Surface and Coatings Technology 167 (2003) 226233

YSZ layers by pulsed-MOCVD on solid oxide fuel cell electrodes

Susan P. Krumdiecka,*, Orfeo Sbaizeroa, Angela Bullerta, Rishi Rajb
b a Boulder Material Systems LLC, Boulder, CO, USA Department of Mechanical Engineering, University of Colorado, Boulder, CO, USA

Abstract An experimental pulsed-MOCVD system was used to produce solid zirconia, and yttria-stabilized-zirconia (YSZ) films on porous nickel-cermet samples. A total of six candidate metalorganic precursors for zirconia and three for yttria were investigated. Three precursor solutions for YSZ were identified as desirable for pulsed-MOCVD processing. Under optimal deposition conditions, precursor conversion efficiency of 90% was achieved at film growth rates of 67.5 mm hy1 at deposition temperature of 525 8C. Film growth rates were determined from in situ color shift method, and by scanning electron microscope examination of the deposited layer. Powder X-ray diffraction of the film surface identified the layer as YSZ. Layers deposited on Ni-cermet samples remained intact on cooling. Results for thicker (10 mm or greater) YSZ layers indicate the process could be developed for low-cost solid oxide fuel cell electrodes, but co-development of electrode processing and YSZ electrolyte deposition will be crucial. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Pulsed-MOCVD; YSZ; Solid oxide fuel cell; Zirconium alkoxide precursors

1. Introduction Chemical vapor deposition (CVD) from metalorganic precursors (MOCVD) is a rapidly developing method for producing films and coatings of ceramic materials for a variety of applications. Conventional MOCVD methods employ a heated bubbler in liquid precursor solutions, or heated solid precursors, with a carrier gas to transport precursor vapor into the CVD reaction chamber. MOCVD systems operate either at atmospheric pressure or at low pressure. Higher growth rates are achievable at higher pressure, although high conversion efficiency and coverage uniformity are difficult to achieve, as the growth rate is often limited by precursor diffusion. Uniform coverage is achieved with deposition at low pressure, but the growth rate is usually limited by the precursor supply rate, and thus the range of possible microstructure and film thickness are also limited w1,2x. Control of the precursor flow rate and
*Corresponding author. Department of Mechanical Engineering, University of Canterbury, Private Bag 4800, Christchurch, New Zealand. Tel.: q64-3-364-2987x7249; fax: q64-3-364-2078. E-mail address: s.krumdieck@mech.canterbury.ac.nz (S.P. Krumdieck). 0257-8972/03/$ - see front matter PII: S 0 2 5 7 - 8 9 7 2 0 2 . 0 0 9 0 8 - 8

concentration are major technical challenges to industrial application of MOCVD processes. Yttria-stabilized-zirconia (YSZ) has been identified as the target electrolyte layer material for solid oxide fuel cells (SOFCs) w3x. Several processing routes have been investigated for producing a solid YSZ layer directly on either the air or fuel electrode. The electrodes are porous doped ceramic, or noble metalyYSZ cosintered to a porous structure. Figueras et al. report a standard MOCVD process using beta-diketonate precursors, heated and evaporated from a solid into a carrier gas stream and delivered to a horizontal hot wall reactor w4,5x. Zirconia films from alkoxide precursors dissolved in solvents have been reported by Xue et al. delivered from a heated bubbler w6x and by Kim et al. delivered from a pool nebulizer to the reactor via a carrier gas stream w7x. A solid YSZ layer on porous anode substrate has been produced by Di Giuseppe and Selman using plasma-enhanced MOCVD and subsequent sintering at 1400 8C from zirconium tert-butoxide and yttrium hexafluoroacetylacetonate mixed in the carrier gas stream w8x. The method developed by SeimensWestinghouse, electrochemical vapor deposition (EVD), involves corrosive precursor gasses, high reaction temperatures, low deposition rates, and represents a major component of the cost of fabrication of SOFCs w9x. EVD remains the

2003 Elsevier Science B.V. All rights reserved.

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Fig. 1. Functional schematic of the experimental pulsed-MOCVD reactor chamber with a plot of the reactor pressure through one pulse.

most widely used method of producing functional YSZ electrolytes. Growth rates reported in these studies are in the range of 110 mm hy1 for solid cubic phase YSZ films. The unique reactor system design employed in this research utilizes pulsed liquid injection with ultrasonic atomization into a low pressure, vertical cold-wall reaction chamber to accomplish metalorganic CVD on a horizontal, conductively heated substrate w10,11x. In pulsed-MOCVD, the zirconium and yttrium precursors are mixed together in a solvent solution and the liquid is metered and injected directly into the reactor at timed intervals with no carrier gas. The reactor is continuously evacuated by a rotary vacuum pump, and the liquid is delivered through an ultrasonic nozzle to facilitate flash vaporization. The equipment and controls of pulsedMOCVD are relatively simple, and thus the low cost compared to other CVD processes. In previous research of TiO2 film deposition from titanium isopropoxide, the pulsed process achieved high precursor conversion efficiency (over 90% under optimal conditions) and high growth rates (45 mm hy1) w12x. In this study, the feasibility of pulsed-MOCVD for thin (-20 mm) solid YSZ layers on porous ceramic substrates using commercially available precursors was investigated. While this study does not include optimization of the process for SOFC fabrication, solid YSZ films were prepared on porous Ni-cermet substrates from solution mixtures of zirconium n-propoxide

(ZrnP), and zirconium 2-methyl 2-butoxide (ZrMB) with yttrium methoxyethoxide (YMOE). 2. Experimental The pulsed-MOCVD system, shown in Fig. 1 and described in detail elsewhere w1315x utilizes direct liquid injection of a dilute precursor solution using an ultrasonic nozzle (SonoTek model 8700-120MS) to introduce the precursor into a pyrex glass and stainless steel reactor (6 cm f, 30 cm H). The atomization and film growth processes are clearly visible to the operator as the horizontal susceptor is heated conductively from below. The liquid precursor solutions are prepared in a dry glove box under argon, sealed in delivery bottles in the glove box, and then installed into the pulsed-CVD system where the solution is under constant positive pressure in 99.9% purity argon gas. A computer program controls the function and timing of a set of solenoid valves, which operate to meter a set volume of precursor and inject it into the nozzle at a set pulse rate. Atomized injection of 60 ml of suitable solution into the 800-ml reactor volume at 10 Pa results in a mist cloud that evaporates so quickly as to be unobservable. The pressure rises instantaneously to approximately 1.6 kPa and is pumped back down to the initial pressure within 10 s.

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Table 1 Precursors investigated for pulsed-MOCVD of YSZ Precursor name (abbreviation) Zirconium isopropoxide (ZrIP) Zirconium 2-methyl 2-butoxide (ZrMB) Zirconium n-propoxide (ZrnP) Zirconium ethoxide (ZrEO) Zirconium n-butoxide (ZrnB) Zirconium t-butoxide (ZrtB) Yttrium methoxyethoxide (YMOE) Yttrium(2,2,6,6-tetramethyl-3,5-heptanedionate) (Ythd) Yttrium isopropoxide, (YIP) Supplier Alpha Aesar Gelest Alpha Aesar Gelest Aldrich Gelest Gelest Gelest Strem Cat. no. 2171-98-4 AKZ 965 23519-77-9 AKZ 950 1071-76-7 AKZ 945 AKY 927 AKY 932 39-3000

2.1. Commercial precursor suitability A suitable precursor for pulsed-MOCVD must be soluble in a high volatility solvent, chemically stable in a mixture, have good atomization characteristics, and evaporate readily in the reactor pressure range of 10 150 Pa. Commercially available precursors were identified through the catalogues of metalorganic chemical suppliers, including Alfa Aesar, Gelest, Aldrich, and Strem. The six zirconium precursors, and three yttrium precursors investigated in this study are shown in Table 1. The first element of suitability for a candidate precursor was cost. Zirconium(thd) was eliminated from further consideration, because the resulting YSZ layer could not be produced within the cost target of US$0.50 cmy2 set for SOFC manufacture. The number of moles of YSZ per micron thickness of film, per square centimeter of surface area, can be calculated from the density (5.89 g cmy3) and the molecular weight (123.22 g gmoley1). Assuming a deposition process with 50% precursor conversion efficiency, the cost of the precursor per unit area and per micron thickness can then be calculated from quoted supplier prices. The only precursor rejected on the basis of price was the b-diketonate, Zr(thd), which would cost US$130.95 cmy2.
Table 2 Zirconium and yttrium precursor evaluation Name Zr isopropoxide Zr n-propoxide Zr 2-methyl 2-butoxide Zr ethoxide Zr n-butoxide Zr t-butoxide Zr (thd) Y methoxyethoxide Y isopropoxide Y(thd) Alias ZrIP ZrnP ZrMB ZrEO ZrnB ZrtB Zrthd YMOE YIP Ythd Chemical formula Zr(OC3H7)4 Zr(OC3H7)4 Zr(OC5H11)4 Zr(OC2H5)4 Zr(OC4H9)4 Zr(OC4H9)4 Zr C28H52O6 Y(CH3OC2H4O)3 Y(OC3H7)3 Y(OC11H19)3

2.2. Solubility, atomization and evaporation The solubility of each precursor was assessed through standard chemical solubility tests, carried out under argon in the glove box. Anhydrous solvents were used, due to the moisture sensitivity of the precursors. If the precursor did not readily go into solution, heating and stirring were employed to varying degrees until the precursor either went into solution or was eliminated from further testing. The solution samples were monitored over time for stability, separation, or precipitation. In all cases, the concentration of precursor in solutions was less than 5%M. The atomization characteristics were determined by running the pulsed-MOCVD system with test solutions, starting with mixtures of approximately 2%M of the zirconia precursor and 0.2%M of the yttria precursor. The atomization and evaporation characteristics of each test solution were determined by observation of the nozzle exit, the reactor pressure (Varian convec-Torr), and the impact of any droplets or formation of any deposits on the reactor walls. If visible droplets were observed, the precursor concentration would be reduced and the test repeated until either the evaporation was suitable, or the precursor was rejected as having poor evaporation characteristics. The precursor solution was

Solubility Poor, toluene Toluene, propanol Toluene, butanol None Butanol, toluene Toluene Toluene None Butanol

Evaporation Poor Low conc. Good Poor Good Good Good

Film cost ($) 15.30 0.40 9.08 5.61 0.41 19.14 130.95 0.67 2.11 9.50

Experimental results for suitability for pulsed-MOCVD of prospective precursors. Cost in US$ is calculated for 10 mm thick film per 100 cm2 surface area, assuming 50% conversion efficiency.

S.P. Krumdieck et al. / Surface and Coatings Technology 167 (2003) 226233 Table 3 Maximum growth rate and efficiency results y Alias Max. growth rate (mm h 1) Temperature (8C) Conversion efficiency Concentration (%M) Zr ZrIP ZrnP ZrMB 2.2 6.4 7.5 575 550 525 24 90 90 1.5 1.2 0.9 Y 0.2 0.2 0.2

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Cow%Mx, the precursor molar density, rmowmole mly1x, and the total number of pulses for the deposition, Npw pulsesx. Eq. (1) gives the simple equation used to calculate conversion efficiency. Conversion Efficiencys GRtAsrox ? vpCormoNp (1)

3. Results Three precursors for zirconia, zirconium isopropoxide (ZrIP), ZrnP and ZrMB, and one for yttria, YMOE, were identified as suitable for low-cost YSZ films by pulsed-MOCVD. For each precursor, films were deposited over a range of temperature to identify the conditions for high growth rate. Analysis of deposited materials was performed for films grown at the highest growth rates. A comparison of the performance of the precursors is given in Table 3. 3.1. Zirconium isopropoxide Only very thin films were possible with ZrIP, with the growth not sufficient to fill in the porous substrate surface. Heating the precursor solution improved the performance, resulting in higher growth rate and higher density films. The XRD spectrum for the thin films exhibited very broad peaks, and indicated a tetragonal YSZ phase. Preliminary EDS analysis indicated zirconium and yttrium in a proportion of 101 based on principal peak height, and with no detectable carbon in the film. Fig. 2 shows the surface of the YSZ film grown on nickel with 1.4%M ZrIP and 0.8%M YIP. Both the isopropoxide precursors became insoluble after storage for several months under argon. 3.2. Zirconium n-propoxide ZrnP formed a stable solution with YMOE in toluene, and had good atomization and evaporation characteristics. Only one precursor concentration, 1.2%M ZrnP,

also heated and agitated in the supply bottle to assess any improvement in atomization. Table 2 gives the results of the initial screening of candidate precursor suitability for pulsed MOCVD. 2.3. Growth rate, activation energy, morphology and conversion efficiency The suitable precursor solutions were used to deposit films on heated substrates. During a typical experiment, a sample of porous SOFC electrode material was attached to the heater surface. The nickel-cermet substrates were 1 cm diameter disks, prepared by tape casting (ITN Energy Systems Inc.). The deposition temperature was measured by a type-K thermocouple embedded in the heater surface. Growth rate was determined by two methods for each deposition. Film thickness was measured on fracture surfaces by a scanning electron microscope (SEM) (Kevex ISI-SX-30) and an optical microscope (Olympus with stage micrometer). The deposition time, pulse rate, number of pulses and liquid volume per pulse were recorded. With thickness measurements from the microscope, growth rate per pulse, or per hour deposition time was determined. The color shift method involves measuring the time and film fringe color during deposition. The film thickness for each apparent color (red and green) is a function of the color light wavelength and the refractive index of the film, and was calibrated using ellipsometer (Rudolph) on a polished metal target. Apparent activation energy was determined from an Arrhenius plot of growth rate vs. inverse deposition temperature. The composition and phase of the asdeposited film surface were analyzed using powder Xray diffraction (Scintag) and the energy dispersive spectrometry (EDS) feature of the SEM. Precursor conversion efficiency was determined by comparing the solid oxide deposition rate to the alkoxide precursor injection rate. The molar deposition rate per unit surface area of heated susceptor, Aswmm2 x, can be calculated from the growth rate measurement, GRwmm hy1x, the deposition time, tdwhx, and the mole density of the YSZ, roxwmole mmy3 x. The molar injection rate of precursor is found from the liquid solution pulse volume, vpwml pulsey1 x, the concentration,

Fig. 2. ZrO2 Y2O3 films on nickel with tetragonal lattice structure deposited from 1.4%M ZrIPq0.8%M YIP solution. (a) Film surface SEM micrograph; (b) polished section optical micrograph.

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Fig. 3. Results from investigation of zirconia deposition on nickelcermet substrate from 3.74 vol.% ZrnP in toluene. (a) Surface of thin (6 mm thickness) zirconia film; (b) fracture surface showing conformal coverage.

was investigated. The growth rate achieved in this study is not considered the highest attainable, as other concentrations have not been investigated. Conversion efficiency and evaporation characteristics were improved when the precursor solution supply bottle was heated to approximately 80 8C. There were some difficulties with precursor building up on the reactor walls near the nozzle. Further experiments are planned to correct this problem for ZrnP. On porous substrates, low growth rates resulted in conformal coverage of the rough surface, which left larger voids open. Higher growth rates produced leveling of the film surface and bridging of small voids. The thin films produced with ZrnP exhibited wide, indistinct peaks in XRD analysis, possibly due to very small grain size. Fig. 3 shows the surface of a deposit on nickelcermet, and a fracture surface. Three features of the microstructure were common to low deposition rate layers. Cracks formed at some time after deposition, in a cellular pattern, often along the tops of round formations. XRD and optical microscopy provide no evidence of columnar structure in these thin, slow-growth rate films, thus the cracking is attributed to thermal expansion. Many grain edges show growth out of the plane of the surface, which could represent accelerated growth for grains with a preferred orientation. While voids are visible in the surface image, the cross-section shows how the growth conforms to the surface features. 3.3. Zirconium 2-methyl-2-butoxide The ZrMB precursor was soluble in toluene without heating or stirring and demonstrated good long-term chemical stability. Heating of the precursor supply to 70 8C was found to improve evaporation in the reactor, and thus conversion efficiency, possibly by reducing polymerization of the metalorganic compound in the solution. Two concentrations of ZrMB in the solution were investigated. The higher 1.5%M solution had a low conversion efficiency and problems with coating of the reactor walls with precursor. The lower 0.9%M solution

had conversion efficiencies of 90% at substrate temperatures approximately 525 8C and had minimal deposits on the reactor walls. A mixture with 1.9%M ZrMB and 0.2%M YMOE in toluene was found to perform very well in the pulsedMOCVD apparatus. This solution was primarily used in the investigations for solid layers on porous substrates. Fig. 4 shows a 1015 mm layer deposited on electrode material. The layer has a uniform thickness across this fracture surface, with thicker, leveled deposit around corners. Films deposited at lower growth rates, at temperatures both below and above 525 8C exhibited broad XRD peaks for YSZ. Many of the thin films (-5 mm) showed fine cracks along the tops of grains. XRD scan from the 1.5%M ZrMB solutions may indicate tetragonal structure, but the peaks are very weak. 4. Discussion 4.1. Activation energy The activation energy is determined from the first order reaction as expressed in Eq. (2): GRTs.sAexpC
D B yE E
A

RTs

F
G

(2)

where GR is the film growth rate, A is a constant, R is the universal gas constant, Ts is the substrate temperature, and EA is the activation energy. The activation energy for ZrnP was found to be 75"5 kJ moly1 Ky1 for the deposition reaction temperatures below 550 8C, as seen in Fig. 5a. The growth rate above 550 8C decreases slightly with temperature, with conversion efficiency in the range of 90%. Reducing the precursor concentration can enhance the evaporation characteristics of the solution, resulting in higher growth rates. If the evaporation is already satisfactory, then increasing metalorganic precursor concentration in the precursor will result in higher growth rates. In this preliminary

Fig. 4. Fracture surface of YSZ from ZrMBqYMOE in toluene deposited on nickel-cermet at 550 8C. (a) Center of sample; (b) outside edge of sample. High deposition rate is necessary for a solid, leveled layer.

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Fig. 5. Arrhenius plots of growth rate vs. temperature (a) depositions from 4 vol.% ZrnP with observed activation energy is 75"5 kJ moly1 Ky1; (b) deposition rate from two different solutions of ZrMB is independent of precursor concentration with activation energy of 45"5 kJ moly1 Ky1.

study of ZrnP, only one precursor concentration was trialed. Further investigations for other precursor concentrations are indicated to achieve higher growth rates. The activation energy for ZrMB, determined from the data in Fig. 5b was 45"5 kJ moly1 Ky1. The maximum growth rate was attained at deposition temperature of 525 8C for both precursor concentrations. This trend has been observed in previous studies for TiO2 deposition and appears to be due to favorable evaporation characteristics of the lower solution concentration w13x. An optimal concentration for maximum growth rate can be found through further investigation. Most investigations of YSZ films by CVD utilize the more expensive b-diketonate precursors. Alkoxide precursors have been more commonly employed in solgel ceramic processing. However, the liquid delivery system of pulsed-CVD facilitates the use of these lower cost precursors, with chemistry, which does not require added water. Table 4 gives a comparison of the performance,

based on activation energy, for the alkoxide precursors used in this study and b-diketonate precursors from the literature. Given the difference in price of the precursors, as shown in Table 2, the possibility of manufacturing YSZ films with pulsed-CVD is a promising advancement. 4.2. SOFC electrolyte The primary motivation for studying YSZ deposition was to discover a lower cost route to thin solid layers of the cubic phase material for manufacture of SOFCs. While the optimal process remains to be determined, this study has demonstrated the potential use of pulsedMOCVD with alkoxide precursor solutions. Noting that the estimated cost of film manufacture in Table 2 was based on 50% conversion efficiency, the study points up the potential for low-cost electrolyte manufacture. With the 90% conversion efficiency measured for the experiments with ZrnPqYMOE, the cost of a 10-mm thick

Table 4 Activation energy results from this study and literature for various precursors Film ZrO2 YSZ YSZ ZrO2 YSZ YSZ YSZ Ea (kJ moly1 Ky1) 75 45 48 188 58 58 45.5 Temperature range (8C) 450550 400525 300600 -636 500950 500700 6501100 Precursor Zr(OC3H7)4 Zr(OC5H11)4 Y(CH3OC2H4O)3 Zr(O-t-C4H9)4-O2 Y(C11H19O2)3 Zr(C11H19O2)3 Zr(O-t-C4H9)4-O2 Y(C11H19O2)3 Zr(O-t-C4H9)4-O2 Y(C11H19O2)3 Zr(OButn)4 Y(thd)3 H 2O Reference This study This study Matsuzaki w16x Akiyama w17x Figueras w18x Garcia w19x Chour w20x

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Fig. 6. Solid YSZ layer deposited on porous nickel-cermet SOFC electrode. (a) YSZ layer, 17 mm thickness, deposited at 525 8C from 3.74 vol.% ZrMBq0.42 vol.% YMOE. (b) XRD scan for the surface of the coated electrode indicating the presence of only the cubic phase YSZ peaks.

layer of YSZ would be less than US$1.00 per 100 cm2 surface area. The cost for ZrMBqYMOE would be less than US$5.00 per 100 cm2 for chemicals. Fig. 6 shows a 17 mm YSZ layer deposited on a porous nickel cermet substrate at 525 8C from ZrMBqYMOE. The XRD spectrum was taken with the coated sample placed film side up in the powder sample holder. The XRD spectrum for a 17-mm thick layer indicates one peak at 2us 30"0.28 and one other peak at 2us35"0.18. These correspond to the expected (1 1 1) and (0 0 2) peaks for cubic YSZ. The Ni-cermet may be contributing to the spectrum, and the conclusion from this preliminary evidence is limited to the absence of tetragonal YSZ peaks. These initial results indicate that the cubic phase of YSZ is the only phase present in the sample. The pulsed-MOCVD YSZ layers on prototype SOFC electrode material are comparable in morphology and microstructure to electrolytes processed by other deposition methods w21x. 5. Conclusion This study set out to identify a process for manufacturing the YSZ electrolyte layer on porous electrodes for SOFCs. One of the major costs in SOFC manufacture is the processing of the electrolyte. The pulsed-MOCVD technique has demonstrated the capability to use the lower cost alkoxide metalorganic precursors. This research project included an investigation of the suitable commercially available zirconia and yttria precursors for pulsed-MOCVD. Three candidate precursors for zirconia and one for yttria were identified on the basis of the required solubility, atomization and evaporation performance. ZrO2 Y2O3 layers were produced on solid metal and ceramic targets using ZrIP, ZrnP and ZrMB in a solution with YMOE. The best results were obtained for ZrMB, with growth rates as high as 7.5"0.5 mm hy1 and conversion efficiency in the range of 90% (mole oxidey mole precursor).

Solid layers of YSZ were prepared on porous nickelcermet samples provided by SOFC developer, ITN Energy Systems, Inc. XRD analysis indicated the cubic phase for thick films deposited at high growth rates. The growth rates for both ZrnP and ZrMB are high enough to deposit 1020 mm of YSZ at temperatures below 600 8C in a 1-h processing window. Pulsed-CVD provides the necessary flow dynamics to deposit coatings on complex surfaces, three-dimensional shapes, around corners. Larger scale equipment is under investigation for flat-plate and tube coating. Continued codevelopment of electrode and electrolyte processing in the context of the overall system architecture will be necessary for SOFC commercial development. The pulsed-MOCVD technology has the potential for SOFC manufacture with YSZ electrolyte production costs well below the manufacturing cost target. Acknowledgments This research was supported by the National Science Foundation SBIR award No. 9960174 to Boulder Material Systems, LLC, S. Krumdieck, President. The pulsed ultrasonic nozzle method was developed in collaboration with and contribution from Dr Harvey Berger (SonoTek Corp., Milton, NY). Thanks to Jai-Who Kim and Bill Barker (ITN Energy Systems Inc., Wheatridge, CO) for providing Ni-cermet samples. Thanks also to Subhash Singhal for providing direction on YSZ electrolyte development for SOFCs. References
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