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C h emi c al D e p o s i t i onT e c h ni q u e s
Materials with a layer thickness below 1 µm are calledthin ilms, while thicker layers, especially those exceedingdimensions o a transistor in an electronic chip, are deinedas thick ilms. Both thin and thick ilms play an exceptionallyimportant role as elements o electronic and optical devices,computer memory chips, and in other related applications.Additionally, in the case o ceramic ilms, properties such aschemical resistivity and hardness enable their use as coatingson substrate materials and cutting tools or protection againstcorrosion, oxidation, and wear.Typically, CVD/ALD techniques are methods o choice orthe deposition o thin ilms on inorganic substrates, whilesolution-based sol-gel approaches are considered when thickilms or nano-powders are desired. Also, lower equipmentcost and reasonably good conormality o coatings may makesol-gel a low-cost alternative to CVD/ALD. However, the ALDapproach may be required or the preparation o uniormconormal ilms on complex suraces such as those with highaspect ratios.Usually, the nature o the deposition process determines theway in which the thickness o the ilm is controlled. Thus, inconventional CVD, the ilm growth depends on the depositiontime, while in ALD it is controlled by the number o depositioncycles.
In sol-gel processing, the ilms are created using twomajor approaches – spin coating or dip coating. In the irstcase, the substrate is spun at an angular speed
and theprecursor (sol) is directed onto its surace along the rotationaxis. The thickness (
) o the created ilms depends on acomplex combination o the sol’s properties and the rotationspeed o the substrate. In practice, they can be predictedusing a semi-empirical ormula
where A and B are empirical coeicients. The dip coatingprocess consists o the successive dipping and withdrawal othe substrate in and out o the solution. The thickness o theilm obtained in one dipping-withdrawal cycle is determined
by the properties o the solution, i.e. viscosity (
), density (
),surace tension (
) and the withdrawal speed (
}While CVD/ALD techniques produce thin ilms o highuniormity and metal purity, sol-gel processing provides aunique and simple approach to tuning the ilm’s chemicalcomposition and morphology. Sol-gel processing can also oera less expensive alternative to CVD/ALD, especially i in situdoping is required.An example, when solution processing has been usedsuccessully as an alternative to CVD/ALD was in thepreparation o silicon thin-ilm transistors where thedeposition o a polycrystalline silicon used a liquid precursor,cyclopentasilane (Si
The grain size in the ilms obtainedwere ound to be as low as 300 nm, comparable to that orilms typically prepared by CVD. Dr. Viktor P. BalemaSigma-AldrichMaterials ScienceDuring the last decade, chemical deposition techniques haveplayed an exceptionally important role in the design andmanuacture o novel advanced devices. Physical depositiontechniques, such as molecular beam epitaxy (MBE), physicalvapor deposition (PVD) or sputtering, have been used orthese applications. However, they suer rom limitations suchas poor conormality, low throughput, restricted directionalvariation, and reduced compositional control. All o theseissues can and have been addressed using chemical depositiontechniques which oer additional advantages such as ultra-thin ilm growth. This is especially the case when layeredinorganic materials are assembled in order to create anelectronic chip or to modiy the surace o a tool or improvedperormance and durability. Currently, two groups o dierent,yet related, techniques dominate the ield. The irst groupcomprising Chemical Vapor Deposition (CVD) and AtomicLayer Deposition (ALD) uses a gas phase to transport volatilemolecules to the surace serving as a substrate. The secondgroup o deposition techniques, called Chemical SolutionDeposition or Sol-Gel Processing, uses a liquid phase as themass transer media.There is a undamental resemblance between these twogroups - the way that the inal material is created. In bothcases, molecules o chemical compounds serving as precursorsare delivered to the substrate surace and chemically modiiedto obtain the desired ilm. It should be noted, however, thatthe chemical transormations o the precursor in the caseo CVD/ALD can occur in the gas phase and at the gas-solid interace, while in sol-gel processing it is carried out insolution (
). In the CVD/ALD approach, the chemicalmodiication o the precursor is usually achieved via thermalconversion o precursor molecules and/or their reactions withmolecules o other volatile precursors, or reactive gases suchas oxygen or hydrogen.
Sol-gel processing consists o asequence o chemical transormations in solution and solid-state. They include ormation o a colloidal suspension in anappropriate solvent (sol), gelation (gel), evaporation o thesolvent (drying), and thermal treatment (sintering).
. Schematic illustrating chemical deposition o ceramic ilms.
Chemical Deposition Techniques in Materials Design