Tungsten atomic layer deposition on cobalt nanoparticles

C. A. Wilson and D. N. Goldstein

Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215

J. A. McCormick
Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0424

A. W. Weimer
Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0424

S. M. Georgea
Department of Chemistry and Biochemistry, and Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309-0215

Received 13 August 2007; accepted 4 March 2008; published 8 April 2008 Tungsten W atomic layer deposition ALD was performed on cobalt Co nanoparticles using WF6 and Si2H6 as reactants. A variety of techniques were then applied to analyze both the Co nanoparticles and at Co substrates after W ALD. Analysis of the W ALD-coated Co nanoparticles is complicated because a CoO layer may exist on the Co nanoparticles and a WO3 layer may be present on the W ALD coating. LECO measurements quantied the oxygen weight percent in the W ALD-coated Co nanoparticles. The oxygen weight percent decreased with increasing number of W ALD AB cycles. To determine the location of this oxygen, x-ray reectivity XRR investigations measured the WO3 lm thickness on at W ALD lms. The XRR measurements yielded a WO3 lm thickness on at W ALD lms of 20 . X-ray photoelectron spectroscopy XPS studies also quantied the relative oxygen abundance at the W / Co interface for W ALD on at Co lms. The XPS measurements revealed that nearly all the oxygen was in the WO3 layer on the W ALD lm. Only an immeasurably small amount of oxygen was bonded as CoO at the W / Co interface. To determine the thickness of W ALD lm on the Co nanoparticle, surface prolometry of W ALD on at Co substrates measured a W ALD growth rate of 3.9 per AB cycle. A geometric model was then constructed to incorporate the information from all the measurements on Co nanoparticles and at Co substrates. Excellent agreement between the geometrical model and the oxygen weight percent versus the number of W ALD cycles was obtained when the CoO thickness was negligible and the WO3 thickness on the W ALD layer on the Co nanoparticles was 28.5 . This agreement indicates that the details of ALD on nanoparticles can be unraveled by a concert of techniques even when interfacial layers can form due to the high reactivity of nanoparticles. The W ALD-coated Co nanoparticles may be useful in fabricating WCCo hardmetals with enhanced mechanical properties. 2008 American Vacuum Society. DOI: 10.1116/1.2902956

I. INTRODUCTION Nanoparticles are increasingly important to modern technology. The small size of nanoparticles often results in very different physical properties for nanoparticles compared to the constituent bulk material.13 The high surface-to-volume ratio of nanoparticles can also lead to much larger chemical reactivity for nanoparticles than for much larger particles.46 The properties and reactivity of nanoparticles can be tuned by depositing thin coatings on their surfaces. Analysis of these coatings can be challenging because the coating may signicantly alter the nanoparticle size and composition. Atomic layer deposition ALD is a thin lm growth technique that can coat nanoparticles.711 ALD is based on sequential self-limiting surface reactions.12 In the typical ALD
a

process, two gas phase molecules are alternatively exposed to a substrate in an ABAB . . . sequence. The A gas exposure reacts with surface species, adds the rst desired atomic element, and changes the surface species. The subsequent B gas exposure reacts with the new surface species and adds the second desired atomic element. This second reaction also changes the surface species back to the original surface species. The ABAB . . . sequence can deposit thin lms conformably with atomic layer control.12 A variety of binary materials can be grown using various ALD surface chemistries.13 Single element metal lms can also be deposited using ALD techniques.14 Tungsten W ALD can be performed using WF6 and Si2H6 as the reactants. The self-limiting surface reactions for W ALD can be described as1517

Electronic mail: steven.george@colorado.edu J. Vac. Sci. Technol. A 263, May/Jun 2008

* WF3 + Si2H6 WSiH* + SiHF3 + 2H2 ,

2008 American Vacuum Society

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* WSiH* + WF6 WWF3 + SiHF3 ,

where the asterisks denote the surface species. By repeating the surface reactions in an ABAB . . . sequence, W ALD growth occurs very linearly with the number of AB cycles. The surface chemistry for W ALD is different than the ALD surface chemistry for binary materials because the silicon species deposited by Si2H6 are removed from the surface by WF6. The typical measured W ALD growth rate is 4 per AB cycle.18 W ALD on Co nanoparticles was utilized as a model system to explore the application and analysis of ALD coatings on nanoparticles. W ALD coating on Co nanoparticles may also help to fabricate and improve the properties of nanostructured tungsten carbidecobalt WCCo hardmetals. Nanograined WCCo coatings exhibit increased hardness and toughness.19,20 However, the WC and Co nanoparticles that can be used to make the WCCo composites have higher reactivity than larger particles. In particular, cobalt nanoparticles easily oxidize at low temperatures.2123 Earlier studies have protected cobalt nanoparticles from oxidation for magnetic applications using polysiloxane polymer coatings.24,25 The W ALD may help to protect the Co nanoparticle from oxidation without introducing any additional constituents to the WCCo composite. The typical WCCo hardmetal consists of WC with a range of 3 30 wt % Co binder depending on the application.26 The WC is hard but brittle and the Co binder is soft but ductile. In the WCCo sintering process, the cobalt initially melts and wets the WC grains.27 The oxidation of cobalt may have a deleterious effect on the sintering of WCCo.27 At the sintering temperatures, the WC particles can also experience signicant grain growth28 that degrades the mechanical properties. Conformal W ALD on the Co nanoparticles may both protect the Co nanoparticles from oxidation and delay the wetting of cobalt on the WC grains that may lower the WC grain growth. This study examined W ALD on Co nanoparticles with the goal to limit the oxidation of cobalt and with special focus on the extent and location of oxidation after W ALD. The W ALD-coated Co nanoparticle can be described as shown in Fig. 1. The initial Co nanoparticle may have a CoO layer as a result of previous exposure to air. The W ALD surface chemistry may also impact this CoO layer. The W ALD layer may also oxidize upon exposure to air and produce a WO3 layer. Figure 1 denes the possible Co, CoO, W, and WO3 layers with a radius or thickness dened by r1, r2, r3, and r4, respectively. The challenge of this paper will be to determine these values to understand W ALD on Co nanoparticles. II. EXPERIMENT
A. Rotary reactor and ALD chemistry

FIG. 1. Schematic representation of the W ALD-coated Co nanoparticle with Co radius or layer thicknesses dened by r1, r2, r3, and r4.

cursors. For efcient reactant usage, the necessary gas conductance to the high surface area nanoparticles can be obtained using a rotary reactor.11 In brief, this reactor consists of a rotating tube containing the particles that is situated in a vacuum chamber. The rotating tube has porous walls and the gases can ow in and out of the rotating tube. The principal ALD chemistry used in this study was W ALD with WF6 and Si2H6.1517 The WF6 was obtained from Aldrich in a stainless steel cylinder. The ow of the WF6 into the reactor was regulated with a corrosive gas stainless steel regulator, typically set to a pressure of 100 Torr. The Si2H6 was obtained from Voltaix in a large steel cylinder. The ow of Si2H6 into the reactor was regulated in the same manner with a regulator and set pressure. For experiments that involved in situ reduction of the Co nanoparticles, a steel cylinder of H2 was also obtained from Aldrich and regulated for ow into the reactor. The WF6 and Si2H6 precursors were alternatively introduced into the reactor using pneumatic switching valves. For comparison with W ALD on Co substrates, W ALD was also performed on Al2O3 ALD lms. The Al2O3 ALD lm growth was accomplished by two self-limiting surface reactions that have been described in previous work:2931 A B
* AlOH* + Al CH3 3 AlOAl CH3 2 + CH4 , * AlCH3 + H2O AlOH* + CH4 ,

3 4

Atomic layer deposition of thin lms on nanoparticles with large surface area is a challenging problem.11 For uniform deposition without aggregation, all the particles must be agitated as they are exposed to the gaseous reactant preJVST A - Vacuum, Surfaces, and Films

where the asterisks denote the surface species. By repeating the surface reactions given by Eqs. 3 and 4 , Al2O3 ALD growth occurs very linearly with the number of AB cycles.

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Typical measured Al2O3 ALD growth rates are 1.1 1.2 per AB cycle.30,31 The Al2O3 ALD lms are very smooth and extremely conformal to the underlying substrate.31,32 The reactants for Al2O3 ALD were attached to the reactor. Al CH3 3 trimethylaluminum TMA with a 97% purity was obtained from Aldrich. High-performance liquid chromatography grade H2O was obtained from Fischer Scientic. The TMA was held in a stainless steel vessel and connected to the reactor using stainless steel tubing. The H2O was contained in a 25 ml glass bulb and attached to stainless steel tubing leading to the reactor using an Ultratorr union. Both reactants were maintained at room temperature at 20 C. The TMA and H2O precursors were also alternatively introduced into the reactor using pneumatic switching valves. Due to the large surface area of the cobalt nanoparticles, large exposures of the reactant gases were needed for the ALD surface reactions to reach completion. The introduction of WF6 and Si2H6 was adjusted using conductance-limiting valves to ensure a constant precursor pressure for each exposure. The pressure transients were measured by a 10 Torr capacitance manometer attached to the ow tube between the pneumatic switching valves and the rotary reactor. The TMA and H2O had lower vapor pressures and did not require regulation to ll the reactor.

the reactor. The powder samples or at substrates were then maintained in the evacuated reactor until reaching the temperature of 125C for the ALD reactions.
C. Analysis of W ALD on cobalt nanoparticles

B. Processing cobalt nanoparticles

Cobalt nanoparticles were obtained from Nanomat, Inc. North Huntingdon, PA . The nanoparticles were initially sealed under argon but were exposed to air during sample loading. Only 1 g of the particles was used in each experiment. The nanoparticles had an average diameter of 100 nm. Processing in the rotary reactor allowed the nanoparticles to be agitated and provided high gas conductance for the reactants to access the high surface area of the nanoparticles.11 For W ALD, WF6 was dosed through the pneumatic valve into the evacuated rotary reactor. The reaction chamber was isolated from the pump using the gate valve. The WF6 was dosed into the chamber to achieve a pressure of 1.5 Torr for 1 g of Co powder. The WF6 gas was allowed to react in the reactor for 1 min. Subsequently, the system was evacuated by opening the gate valve. After the WF6 exposure, the N2 purge was dosed into the chamber and obtained a pressure of 25 Torr for 5 s. Subsequently, the N2 was evacuated from the chamber and the pressure was reduced to the initial base pressure of 25 50 mTorr. This evacuation required 1 min. The Si2H6 and N2 purge sequence then immediately followed the WF6 and N2 purge sequence described above. The pressures and times were identical. One complete cycle of WF6 N2 Si2H6 N2 required 6 min. The Co nanoparticles and the Co substrates were also exposed to H2 to attempt to reduce the CoO overlayer in some experiments prior to W ALD. The possible H2 reduction involved three sequential 40 Torr static exposures of a 5% H2 in N2 mixture at 180 C for 3 min. This H2 reduction procedure was followed by evacuation to the base pressure of
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The oxygen content of the W ALD-coated cobalt nanoparticles was obtained using a LECO model TC 600 oxygen analyzer instrument. This instrument operates according to the inert gas fusion principle.33 The sample was weighed and placed in a high purity graphite crucible. A high temperature helium gas stream then owed over the sample to cause the release of all the oxygen in the sample. After combining with the carbon of the crucible to form CO, the CO gas was quantied by infrared absorption spectroscopy. To correct for the presence of oxygen as CO2 and to maximize measurement accuracy, a second pass through the detector was made by the sample gas. The LECO instrument reported a precision to below 1 ppm of oxygen for a given sample. The thickness of the WO3 lm on the surface of a W ALD-coated nanoparticle was determined by x-ray reectivity XRR analysis with a Bede D1 high resolution x-ray diffractometer from Bede Scientic Inc. The instrument was equipped with a Cu x-ray tube operating at = 1.54 . The lament current was 40 mA at a voltage of 40 kV. Raw data were tted using REFS software from Bede Scientic Inc. The XRR ts determined the lm thickness, lm density, and surface roughness. These results from XRR analysis on at substrates were then used as a reference for estimation of the WO3 lm thickness on the W ALD-coated Co nanoparticles. The estimation of the W ALD lm thickness on the cobalt nanoparticles relies on the measurement of the W ALD lm thickness on sputtered Co lms on at Si 100 substrates. A portion of the at cobalt substrate was masked prior to the W ALD. After the W ALD, the mask was removed to reveal a step edge. This step edge allowed accurate lm thickness measurements to be performed using a Veeco Dektak 3 stylus prolometer. The nature of the CoO at the WCo interface was analyzed with x-ray photoelectron spectroscopy XPS using a PHI 5600 x-ray photoelectron spectrometer instrument. This method allowed an estimation of the amount of oxygen bound either to W or Co in the W ALD-coated Co nanoparticles. A monochromatic Al K source was used to analyze the W ALD-coated at Co substrates during depth-proling XPS. A pass energy of 187.5 eV and a step size of 0.8 eV was used for the survey scans. For the high resolution scans, the pass energy was 23.5 eV and the step size was 0.025 eV. All scans were calibrated by referencing the adventitious C 1s peak to 285 eV. III. RESULTS Oxygen content analysis was performed on samples of Co nanoparticles after 0, 15, 20, 30, 45, 50, 60, 75, 90, and 100 AB cycles of W ALD at 125C. The results are presented in Fig. 2. The decreasing oxygen content with increasing number of AB cycles are tted with an exponential curve. The oxygen weight percent of the sample after no W ALD is the

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FIG. 2. Oxygen weight percent of W ALD-coated Co nanoparticles vs number of W ALD AB cycles at 125 C.

FIG. 4. W ALD lm thickness vs number of W ALD AB cycles at 125 C measured using x-ray reectivity and surface prolometry.

control sample. The oxygen on this sample is attributed to a CoO lm on the surface of the Co nanoparticles. XRR was utilized to analyze samples after 5, 10, 15, 20, and 25 AB cycles of W ALD on an Al2O3 ALD lm on a at Si 100 wafer at 125C. The XRR results are shown in Fig. 3. The number of fringe features grows with the increasing number of AB cycles. There are 1, 2, 3, 4, and 6 fringes after

FIG. 3. X-ray reectivity scans of W ALD lms on Al2O3 ALD on Si 100 wafers vs number of W ALD AB cycles at 125 C. JVST A - Vacuum, Surfaces, and Films

5, 10, 15, 20, and 25 cycles, respectively. Estimations of the Al2O3, W, and WO3 lm thicknesses and densities can be obtained from the tting of the XRR scans using the Bede REFS software. The W ALD lm thicknesses on the Al2O3 ALD lms obtained from the XRR analysis are shown as the open squares in Fig. 4. The density of the W ALD layer was 16.2 16.4 g / cm3. A WO3 layer was also present on top of the W ALD layer. This WO3 layer had a thickness of 17 20 . This native oxide layer is formed during exposure of the W ALD layer to air when the sample is removed from the reactor. The initial Al2O3 ALD layer had a thickness of 1221 after 1000 AB cycles of Al2O3 ALD. The native oxide thickness on W ALD lms is known to vary considerably depending on the instrument and analysis conditions. For example, XPS measurements of W ALD lms on at Si 100 wafers determined a native oxide thicknesses of 12.5 .34 XPS measurements of W ALD lms grown on polymer particles were consistent with a larger WO3 layer thickness of 29.5 on the underlying W ALD lm.34 The larger WO3 thickness on the particles suggests that the WO3 thickness may be dependent on the radius of curvature of the substrate. Supporting this possibility, transmission electron microscopy images of crystalline W tips used in scanning tunneling microscopy experiments have observed a surface layer of 30 40 believed to be a WOx material.3537 W ALD was also grown on SiO2 substrates for comparison with the results on Al2O3 ALD substrates. The W ALD required more AB cycles to nucleate on the SiO2 substrate in agreement with previous observations.16,38 However, the effect of this longer nucleation did not produce a substantial decrease in the W ALD lm thickness after 35 AB cycles.

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TABLE I. Volumes and masses for the Co, CoO, W, and WO3 components of the W ALD-coated Co nanoparticle Co CoO W WO3 r1 r2 r3 r4 V1 = 4 / 3 V2 = 4 / 3 V3 = 4 / 3 V4 = 4 / 3 r3 1 r1 + r2 3 V1 r1 + r2 + r3 3 V2 + V1 r1 + r2 + r3 + r4 3 V3 + V2 + V1 M1 = M2 = M3 = M4 =
1 2 3 4

V1 V2 V3 V4

IV. DISCUSSION
A. Understanding W ALD on Co nanoparticles

FIG. 5. Atomic percent composition for W, Co, O, C, and Si vs sputter time of W ALD-coated Co at substrates.

The W ALD-coated Co nanoparticle with concentric shells for the WO3, W, and CoO layers on a core Co nanoparticle is represented in Fig. 1. The LECO oxygen weight percent, XRR, prolometry, and depth-proled XPS results can be combined to determine the layer thicknesses after W ALD on the Co nanoparticles. The variables needed to describe completely the system are the radius and thicknesses dened by r1, r2, r3, and r4 in Fig. 1. The oxygen weight percent %O can be dened in terms of these four parameters. The equation for the %O is the total mass of oxygen divided by the total mass of all the elements. The %O is based on an accounting of all of the atoms of each element in all the concentric shells of the coated nanoparticle. The equation is %O = 100 % M O 2+M O
4

/ M O 2+M O
4

The W ALD lm thicknesses determined by XRR on SiO2 substrates versus number of AB cycles are displayed as the closed triangles in Fig. 4. W ALD lms were also deposited on at Co substrates for XRR analysis. However, the sputtered Co lms were too rough for accurate XRR analysis. W ALD lm thicknesses measured by prolometry on Co, Al2O3, and SiO2 substrates are also shown in Fig. 4. The W ALD lm thickness grows progressively with number of AB cycles. The measurements on Co, Al2O3, and SiO2 are displayed by the solid circles, squares, and triangles, respectively. A t of the W ALD lm thickness versus number of AB cycles on the at Co substrates yields a W ALD growth rate of 4.3 per AB cycle. The W ALD growth rate obtained from all points on Fig. 4 is 3.9 per AB cycle. The expected growth rate for W ALD is 4 per AB cycle under similar reaction conditions.18 X-ray photoelectron spectroscopy was performed after W ALD on the sputtered Co lms on at Si 100 substrates. Sputter depth-proling results are shown in Fig. 5 after 50 cycles of W ALD on a Co sample previously exposed to H2 to reduce the CoO overlayer. Very little oxygen is observed at the W / Co interface. This insignicant oxygen signal indicates that negligible CoO is present. The crossover point for the W and Co concentrations is at a sputtering time between 400 and 500 s. The prolometry measurements indicate that this sputtering time corresponds to a W ALD lm thickness of 200 .
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+ M Co 1 + M Co 2 + M W 3 + M W

M O 2 is the mass of oxygen in the cobalt oxide and M O 4 is the mass of oxygen in the tungsten oxide. M Co 1 is the mass of cobalt in the core cobalt nanoparticle and M Co 2 is the mass of cobalt in the cobalt oxide lm. M W 3 is the mass of tungsten in the tungsten lm deposited by W ALD, and M W 4 is the mass of tungsten in the tungsten oxide lm. The determination of the masses in the W ALD-coated Co nanoparticles requires the Co radius, layer thicknesses, and densities. The densities used in the calculations are 8.92 g / cm3 for Co, 6.20 g / cm3 for CoO, 16.6 g / cm3 for W, and 7.20 g / cm3 for WO3. The masses of the layers M 1, M 2, M 3, and M 4 are related to the masses in the %O equation using the atomic masses, ma, for Co, W, and O. M Co 1 = M 1 , M Co 2 = M 2 M W 3 = M3 , M W 4 = M4 M O 2 = M2 ma W / ma W + 3 ma O , ma Co / ma Co + ma O , 6 7 8 9 10

ma O / ma Co + ma O ,

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FIG. 6. Calculated WO3 thickness vs number of W ALD AB cycles determined from the model either without a CoO layer r2 = 0 or with a CoO layer r2 = 27 .

FIG. 8. Calculated weight percent of W, Co, and O vs number of W ALD AB cycles determined from the model without a CoO layer r2 = 0 and with a WO3 thickness of r4 = 28.5 .

M O 4 = M4

ma O / ma W + 3

ma O ,

11

The masses are determined by the volume of each material times the density of the material. The volumes of each material are dependent on the Co nanoparticle radius and the layer thicknesses. The volumes and masses are given in Table I. The oxygen weight percent is calculated from the Co

nanoparticle radius and layer thicknesses using the masses and volumes. The Co nanoparticle radius and CoO lm thickness, r1 and r2, respectively, can be determined from the experimental data. The oxygen weight percent of the sample with 0 cycles of W ALD in Fig. 2 corresponds only to Co and its oxide, CoO. This number for the %O can be used to determine the thickness of the initial CoO thicknesses on the Co nanoparticles. In the absence of W or WO3, Eq. 5 is %O = 100 % M O
2

/ M O 2 + M Co 1 + M Co

. 12

FIG. 7. Calculated oxygen weight percent vs number of W ALD AB cycles determined from the model with various WO3 thicknesses. JVST A - Vacuum, Surfaces, and Films

The initial Co nanoparticle radius before oxidation is 500 . Because some of the surface atoms will form the CoO oxide, the equations for the masses are constrained by conserving the initial mass of the Co: M Co 1 + M Co 2 = 1 4/3 500 .3 M O 2 can then be determined using Eq. 10 and %O = 2.4%. The resulting M O 2 can subsequently be converted to a volume of CoO using the CoO density of 6.2 g / cm3. This volume represents a thickness of CoO on the initial Co nanoparticle. The results of this analysis yield r1 = 486 and r2 = 27 . The total nanoparticle radius is 513 before W ALD. If the H2 reduction procedure is successful, then the Co nanoparticle would contain only a core of Co where r1 = 500 and r2 = 0 . The mass of Co is the same whether or not there is a CoO layer. Fixing r1 and r2 leaves only the W and WO3 layer thicknesses, r3 and r4, respectively. The surface prolometry measurements in Fig. 4 yield the total lm thickness of the W and WO3 layers. The lm thickness closely follows the equation r3 + r4 = C 4 where C is the number of W ALD

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cycles. The LECO results for oxygen weight percent then constrain the WO3 thickness, r4, since oxygen only originates from the CoO and WO3 layers. Figure 6 shows the WO3 thickness obtained from the LECO results with either a CoO layer thickness of r2 = 27 with CoO or r2 = 0 without CoO . Without the CoO layer, the WO3 lm thickness is fairly constant. The dashed line shows the best constant WO3 lm thickness of r4 = 28.5 . With a CoO layer thickness of r2 = 27 , the WO3 layer is thinner because less oxygen is required in the WO3 layer. Figure 6 also shows that a variable WO3 thickness is predicted if there is a CoO layer thickness of r2 = 27 . There is no apparent reason why there should be a variable WO3 layer thickness versus number of AB cycles. Consequently, Fig. 6 argues for no CoO layer thickness since this assumption yields a nearly constant WO3 layer thickness. The absence of a CoO layer between the Co and W layers is supported by the XPS depth-proling results. Only negligible oxygen is present in the XPS results shown in Fig. 5 at the W / Co interface. Similar XPS depth-proling results were observed both with and without the H2 reduction procedure prior to W ALD. These results argue that the W ALD chemistry can reduce the CoO native oxide layer on the Co nanoparticle during W ALD. The sensitivity of the LECO oxygen weight percent results to the WO3 thickness can also be explored assuming that there is no CoO layer thickness, i.e., r2 = 0. Figure 7 shows the predicted oxygen weight percent with r1 = 500 , r2 = 0 and r3 + r4 = C 4 for representative WO3 thicknesses of r4 = 20, 25, 30, and 35 . A WO3 thickness of r4 = 30 gives good agreement with the measured values. WO3 thickness values just 5 lower or higher than r4 = 30 display much poorer ts to the experimental results. A WO3 lm thickness of r4 = 30 is also in agreement with the best constant WO3 lm thickness of r4 = 28.5 obtained from Fig. 6 assuming no CoO layer. The thicknesses r1 = 500 , r2 = 0 , r3 + r4 = C 4 and r4 = 28.5 can be used to predict the weight percent of W, Co, and O versus number of AB cycles. The predictions for oxygen shown in Fig. 8 match the experimental data for oxygen weight percent in Fig. 2. Figure 8 also shows the change in weight percent for W and Co versus the number of AB cycles. The W weight percent increases rapidly because of the high atomic weight of W. The W weight percent is 5% at 3 AB cycles, 10% at 6 AB cycles and 50% at 24 AB cycles. Likewise, the oxygen weight percent decreases versus the number of AB cycles. This trend is observed because the increase in W mass offsets the oxygen increase from the WO3 layer.
B. Application of W ALD-coated Co nanoparticles in WCCo hardmetals

mately 12% Co and 88% WC. This composition yields elemental weight percentages of 82.7% W, 12% Co, and 5.3% C. The cobalt nanoparticle samples with 20 cycles of W ALD produce a W ALD lm with an 80 thickness on the 100 nm diameter Co nanoparticles. These W ALD-coated Co nanoparticles have a particle composition by weight percent of 50.2% W and 49.8% Co. A mass quantity, X, of these W ALD-coated Co nanoparticles could then be mixed with a mass quantity, Y, of WC material and a mass quantity, Z, of excess carbon black. This mixture would yield a hardmetal mass quantity, F, with the nal mass percentages given by the linear equations: 0.502X + 0.94Y = 0.827F 0.498X = 0.12F cobalt carbon tungsten

0.06Y + Z = 0.053F

The W ALD-coated cobalt nanoparticles fabricated in this work could be used as a starting material to achieve more homogeneous WCCo nanostructured hardmetals. The typical composition of such an industrial hardmetal is approxiJ. Vac. Sci. Technol. A, Vol. 26, No. 3, May/Jun 2008

To yield a 1 kg quantity of WCCo hardmetal F = 1000 g with the optimum ratios of 82.7% W, 12% Co, and 5.3% C, the starting mixture should be X = 241 g of W ALD-coated Co nanoparticles, Y = 751 g of WC, and Z = 8 g of excess carbon black. Oxygen on the surface of the W ALD-coated Co nanoparticles is 2% by mass of the W ALD-coated Co nanoparticles. This weight percent indicates that 4.8 g of the 241 g is oxygen. Given that the total mass of the nal mixture is 1000 g, the oxygen weight percent in the nal WCCo hardmetal is 0.48%. This oxygen weight percent could be reduced even further by using Co nanoparticles that are coated by more than 20 AB cycles of W ALD. However, correspondingly, more carbon black would then be needed in the nal mixture to obtain the desired weight percentages for W, Co, and C. Alternative approaches could also be employed to reduce the oxygen content of the W ALD-coated Co nanoparticles without adding new elements to the WCCo hardmetal. For example, the W ALD coating on the Co nanoparticles could be protected from forming the WO3 native oxide at room temperature by depositing a carbon coating on the W ALD surface. This carbon coating could be applied by reacting ethylene with the W ALD surface. Earlier studies suggest that the ethylene decomposition reaction would be successful at temperatures 250 C.39,40 At higher temperatures, this carbon coating may also start to form a WC coating on the W ALD surface. WC coatings could also be deposited on the W ALD surface with chemical vapor deposition using W CO 6 and ethylene.41 The WC coatings would be expected to be resistant to oxidation at room temperature.42 Another strategy to reduce the oxygen content of the W ALD-coated Co nanoparticles would be to reduce the WO3 native oxide to W. This reduction could be accomplished using H2 or H2 / CH4 exposures at temperatures 600 C.4345 However, the W ALD-coated Co nanoparticles would need to be used immediately after this H2 reduction. The tungsten surface will reform the WO3 native oxide again after air exposure.

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These W ALD-coated Co nanoparticles could be used to improve the homogeneity and strength of WCCo hardmetals. The cemented carbide industry has attempted to improve WCCo hardmetal mechanical properties through increased carbide content and lower Co binder content. Unfortunately, fracture resistance is greatly reduced and the hardmetal becomes brittle at these higher WC percentages. The solution has been to fabricate the WCCo hardmetals using nanoparticles.20,28 However, the oxidation of Co nanoparticles introduces signicant oxygen impurities into the hardmetal. The W ALD-coated Co nanoparticles may prevent the oxidation of the Co nanoparticles and allow their use in forming nanostructured WCCo hardmetals. V. CONCLUSIONS W ALD was conducted on Co nanoparticles to demonstrate the feasibility of metal ALD on nanoparticles and to develop a coated Co nanoparticle that may have value for the fabrication of WCCo hardmetals. Because both the Co nanoparticles and the W ALD coating are susceptible to oxidation, a CoO layer may exist on the Co nanoparticle and a WO3 layer may reside on the W ALD coating. This study evaluated W ALD on Co nanoparticles by carefully analyzing the W ALD-coated Co nanoparticles for oxygen and performing a variety of experiments to determine the location of this oxygen. XPS measurements suggested that nearly all of the oxygen was located in the WO3 native oxide layer on the W ALD surface. A geometric model that considered all the experimental data was consistent with a W ALD growth rate of 3.9 per AB cycle and a WO3 native oxide thickness of 28.5 on the W ALD surface on the Co nanoparticles after air exposure. The experimental data and analysis demonstrate that metal ALD can be performed on nanoparticles. The conformal W ALD on Co nanoparticles may help prevent the oxidation of the Co nanoparticles or delay the sintering of WCCo nanoparticles. These results suggest that W ALD-coated Co nanoparticles could be employed to improve the mechanical properties of the WCCo hardmetals. ACKNOWLEDGMENTS This work was funded by the Air Force Ofce of Scientic Research. Additional support was obtained from ALD NanoSolutions. The authors thank Beau B. Burton and Franois H. Fabreguette for assistance with the XRR analysis and Stephen D. Davidson for help with sample preparation and reactor maintenance.
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JVST A - Vacuum, Surfaces, and Films