35 Chemical Vapor Deposition 35.1 Introduction 35-1 35.2 Process. 35-1 35.3 Applications 35-3 Deepak G. Bhat 354 Summary’ 35-9 GTE Valente Corporation Bibliography 35-10 35.1 Introduction Chemical vapor deposition (CVD) is a technique of modifying properties of surfaces of engineering components by depositing a layer or layers of another metal or compound through chemical reactions in a gaseous medium surrounding the component at an elevated temperature. In formal terms, CVD. may be defined as a technique in which a mixture of gases interacts with the surface of a substrate at a relatively high temperature, esulting in the decomposition of some of the constituents of the ges mixture and the formation of a solid film of coating of a metal or a compound on the substrate 35.2 Process ‘A modern CVD system includes a system of metering a mixture of reactive and carrier gases, a heated. reaction chamber, and a system for the treatment and disposal of exhaust gases. Figure 35.1 shows the basic arrangement of various components of industrial CVD systems. ‘The gas mixture (which typically consists of hydrogen, nitrogen, or argon, and reactive gases such as ‘metal halides and hydrocarbons) is carried into a reaction chamber that is heated to the desired temper- ature by suitable means. The various techniques include resistance heating with Kanthal, Globar (SiC) or graphite heating elements, or induction. In some cases, the substrate is heated directly by passing an electric current through it, ‘Typical operating parameters for a conventional CVD process are shown in Table 35.1, Different variations of the conventional method have been developed over the last few decades. These include ‘moderate-temperature CVD (MTCVD), plasma-assisted CVD (PACVD), and laser CVD (LCVD). In the MICVD process, the reaction temperature is reduced to below about 850°C by the use of metalorganic compounds as precursors. Therefore, this technique is also referred to as metalorganic CVD (MOCVD). In the microelectronics field where this technique of widely used, it is also commonly referred to as ‘organometallic vapor phase epitaxy (OMVPE). In the PACVD technique, the heating of the gas mixture is accomplished by creating a high energy plasma that activates the chemical reactions at considerably reduced temperatures as compared to the conventional CVD. In the case of LCVD techniques, the same effect is achieved by using a laser beam to heat the gas volume or the substrate,35.2 Coatings Technology Handbook, Third Edition c To e Vent @|/o b FIGURE 35.1 Schematic diagram showing various components of a typical chemical vapor deposition system operating at one atmosphere pressure: I: Reactor, 2: Heating elements, 3: Reaction chamber, 4: Wat cooled end cursor gas 9: Metal halide (Liqui) vaporizer, 12: Particulate tap, 13: Gas scrubber, 14: Flow meters, 15: low control valves, 16: Gas tank regulators, 17: Substrate support, 1: Substrate. Fora system operating at low pressures, the ‘acum pumping system is connected betwsen 12 and 13. flanges, 5: Power controller, 6: Pressure gauge, 7: Temperature sensor and controller, 8, 10, and 11 ‘TABLE 35.1 Typical Parameters in Conventional Chemical Vapor Deposition “Temperature Pressure Precursors 2SOO"Crypically upto <0 tore to 1 Reactive gases: metal halides, carbonyls] 000% Reducing gses:H Inert gets At N, Other gases CH, CO,, NH, other hydrocarbons All CVD systems requite a mechanism by which the products of the chemical reaction are treated. ‘These products contain various reactive and potentially hazardous constituents, as well as particulate matter, which must be trapped and neutralized before the gases are exhausted to the atmosphere. In addition, as most CVD processes are carried out at subatmospheric pressures, the pumping equipment ‘must be protected from the relatively hot, corrosive gases. This is usually done by using nonreactive materials for the pump components. ‘The deposition of coatings by CVD can be achieved in a number of ways. The chemical reactions utilized in CVD are shown in Table 35.2. These reactions between various constituents occur inthe vapor phase over the heated substrate, and a solid film is deposited on the surface. The coatings are, therefore, termed “overlay” coatings. On the other hand, a surface film can also be deposited by causing a reaction between the substrate surface and one or more of the constituents of the vapor phase. One example of this technique is the formation of a nickel aluminide film on the surface of nickel by a reaction of aluminum trichloride and hydrogen from the vapor with the sueface of nickel at a high temperature Such a coating may, therefore, be called a conversion coating.Chemical Vapor Deposition 35.3 ‘TABLE 35.2 Chemical Reactions in CVD Reaction Equation ‘Thermal decomposition, or pyrolysis CHSICl, SiC + 3HCL Reduction WE43HP 3 W + 6HE Oxidation Si, +0, — 80, + 2H, Hydrolysis BAC + 34,0 ALO, 6H Coreduction TiC + 28C1, + 5H, THB, + 10H ‘TABLE 35.3 Typical Materials Deposited by CVD Material Example Meals AAs, Be, Bi, Co, Cx, Ca, Fe, Ge HE, ly Mo, Nb, Ni, Os, Pb F,Re, Rh, Ru, Sb, Si, Sn T,Th, TU V,W, 2 also caybon and boron Compounds Vi and II-V compounds, borides, carbides, sittdes, and slides of tansion ‘metals ela ude, phosphdesauninides, Ceramics _AL.O,,AIN, B.O,, BN, SIC SiN, UO, ¥.0, 210, ‘TABLE 35.4 Applications ofthe CVD Technique “Tiblogial coatings Decorative file Wear-resistant costings Superconducting fms High-temperature coatings for oxidation resistance Emisive coatings Distecric insulating fms Coatings for fiber composites Opticallefctive fils Freestanding suctural shapes Photovoltaic films Powders and whiskers 35.3. Applications ‘The CVD technique is applicable for the deposition of a wide variety of materials, such as metals, compounds, ceramics, powders, and whiskers. Typical materials deposited by CVD and applications of the CVD technique are summatized in Table 35.3 and Table 35.4. One of the earliest applications of CVD. was in the manufacture of pigments, Powders of TiO,, SiO. carbon black, and other materials such as AL,O,, Si,Ny and BN, have been routinely made by CVD. In a vatiation of the conventional CVD. technique, powders of nuclear fuel materials from the fuel rods used in nuclear reactors have been coated. in a fluidized bed with coatings of SiC, graphite, and Zr for containment of fission products, Because of the nature of the process, CVD is used to deposit high-purity metals from their halide or carbonyl precursors, and the technique has been especially useful for synthesizing refractory metals. The most commonly used precursors for CVD are metal halides. For a successful application of CVD, i is necessary to be able to decompose the halides at relatively moderate temperatures (e-.,<1000°C). Thus, ‘many metals with halides that are stable inthis temperature range are difficult to deposit successfully. In ‘many of these cases, organometallic compounds have been used successfully. Typical examples of metallic components deposited by CVD are shown in Figute 35.2 In recent years, another interesting application of the CVD technology has achieved prominence Deposition of whiskers of metals and refractory compounds is of significant technological importance because of the potential for development of composite materials. Composites have become a very important new class of engineering materials for aerospace structural applications. ‘Whiskers are needle-shaped single crystals of materials, typically 1 yim of less in diameter and several ‘micrometers long. It has been demonstrated that the addition of whiskers to ceramics, which are inher: ently brite, significantly improves their fracture toughness. Various refiactory compounds have been deposited in the form of whiskers by CVD. These include Al,O,, Cr,Cy SiC, SiN TiB,, TIC, TIN, Z1C, ZN, and Z1O,, Figure 35.3 shows an example of TIC whiskers deposited by CVD. It is to be expected.354 Coatings Technology Handbook, Thied Edition FIGURE 38.2. Metallic compounds deposited by CVD. (A) Iriim-coated rhenium thrust chamber for liguid rockets, 75 mm major diameter 175 mm length > 0.75 mim wal thickness; (B) Tungsten crucible, 325 mm diameter % 575 mm height x 1 mm wall thickness; (C) Tungsten manifold, about 175 mm long. (Photographs courtesy of Utramet Corporation, Pacoima, California reprinted with permission, Figure 2 of “A review of chemical vapor ‘deposition techniques, materials & applications” by D. G. Bhat, Surface Modification Technologies, pp. 1-21, The “Metalurgieal Society, 420 Commonwealth Drive, Warrendale, PA 15086) that with the increasing prominence of the composite materials in the advanced engineering components, ‘many more materials will be synthesized in the whisker and fiber forms for these applications. ‘Asstated earlier, the conventional CVD calls for relatively high temperatures. This requirement imposes certain limitations on the type of substrate that can be successfully used for deposition. Typically, most ceramic materials, graphite, and refractory metals such as tungsten and molybdenum are found to be Auite suitable hecause oftheir high thermal and chemical stability in typical CVD process environments Steels have also heen used successfully, but certain precautions must be taken for best results. For example, ‘most steels other than austenitic or ferritic steels undergo solid state phase transformation in the 700 to 800°C temperature range. This transformation is accompanied by changes in microstructure, physical properties, and dimensions that could be detrimental for the coating or the component in the intended application. In addition, the chemical stability of steel may be compromised in some CVD coating operations, as inthe case of tungsten deposition as a result ofthe reaction of steel with the fluoride gases. ©2009 Tyr Ar Gap.Chemical Vapor Deposition 35.5 FIGURE 35.3 Scanning electron micrograph showing whiskers of TiC deposited by CVD from a gas mixture containing TiC), H, and CH, at about 1100°C. The formation of whiskers is enhanced by nickel, which acts as a catalyst during the growth of whiskers bythe vapor-liqui-solid (VIS) mechanism. Methods to avoid these possibilities exist; for example, one can deposit a film of nickel by electrolytic oF electroless means to protect the substrate, Figure 35.4 shows an example ofa stainless steel compressor blade coated with a CVD tungsten carbide coating by a moderate-temperature CVD process. The com ponent was electroless nickel plated before CVD. ‘One of the most widely known and practiced applications of CVD is in the manufacture of coated cemented carbide cutting tools. These tools are made of tungsten carbide-cobalt alloys on which a weae: resistant coating of a refractory compound is applied by CVD. The commonly used coatings include TiC, TIN, and Al,O, and their combinations. Other coatings include Ti(C.N), TaC, HIN, and ZiN. Figure 35.5 shows several cemented carbide cutting tool inserts coated with TiC and TN. Another application of wear-resistant CVD coatings is in areas involving erosion and abrasion, such as sand blast nozzles, slurry transport and handling equipment, coal gasification equipment, and mining equipment. In these applications, air- or waterborne particles of sand, fly ash, or other particulate matter traveling at speed and under pressure can cause abrasion and erosion of surfaces they contact. Conven- tionally, many ofthese surfaces are protected by applying wear-resistant coatings by various means, such as electroplating, lame or plasma spraying, laser cladding, and weld overlay coating techniques. Chemical vapor deposition has also been used successfully in many of the applications, The graph in Figure 35.6 shows the relative wear rates of various coatings, other hardfacing materials, and ceramics against sand, indicating that CVD coatings can be successfully used in these applications ‘Tribological coatings present another use for CVD coatings: to improve the coefficient of friction between sliding or rolling surfaces in contact, thereby reducing wear due to adhesion, abrasion, or other causes. Typical coatings used in these applications include refractory compounds such as carbides, nitrides, and borides of transition metals. The important properties of coatings in these applications include hardness, elastic modulus, fracture toughness, adhesion, grain size, and to a certain extent, chemical stability depending on the service environment ‘One of the elegant applications of CVD tribological coatings is for ball bearings. As shown in Figure 35.7, the wear resistance and service life of a stel ball bearing improved dramatically when either the balls, or the races were coated with CVD TiC. Other applications of tribological coatings include various steel components such as coatings on dies used in molding, extrusion, and similar metalworking operations35.6 Coatings Technology Handbook, Third Edition FIGURE 35.4 Photography shoving a 17-4 PH stainless steel compressor blade coated with a tungsten carbide coating in a MTV process. The blade is frst coated with a interlayer of nickel by electrolytic or electroless plating ive action of hydeofluoric acd gas generated during the deposition reaction. techniques to protect from the cor FIGURE 35.5. Photography showing cemented tungsten carbide cutting tool inserts costed with TiC and TIN coating ina conventional CVD process. These coatings impart improved wea resistance to the carbide tools, allowing them to run at higher speeds and chip loads in the machining of various materials ‘Coatings used for high-temperature applications require high thermal stability. Refractory compounds having low vapor pressure and high decomposition temperature ate generally suitable in these cases, depending on service environment, Other properties, such as abe an thermal shock resistance, and compatible thermal expansion characteristic, are also important. Thus, typical coatings used in these applications include certain refractory metals, Al,Os, B\C, SIC, SiNy SiO, and refractory metal silcides. Composite coatings such as ALO, + Z:O, 0, +¥,0, have also been studied. Most of these coatings can be deposited by CVD. Typical applications for these coatings include rocket nozzles reentry cones, ceramic heat exchanger components, afterburner parts in rocket engines, and gas turbine and automotive engine components. Another well-known example of a protective refractory coating isthe SiC-coated hardware used in the microelectronics field for manufac- turing coated silicon wafers. Figure 35.8 shows typical examples of graphite susceptor components coated ©. An iridium-coated rhenium thrust chamber for spacecraft was shown in Figure 35.2 oxidation resistance, with $Chemical Vapor Deposition 357 8 Bg oa z 150, a8 vEN Bg we van of . L oe 8 % 0a sez & 2 ae 8 & 5 22 9g 2 2 2m7 g a un 29 g § gs ORE 3 32 GS a 4791 ae 3 ge 2 vn 2S & 6 : z §9 28 3 a $3 32 : 5 asc 3 3 za Sp? 8 u = OB ses op E68 £8 58 og vy gaa 3s a8 hi age 3 1400 2 8 206 vHN a0 S12 OT VIN van VAN 409 vaN z= fe) EE Be) eel ite El ele} ae oL O11 90° 20°90" 20°90" 30°90" 30°90" BOSD" 90" 96" ad" 090" Angle of impingement FIGURE 35.6 Steady state erosive wear rate of ultrafine-grained CVD tungsten-carbon (CM S00L) and SiC (CM ind ceramic. The eroding medium is 200-micron SiC particles impinging at a velocity of 30 ms at oom temperature. [Data from Hickey etal, Thin Soli Films, ol. 118 p. 321 (1984) Reprinted with permission from Elsevier Sequoia, $A, Switzerland. 4000) coatings and other hardacing materials, coatings,35.8 Coatings Technology Handbook, Thied Edition Helium Atmosphere 300 Revolutions at 100 RPM Oo © © © @ Standard ste batbearing complete seizure. @ Standard steel bal bearing wih MoS, spray - complete seizure, ‘all bearing with TiC-coated races - wear ‘of balls but no Seizuce. ‘Ball bearing with TiC-coated balls - wear ‘of races but no seizure FIGURE 35.7 Elfect of CVD TiC coating on the frictional and wear behavior of stel ball bearing com- ponents, (Data from Hintermann, H.E., Thin Solid Films, vol. 84, p. 215 (1981). Reprinted with permis- sion from Elsevier Sequoia, S.A., Switzerland.) FIGURE 35.8. Photograph of graphite susceptor components coated with CVD SiC, These components are used in the microelectronic industry as supports for wafers during deposition of various thin fils. oxy Tay ara a LCChemical Vapor Deposition 35.9 Heating Element Retaining Fing? [Composite Ne Ri Water-Cooled Holder FIGURE 35.9 Schematic diagram showing a technique of chemical vapor infltration of porous fiber preforms, in which a costing of a protective material such as SiC is deposited, In this method, a thermal gradient acrose the preform allows difusion ofthe reactive gas mixture progressively from the hot surface othe cold surface, uniformly coating the preform. (Data from Stinton etal, Ceramic Bulletin, vol. 65, p. 347 (1986). Reprinted with permission feom The American Ceramic Society. In recent years, advances in the technology of carbon-carbon composites have led to the fabrication of components out of these materials, which are then coated by CVD or the new technology of chemical vapor infiltration (CV1) with various refractory compound coatings, most notably SiC. Other ceramic fiber composites based on alumina and silica have also been coated in a similar manner for high temperature service. Figure 35.9 illustrates one of the techniques used for coating of porous fiber preforms by CVL ‘The more exotic CVD techniques that were mentioned earlier, such as PACVD and LCVD, have found important applications for the deposition of new types of coatings. One of the most interesting applica- tions is the deposition of diamond films by PACVD. The diamond films have unique properties and. application potential ranging from wear-resistant coatings for cutting tools to coatings for laser mirrors, fiber-opties, dielectric films, and heat sinks in microelectronic circuits, Figure 35.10 shows an example of a diamond film deposited on silicon, with the characteristic Raman peak at 1332 cm, Coatings deposited by the LCVD technique find applications in laser photolithography, repair of VLSIC masks, laser metallization, and laser evaporation deposition, 35.4 Summary ‘The chief characteristics of CVD may be summarized as follows: 1. The solid is deposited by means of a vapor phase chemical reaction between precursor compounds in gaseous form at moderate to high temperatures. 2. The process can be carried out at atmospheric pressure as well as at low pressures. 3, Useof plasma and laser activation allows significant energization of chemical reactions, permitting deposition at very low temperatures 4. Chemical composition of the coating can be varied to obtain graded deposits or mixtures of coatings35-10 Coatings Technology Handbook, Third Edition c Raman Spectrum of ‘Diamond Film 12 Diamond 19 1392 i Substrate 519 a0 760000 125015001750 Wavenumbers Laser 50 MW. $14,532 NM. Sits: 200 Mic. Date: Junea7 1 Scan (8). Time: 1 SeclPT, PTS Spaced by 1 Wavenumbers FIGURE 35.10. Photographs showing diamond crystals (A) and polycrystalline diamond film (B) deposited on a silicon wafer substrate by microwave plasma-enhanced CVD, from a gas mixture containing hydrogen and methane. “The Raman spectrum (C) cleaely shows the characteristic Raman shift for diamond at 1332 cm (Data courtesy of Drs. R Messier, Materials Research Laboratory, The Pennsylvania State University, and P. K. Bachmann, Philips Reseatch Laboratories, Hindhoven, The Netherlands.) 5. Control varaton in densty an purity ofthe coating can be achieved 6. Coatings on sbstas of complex shapes and on parila mats can be deposited ina Aine stem 2. Gas conditions re wally ania resungin thick boundary yest he substrate sure. The depois usualy have «colurcar gun ruture, which i weak in eure, Fine grined, crue deposits can be obtained by gas-phase perturbation of ches ection by various tchnans 9. Coto of yapor phase etions is rica fr ahievng dsl properties in the deposit 10, A wide variety of meals los, ceramic and omounds canbe manfred coatings os fee standing component Its clear that chemical vapor deposition is a versatile technique for the deposition of coatings of a wide variety of materials, as well as for the fabrication of free-standing structural components Bibliography Besmmann, T. M.D. PStnfon, and R.A. Lowden,“Chemical vapor deposition techniques? MRS Bulletin, ‘November 1988 Bhat, D. G, “Chemical vapor depositon” chap. 2, in Surface Modification Technologies — An Engineer’ Guide. S. Sudarshan, Ed, New York: Marcel Dekker, 1989, p. 141 Blocher, |. M.Ji,“Chemical vapor deposition” chap 8, in Deposition Tehologis for Fils and Coatings Developments and Applications. R.F Bunshah etal Eds, Park Ridge, NJ: Noyes Publications 1982, p35, Bryant, W. A, “Chemical vapor deposition,” chap. 6, in Surface Modification Engineering, Vol. 1: Funda- ‘mental Aspects. R. Kossowsky, Ed. Boca Raton, FL: CRC Press, 1989, p. 189,Chemical Vapor Deposition 35-11 Holz, R.A., "Chemical vapor deposition techniques,” Techniques of Materials Preparation and Handling — Part 3 (Techniques of Metals Research Series, vol. 2). RF Bunshah, Fd, New York: Interscience Publishers, 1968, p. 1377. Pierson, H. O. (Ed.), Chemically Vapor Deposited Coatings. Columbus, OH: American Ceramic Society, 1980. Powell, C FJ. H. Oaley, and J. M. Blocher, Jr. (Eds.), Vapor Deposition. New York: John Wiley & Sons, 1966. Yee, KK, International Metals Reviews, Review No. 26 (1978). ©2009 Tyr Ar Gap.