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Surface and Coatings Technology 167 (2003) 226–233

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 metal–organic 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 6–7.5 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 metal–organic 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.P. Krumdieck). 0257-8972/03/$ - see front matter PII: S 0 2 5 7 - 8 9 7 2 Ž 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 Seimens–Westinghouse, 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.

P. and then installed into the pulsed-CVD system where the solution is under constant positive pressure in 99. solid YSZ films were prepared on porous Ni-cermet substrates from solution mixtures of zirconium n-propoxide (ZrnP). Krumdieck et al. 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 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.9% purity argon gas. In this study. The atomization and film growth processes are clearly visible to the operator as the horizontal susceptor is heated conductively from below. Experimental The pulsed-MOCVD system. The equipment and controls of pulsedMOCVD are relatively simple. sealed in delivery bottles in the glove box. 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 metal–organic CVD on a horizontal.6 kPa and is pumped back down to the initial pressure within 10 s. and zirconium 2-methyl 2-butoxide (ZrMB) with yttrium methoxyethoxide (YMOE). While this study does not include optimization of the process for SOFC fabrication. / Surface and Coatings Technology 167 (2003) 226–233 227 Fig. The pressure rises instantaneously to approximately 1. conductively heated substrate w10. and thus the low cost compared to other CVD processes.11x. A computer program controls the function and timing of a set of solenoid valves. The liquid precursor solutions are prepared in a dry glove box under argon. . 1 and described in detail elsewhere w13–15x 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. and the liquid is delivered through an ultrasonic nozzle to facilitate flash vaporization. which operate to meter a set volume of precursor and inject it into the nozzle at a set pulse rate. the pulsed process achieved high precursor conversion efficiency (over 90% under optimal conditions) and high growth rates (45 mm hy1) w12x. shown in Fig. In previous research of TiO2 film deposition from titanium isopropoxide. most widely used method of producing functional YSZ electrolytes. The reactor is continuously evacuated by a rotary vacuum pump. the feasibility of pulsed-MOCVD for thin (-20 mm) solid YSZ layers on porous ceramic substrates using commercially available precursors was investigated. 30 cm H). 2.S. Growth rates reported in these studies are in the range of 1–10 mm hy1 for solid cubic phase YSZ films. Functional schematic of the experimental pulsed-MOCVD reactor chamber with a plot of the reactor pressure through one pulse. 1. In pulsed-MOCVD.

228 S. the reactor pressure (Varian convec-Torr). The six zirconium precursors.30 0. Solubility. The atomization characteristics were determined by running the pulsed-MOCVD system with test solutions. or precipitation. Anhydrous solvents were used. the cost of the precursor per unit area and per micron thickness can then be calculated from quoted supplier prices. can be calculated from the density (5. no. starting with mixtures of approximately 2%M of the zirconia precursor and 0.61 0. . If the precursor did not readily go into solution. Zr(thd).2.40 9. 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%M of the yttria precursor.1.6-tetramethyl-3.2. / Surface and Coatings Technology 167 (2003) 226–233 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. heating and stirring were employed to varying degrees until the precursor either went into solution or was eliminated from further testing. or the precursor was rejected as having poor evaporation characteristics. The first element of suitability for a candidate precursor was cost. The precursor solution was Solubility Poor.6.P.95 0. If visible droplets were observed. and the impact of any droplets or formation of any deposits on the reactor walls. Krumdieck et al. due to the moisture sensitivity of the precursors. (YIP) Supplier Alpha Aesar Gelest Alpha Aesar Gelest Aldrich Gelest Gelest Gelest Strem Cat. propanol Toluene. Zirconium(thd) was eliminated from further consideration.50 cmy2 set for SOFC manufacture. carried out under argon in the glove box. Gelest. assuming 50% conversion efficiency. and three yttrium precursors investigated in this study are shown in Table 1. 2171-98-4 AKZ 965 23519-77-9 AKZ 950 1071-76-7 AKZ 945 AKY 927 AKY 932 39-3000 2. Aldrich. The atomization and evaporation characteristics of each test solution were determined by observation of the nozzle exit. the concentration of precursor in solutions was less than 5%M. toluene Toluene.67 2.5-heptanedionate) (Ythd) Yttrium isopropoxide. toluene Toluene – Toluene None Butanol Evaporation Poor Low conc. butanol None Butanol. and evaporate readily in the reactor pressure range of 10– 150 Pa. which would cost US$130. per square centimeter of surface area.50 Experimental results for suitability for pulsed-MOCVD of prospective precursors. separation. Commercially available precursors were identified through the catalogues of metal–organic chemical suppliers.22 g gmoley1). have good atomization characteristics.08 5.95 cmy2. chemically stable in a mixture. Commercial precursor suitability A suitable precursor for pulsed-MOCVD must be soluble in a high volatility solvent. including Alfa Aesar. The number of moles of YSZ per micron thickness of film. In all cases. Assuming a deposition process with 50% precursor conversion efficiency. The only precursor rejected on the basis of price was the b-diketonate.41 19.11 9.89 g cmy3) and the molecular weight (123. because the resulting YSZ layer could not be produced within the cost target of US$0. Cost in US$ is calculated for 10 mm thick film per 100 cm2 surface area. Good – Poor Good – Good – Good Film cost ($) 15. atomization and evaporation The solubility of each precursor was assessed through standard chemical solubility tests. The solution samples were monitored over time for stability. and Strem. the precursor concentration would be reduced and the test repeated until either the evaporation was suitable.14 130.

3. Growth rate was determined by two methods for each deposition.4 7.2 0. GRwmm hy1x. 2. the precursor molar density. YMOE. Zirconium n-propoxide ZrnP formed a stable solution with YMOE in toluene.2 0. can be calculated from the growth rate measurement. a sample of porous SOFC electrode material was attached to the heater surface. resulting in higher growth rate and higher density films. 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. The deposition temperature was measured by a type-K thermocouple embedded in the heater surface. number of pulses and liquid volume per pulse were recorded. Fig. the concentration. A comparison of the performance of the precursors is given in Table 3.2 229 Cow%Mx.).2 6. roxwmole mmy3 x. 3. Both the isopropoxide precursors became insoluble after storage for several months under argon. The molar deposition rate per unit surface area of heated susceptor. ZrO2 –Y2O3 films on nickel with tetragonal lattice structure deposited from 1. 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).S. Krumdieck et al. and with no detectable carbon in the film. rmowmole mly1x. 1. zirconium isopropoxide (ZrIP). 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. Zirconium isopropoxide Only very thin films were possible with ZrIP. The nickel-cermet substrates were 1 cm diameter disks. Aswmm2 x. With thickness measurements from the microscope. 2 shows the surface of the YSZ film grown on nickel with 1. During a typical experiment. . Preliminary EDS analysis indicated zirconium and yttrium in a proportion of 10–1 based on principal peak height.8%M YIP. activation energy. were identified as suitable for low-cost YSZ films by pulsed-MOCVD. The deposition time. Table 2 gives the results of the initial screening of candidate precursor suitability for pulsed MOCVD.P. Npw pulsesx. 2. Growth rate.5 575 550 525 24 90 90 1.2 0.9 Y 0.1. and indicated a tetragonal YSZ phase. Eq. The XRD spectrum for the thin films exhibited very broad peaks. Conversion Efficiencys GRtAsrox ? vpCormoNp (1) 3.8%M YIP solution.3. For each precursor. / Surface and Coatings Technology 167 (2003) 226–233 Table 3 Maximum growth rate and efficiency results y Alias Max. Only one precursor concentration.4%M ZrIPq0. Analysis of deposited materials was performed for films grown at the highest growth rates. the deposition time. morphology and conversion efficiency The suitable precursor solutions were used to deposit films on heated substrates. (b) polished section optical micrograph. Apparent activation energy was determined from an Arrhenius plot of growth rate vs. Fig. growth rate (mm h 1) Temperature (8C) Conversion efficiency Concentration (%M) Zr ZrIP ZrnP ZrMB 2. Precursor conversion efficiency was determined by comparing the solid oxide deposition rate to the alkoxide precursor injection rate. The color shift method involves measuring the time and film fringe color during deposition.2%M ZrnP. and was calibrated using ellipsometer (Rudolph) on a polished metal target.5 1. and had good atomization and evaporation characteristics. and one for yttria. (a) Film surface SEM micrograph.2. ZrnP and ZrMB. films were deposited over a range of temperature to identify the conditions for high growth rate. and the total number of pulses for the deposition. and the mole density of the YSZ. (1) gives the simple equation used to calculate conversion efficiency. Results Three precursors for zirconia. inverse deposition temperature. tdwhx.4%M ZrIP and 0. prepared by tape casting (ITN Energy Systems Inc. also heated and agitated in the supply bottle to assess any improvement in atomization. The molar injection rate of precursor is found from the liquid solution pulse volume. Heating the precursor solution improved the performance. pulse rate. or per hour deposition time was determined. with the growth not sufficient to fill in the porous substrate surface. vpwml pulsey1 x. growth rate per pulse.

(b) outside edge of sample. the cross-section shows how the growth conforms to the surface features. Ts is the substrate temperature.74 vol. and thus conversion efficiency. 3 shows the surface of a deposit on nickelcermet. often along the tops of round formations. The activation energy for ZrnP was found to be 75"5 kJ moly1 Ky1 for the deposition reaction temperatures below 550 8C. Fig. low growth rates resulted in conformal coverage of the rough surface. possibly by reducing polymerization of the metal–organic compound in the solution. 3. Heating of the precursor supply to 70 8C was found to improve evaporation in the reactor. which left larger voids open. Three features of the microstructure were common to low deposition rate layers. (2): GRŽTs. Many grain edges show growth out of the plane of the surface.1. with thicker. (b) fracture surface showing conformal coverage. High deposition rate is necessary for a solid.230 S. and a fracture surface. The lower 0. The growth rate achieved in this study is not considered the highest attainable. R is the universal gas constant. XRD scan from the 1. as seen in Fig. with conversion efficiency in the range of 90%. 4. in a cellular pattern. 4 shows a 10–15 mm layer deposited on electrode material. The layer has a uniform thickness across this fracture surface. 5a. (a) Center of sample.5%M solution had a low conversion efficiency and problems with coating of the reactor walls with precursor.9%M solution had conversion efficiencies of 90% at substrate temperatures approximately 525 8C and had minimal deposits on the reactor walls. (a) Surface of thin (6 mm thickness) zirconia film. 3.2%M YMOE in toluene was found to perform very well in the pulsedMOCVD apparatus. In this preliminary Fig. XRD and optical microscopy provide no evidence of columnar structure in these thin. Cracks formed at some time after deposition. If the evaporation is already satisfactory. Reducing the precursor concentration can enhance the evaporation characteristics of the solution. Further experiments are planned to correct this problem for ZrnP. Krumdieck et al. and EA is the activation energy. then increasing metal–organic precursor concentration in the precursor will result in higher growth rates. Fracture surface of YSZ from ZrMBqYMOE in toluene deposited on nickel-cermet at 550 8C. but the peaks are very weak.3. was investigated. leveled deposit around corners. slow-growth rate films. The higher 1.5%M ZrMB solutions may indicate tetragonal structure. thus the cracking is attributed to thermal expansion. possibly due to very small grain size. as other concentrations have not been investigated. Two concentrations of ZrMB in the solution were investigated. which could represent accelerated growth for grains with a preferred orientation. Films deposited at lower growth rates. indistinct peaks in XRD analysis. Higher growth rates produced leveling of the film surface and bridging of small voids. There were some difficulties with precursor building up on the reactor walls near the nozzle. Conversion efficiency and evaporation characteristics were improved when the precursor solution supply bottle was heated to approximately 80 8C. Discussion 4.% ZrnP in toluene. Fig. This solution was primarily used in the investigations for solid layers on porous substrates. The thin films produced with ZrnP exhibited wide.P. A is a constant. Zirconium 2-methyl-2-butoxide The ZrMB precursor was soluble in toluene without heating or stirring and demonstrated good long-term chemical stability. leveled layer. / Surface and Coatings Technology 167 (2003) 226–233 Fig. While voids are visible in the surface image. at temperatures both below and above 525 8C exhibited broad XRD peaks for YSZ. Activation energy The activation energy is determined from the first order reaction as expressed in Eq.sAexpC D B yE E A RTs F G (2) where GR is the film growth rate. On porous substrates.9%M ZrMB and 0. 4. The growth rate above 550 8C decreases slightly with temperature. A mixture with 1. Results from investigation of zirconia deposition on nickelcermet substrate from 3. resulting in higher growth rates. Many of the thin films (-5 mm) showed fine cracks along the tops of grains. .

study of ZrnP. this study has demonstrated the potential use of pulsedMOCVD with alkoxide precursor solutions. only one precursor concentration was trialed. which does not require added water. 4. While the optimal process remains to be determined. the possibility of manufacturing YSZ films with pulsed-CVD is a promising advancement. Krumdieck et al. 5b was 45"5 kJ moly1 Ky1. Noting that the estimated cost of film manufacture in Table 2 was based on 50% conversion efficiency.P. Arrhenius plots of growth rate vs. Table 4 gives a comparison of the performance. The activation energy for ZrMB. Given the difference in price of the precursors. 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.S. With the 90% conversion efficiency measured for the experiments with ZrnPqYMOE. / Surface and Coatings Technology 167 (2003) 226–233 231 Fig. based on activation energy. 5. as shown in Table 2. the study points up the potential for low-cost electrolyte manufacture. However. temperature (a) depositions from 4 vol. with chemistry. the liquid delivery system of pulsed-CVD facilitates the use of these lower cost precursors. The maximum growth rate was attained at deposition temperature of 525 8C for both precursor concentrations. Further investigations for other precursor concentrations are indicated to achieve higher growth rates. Most investigations of YSZ films by CVD utilize the more expensive b-diketonate precursors.2. determined from the data in Fig. for the alkoxide precursors used in this study and b-diketonate precursors from the literature.5 Temperature range (8C) 450–550 400–525 300–600 -636 500–950 500–700 650–1100 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 . An optimal concentration for maximum growth rate can be found through further investigation. 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. Alkoxide precursors have been more commonly employed in sol–gel ceramic processing. 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. (b) deposition rate from two different solutions of ZrMB is independent of precursor concentration with activation energy of 45"5 kJ moly1 Ky1.% ZrnP with observed activation energy is 75"5 kJ moly1 Ky1.

Fig. layer of YSZ would be less than US$1.00 per 100 cm2 for chemicals. The cost for ZrMBqYMOE would be less than US$5. 6 shows a 17 mm YSZ layer deposited on a porous nickel cermet substrate at 525 8C from ZrMBqYMOE. w2x K. The pulsed-MOCVD technique has demonstrated the capability to use the lower cost alkoxide metal–organic precursors. NY). Larger scale equipment is under investigation for flat-plate and tube coating. The pulsed ultrasonic nozzle method was developed in collaboration with and contribution from Dr Harvey Berger (SonoTek Corp.5 mm hy1 and conversion efficiency in the range of 90% (mole oxidey mole precursor). Academic Press. Jensen (Eds. Krumdieck et al.232 S. w3x S.% YMOE. Madison. Proceedings of the 1998 International Gas Research Conference.F. Morosanu. 17 mm thickness.28 and one other peak at 2us35"0. S. WI. Three candidate precursors for zirconia and one for yttria were identified on the basis of the required solubility. Thin Films by Chemical Vapor Deposition. XRD analysis indicated the cubic phase for thick films deposited at high growth rates. Inc.42 vol.18. Acknowledgments This research was supported by the National Science Foundation SBIR award No. Chemical Vapor Deposition Principles and Applications. Thanks to Jai-Who Kim and Bill Barker (ITN Energy Systems Inc. 1993. These correspond to the expected (1 1 1) and (0 0 2) peaks for cubic YSZ. with growth rates as high as 7. 9960174 to Boulder Material Systems.P.C. London. Continued codevelopment of electrode and electrolyte processing in the context of the overall system architecture will be necessary for SOFC commercial development. 822–833. 1990. President..F. in: M.).. 1998. The growth rates for both ZrnP and ZrMB are high enough to deposit 10–20 mm of YSZ at temperatures below 600 8C in a 1-h processing window. Krumdieck. Wheatridge. (a) YSZ layer. The Ni-cermet may be contributing to the spectrum. Solid layers of YSZ were prepared on porous nickelcermet samples provided by SOFC developer. 6. Jensen.5"0. ZrO2 –Y2O3 layers were produced on solid metal and ceramic targets using ZrIP. Hitchman. Amsterdam. The pulsed-MOCVD YSZ layers on prototype SOFC electrode material are comparable in morphology and microstructure to electrolytes processed by other deposition methods w21x.% ZrMBq0. Conclusion This study set out to identify a process for manufacturing the YSZ electrolyte layer on porous electrodes for SOFCs. Thanks also to Subhash Singhal for providing direction on YSZ electrolyte development for SOFCs. Solid YSZ layer deposited on porous nickel-cermet SOFC electrode. 5. K. / Surface and Coatings Technology 167 (2003) 226–233 Fig. ITN Energy Systems. and the conclusion from this preliminary evidence is limited to the absence of tetragonal YSZ peaks. . (b) XRD scan for the surface of the coated electrode indicating the presence of only the cubic phase YSZ peaks. around corners. LLC. ZrnP and ZrMB in a solution with YMOE. This research project included an investigation of the suitable commercially available zirconia and yttria precursors for pulsed-MOCVD.00 per 100 cm2 surface area.E. atomization and evaporation performance. Omnipress. The XRD spectrum was taken with the coated sample placed film side up in the powder sample holder.74 vol. three-dimensional shapes. The XRD spectrum for a 17-mm thick layer indicates one peak at 2us 30"0. The best results were obtained for ZrMB. The pulsed-MOCVD technology has the potential for SOFC manufacture with YSZ electrolyte production costs well below the manufacturing cost target. CO) for providing Ni-cermet samples. Milton. These initial results indicate that the cubic phase of YSZ is the only phase present in the sample. One of the major costs in SOFC manufacture is the processing of the electrolyte. deposited at 525 8C from 3.L. References w1x C. pp. Singhal. Elsevier. Pulsed-CVD provides the necessary flow dynamics to deposit coatings on complex surfaces.

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