistance heater to melt the material and raise its vapor pressure to a useful range. This is done in a high vacuum, both to allow the vapor to reach the substrate without reacting with or scattering against other gas-phase atoms in the chamber, and reduce the incorporation of impurities from the residual gas in the vacuum chamber. Obviously, only materials with a much higher vapor pressure than the heating element can be deposited without contamination of the film. Molecular beam epitaxy is a particularly sophisticated form of thermal evaporation.
  • An electron beam evaporator fires a high-energy beam from an electron gun to boil a small spot of material; since the heating is not uniform, lower vapor pressure materials can be deposited. The beam is usually bent through an angle of 270° in order to ensure that the gun filament is not directly exposed to the evaporant flux. Typical deposition rates for electron beam evaporation range from 1 to 10 nanometres per second.

• Sputtering relies on a plasma (usually a noble gas, such as argon) to knock material from a "target" a few atoms at a time. The target can be kept at a relatively low temperature, since the process is not one of evaporation, making this one of the most flexible deposition techniques. It is especially useful for compounds or mixtures, where different components would otherwise tend to evaporate at different rates. Note, sputtering's step coverage is more or less conformal.It is also widely used in the optical media. The manufacturing of all formats of CD, DVD, and BD are done with the help of this technique. It is a fast technique and also it provides a good thickness control. Presently, nitrogen and oxygen gases are also being used in sputtering.

• Pulsed laser deposition systems work by an ablation process. Pulses of focused laser light vaporize the surface of the target material and convert it to plasma; this plasma usually reverts to a gas before it reaches the substrate.

• Cathodic arc deposition (arc-PVD) which is a kind of ion beam deposition where an electrical arc is created that literally blasts ions from the cathode. The arc has an extremely high power density resulting in a high level of ionization (30-100%), multiply charged ions, neutral particles, clusters and macro-particles (droplets). If a reactive gas is introduced during the evaporation process, dissociation, ionization and excitation can occur during interaction with the ion flux and a compound film will be deposited.

• Electrohydrodynamic deposition (Electrospray deposition) is a relatively new process of thin film deposition. The liquid to be deposited, either in the form of nano-particle solution or simply a solution, is fed to a small capillary nozzle (usually metallic) which is connected to a high power source. The substrate on which the film has to be deposited is connected to the ground terminal of the power source. Through the influence of electric field, the liquid coming out of the nozzle takes a conical shape (Taylor cone) and at the apex of the cone a thin jet emanates which disintegrates into very fine and small positively charged droplets under the influence of Rayleigh charge limt. The droplets keep getting smaller and smaller and ultimately get deposited on the substrate as a uniform thin layer.^[3]

Other deposition processes

Some methods fall outside these two categories, relying on a mixture of chemical and physical means:

• In reactive sputtering, a small amount of some non-noble gas such as oxygen or nitrogen is mixed with the plasma-forming gas. After the material is sputtered from the target, it reacts with this gas, so that the deposited film is a different material, i.e. an oxide or nitride of the target material.

• In molecular beam epitaxy (MBE), slow streams of an element can be directed at the substrate, so that material deposits one atomic layer at a time. Compounds such as gallium arsenide are usually deposited by repeatedly applying a layer of one element (i.e., gallium), then a layer of the other (i.e., As), so that the process is chemical, as well as physical. The beam of material can be generated by either physical means (that is, by a furnace) or by a chemical reaction (chemical beam epitaxy).

• In topotaxy, a specialized technique similar to epitaxy, thin film crystal growth occurs in three dimensions due to the crystal structure similarities (either heterotopotaxy or homotopotaxy) between the substrate crystal and the growing thin film material.

Thin-film photovoltaic cells

Further information: Thin film solar cell, Third generation solar cell, and Low-cost photovoltaic cell

Thin-film technologies are also being developed as a means of substantially reducing the cost of photovoltaic (PV) systems. The rationale for this is that thin-film modules are cheaper to manufacture owing to their reduced material costs, energy costs, handling costs and capital costs. This is especially represented in the use of printed electronics (roll-to-roll) processes.

Thin films belong to the second and third photovoltaic cell generations.

Thin-film batteries

Thin-film printing technology is being used to apply solid-state lithium polymers to a variety of substrates to create unique batteries for specialized applications. Thin-film batteries can be deposited directly onto chips or chip packages in any shape or size. Flexible batteries can be made by printing onto plastic, thin metal foil, or paper.^[4]

See also

• Dual Polarisation Interferometry
• Ellipsometry
• Hydrogenography
• Kelvin probe force microscope
• Microfabrication
• Organic LED
• Sarfus
• Thin-film interference
• Thin-film optics
• Virtual Institute of Nano Films

References

1. ^ Thinfilm and InkTec awarded IDTechEx' Technical Development Manufacturing Award IDTechEx, April 15th 2009
2. ^ "Major advance made in transparent electronics". December 28, 2004. http://www.eurekalert.org/pub_releases/2004-12/osu-mam122804.php. Retrieved 2009-09-09. 
3. ^ CIS layer deposition through electrospray process for solar cell fabrication
4. ^ Flexible Cell Construction

Further reading

• Anders, Andre (editor) "Handbook of Plasma Immersion Ion Implantation and Deposition" (2000) Wiley-Interscience ISBN 0-4712-4698-0
• Bach, Hans and Dieter Krause (editors) "Thin Films on Glass" (2003) Springer-Verlag ISBN 3-540-58597-4
• Birkholz, M., with contributions by Fewster, P. F. and Genzel, C. "Thin Film Analysis by X-ray Scattering" (2006) Wiley-VCH, Weinheim ISBN 3-527-31052-5
• Bunshah, Roitan F (editor). "Handbook of Deposition Technologies for Films and Coatings", second edition (1994)
• Glaser, Hans Joachim "Large Area Glass Coating" (2000) Von Ardenne Anlagentechnik GmbH ISBN 3-00-004953-3
• Glocker,and I. Shah (editors), "Handbook of Thin Film Process Technology", Vol.1&2 (2002) Institute of Physics ISBN 0 7503 0833 8 (2 vol. set)
• Mahan, John E. "Physical Vapor Deposition of Thin Films" (2000) John Wiley & Sons ISBN 0-471-33001-9
• Mattox, Donald M. "Handbook of Physical Vapor Deposition (PVD) Processing" (1998) Noyes Publications ISBN 0-8155-1422-0
• Mattox, Donald M. "The Foundations of Vacuum Coating Technology" (2003) Noyes Publications ISBN 0-8155-1495-6
• Mattox, Donald M. and Vivivenne Harwood Mattox (editors) "50 Years of Vacuum Coating Technology and the Growth of the Society of Vacuum Coaters" (2007), Society of Vacuum Coaters ISBN 978-1-878068-27-9
• Westwood, William D. "Sputter Deposition", AVS Education Committee Book Series, Vol. 2 (2003) AVS ISBN 0-7354-0105-5
• Willey, Ronald R. "Practical Monitoring and Control of Optical Thin Films (2007)" Willey Optical, Consultants ISBN 978-6151-3760-5
• Willey, Ronald R. "Practical Equipment, Materials, and Processes for Optical Thin Films" (2007) Willey Optical, Consultants ISBN 978-6151-4397-2
• Ohring, Milton "Materials Science of Thin Films: Deposition and Structure" 2nd edition (2002) Elsevier, Inc. ISBN 978-0-12-524975-1