APPLIED PHYSICS LETTERS 89, 141126 2006

Nanosecond laser ablation of gold nanoparticle lms

Seung H. Ko, Yeonho Choi, David J. Hwang, and Costas P. Grigoropoulosa
Laser Thermal Laboratory, Department of Mechanical Engineering, University of California, Berkeley, California 94720-1740

Jaewon Chungb
Department of Mechanical Engineering, Korea University, Seoul 136-713, South Korea

Dimos Poulikakos
Laboratory of Thermodynamics in Emerging Technologies, Department of Mechanical and Process Engineering, ETH Zurich, 8092 Zurich, Switzerland

Received 1 May 2006; accepted 21 August 2006; published online 6 October 2006 Ablation of self-assembled monolayer protected gold nanoparticle lms on polyimide was explored using a nanosecond laser. When the nanoparticle lm was ablated and subsequently thermally sintered to a continuous lm, the elevated rim structure by the expulsion of molten pool could be avoided and the ablation threshold uence was reduced to a value at least ten times lower than the reported threshold for the gold lm. This could be explained by the unusual properties of nanoparticle lm such as low melting temperature, weak bonding between nanoparticles, efcient laser energy deposition, and reduced heat loss. Finally, submicron lines were demonstrated. 2006 American Institute of Physics. DOI: 10.1063/1.2360241 Nanosecond pulsed laser ablation has been extensively studied as an effective technique for fully data driven and mask-less direct patterning due to precisely localized ablation for a wide variety of materials. However, for materials with high thermal diffusivity such as metals, damage-free patterning can only be achieved with femtosecond pulses.1 In this study, alkanethiol self-assembled monolayer SAM protected gold nanoparticle lm on polyimide substrate was ablated using a frequency doubled neodymnium doped yttrium aluminum garnet nanosecond laser 3 5 ns pulse width . The purpose of this study is to improve functionality and enhance feature resolution of drop-on-demand ink-jet printed electrical microconductors usually limited to 50 100 m resolution 25 for exible electronics in lieu of conventional integrated chip fabrication processing. Nanoparticles are used to exploit the signicant melting temperature depression compared to bulk gold 1063 C due to the thermodynamic size effect.6 This implies reduced and hence plastic-compatible processing temperature. With this goal in mind, nanosecond laser ablation of nanoparticle lm was explored in the current study. SAM protected gold nanoparticles were synthesized using a two-phase reduction method.5,7 SAM is critical for nanoparticles because it controls the size of the nanoparticles in addition to enhancing long term stability and achieving favorable optical properties through Au-thiol chemistry. The size of synthesized nanoparticles is distributed over the range of 1 3 nm as measured by transmission electron microscopy. The nanoparticle sintering characteristics were investigated at various temperatures. Both electrical conductivity and reectivity were increased past the range of 130 140 C where the SAM desorbs and evaporates away veried from thermogravimetry analysis . Based on these results, a nanoparticle lm hereafter referred to as unsintered nanoparticle lm was prepared by spin coating gold nanoparticles susa b

Electronic mail: cgrigoro@me.berkeley.edu Electronic mail: jwon@korea.ac.kr

pended in alpha terpineol on polyimide lm and subsequently dried at 120 C. The resulting nanoparticle lm 2.3 m was ablated using an innity-corrected long working distance objective lens at the incident laser pulse energy of 0.4 40 J. Figure 1 a shows crater proles of unsintered nanoparticle lm ablated at 0.17 J / cm2 uence Fpeak, peak-on-axis beam uence . Notice the absence of elevated rim structure that is often observed in metal lm craters Figs. 1 b and 1 c ablated by nanosecond lasers and also the clean, Gaussian-shaped ablation prole at low laser uence. To investigate the effect of sintering on the ablation of the nanoparticle lm, the unsintered nanoparticle lm was additionally heated at 160 C to obtain highly electrically conductive lm and the resulting sintered nanoparticle lm 1 m was then ablated. Incident laser energy higher than 0.15 0.2 J produced granulated morphology instead of ablation crater recess as shown in Fig. 1 b . Since the sintered nanoparticle lm morphology and structure become similar to a metal lm, melting occurs possibly with minimal evaporation and is followed by redistribution and resolidication to the granulated morphology. At incident peak uence of 1.4 J / cm2, a typical crater prole produced via nanosecond laser ablation of metal lm was obtained Fig. 1 c . The elevated rim prole due to melt expulsion and splashing of the molten pool can be clearly seen in Fig. 1 c . Ablative material removal of sintered nanoparticle lm occurred at incident peak uence higher than 0.7 0.9 J / cm2. Below 0.7 0.9 J / cm2, the sintered nanoparticle lm was melted and pulled outward to expose the underlying polyimide lm. The ablation threshold of the unsintered nanoparticle lm was calculated from atomic force microscopy AFM images taken at different irradiated laser pulse numbers and energy levels Fig. 2 . Assuming a Gaussian incident laser beam prole, the ablation threshold uence FA is related to the ablation radius rA by

0003-6951/2006/89 14 /141126/3/$23.00 89, 141126-1 2006 American Institute of Physics Downloaded 28 Feb 2008 to 129.132.68.243. Redistribution subject to AIP license or copyright; see http://apl.aip.org/apl/copyright.jsp

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FIG. 2. Ablation radius depending on the incident energy and the number of laser pulses. The tting curves were obtained from Eq. 1 for each case.

FIG. 1. Color online a Ablation proles of unsintered nanoparticle lm depending on the number of laser pulses. Cross-sectional proles varying the number of irradiated laser pulses. Each prole corresponds to 1, 2, 4, 6, 8, and 600 pulses as indicated by the arrow. The insets are AFM depth image after irradiation of 8 pulses top image and 600 pulses bottom image . b and c AFM depth image top image and cross sectional proles bottom image of the sintered nanoparticle lm ablation craters after b eight pulse laser irradiance at the incident energy of 0.41 J Fpeak 0.17 J / cm2 and c after a single pulse laser irradiance at the incident energy of 3.42 J Fpeak 1.4 J / cm2 and magnied AFM illumination image of the solid lined square in top area of c . Note that the calculated peak uence is based on approximate dimensions of the elliptical prole of the ablating laser beam.

rA =

w0 2

ln

Fpeak , FA

where Fpeak = 2E / w2 . Multiple pulse effect was consid0 ered by substituting FA in Eq. 1 by FA,N = FANS1.8 According to curve tting, the single shot ablation threshold uence and accumulation coefcient were 0.03 J / cm2 and 0.92, respectively. Note that the ablation threshold is at least one order lower than the reported ablation threshold for deposited gold 0.5 J / cm2 and other metal lms 1 10 J / cm2 for nanosecond laser irradiation at visible wavelength.1 To investigate whether this ablation phenomenon applies to other nanoparticle systems, a lm of polyvinylpyrrolidone-capped silver nanoparticles, synthesized by the Poyol method,9 was ablated. Crater proles for both sintered and unsintered nanoparticle silver lms similar to gold could be observed, while the ablation threshold uence of unsintered lm was measured as 0.03 0.08 J / cm2. The different ablation thresholds and crater morphologies signify that the unsintered nanoparticle lm exhibits different ablation behaviors from sintered nanoparticle lm. To understand the unsintered nanoparticle lm laser ablation mechanism, attention should be paid to the laser energy absorption and thermal diffusion, as well as to physical and chemical properties such as low melting temperature, differ-

ent bonding, optical, and thermal characteristics. Nanomaterials exhibit remarkable properties departing from the bulk material counterparts due to the large surface area to volume ratio, high surface energy, and spatial connement. The incident laser pulse energy is rst absorbed by nanoparticles more efciently due to lower reectance and strong absorption. Gold nanoparticles exhibit a strong absorption peak near the 520 nm wavelength that cannot be observed in bulk material due to surface plasmon oscillation modes of conduction electrons in the nanoparticles.10 Maxwell-Garnett effective medium theory calculation with conduction electron mean free path correction11 revealed that nanoparticle thin lm was less reective and strongly ab: 0.06 and absorption depth l : sorbing reectance 251 nm compared with the bulk gold thin lm : 0.64 and l: 19.3 nm due to electron scattering.12 The theoretical calculations matched well the experimental measurements : 0.058 and l: 150 nm at the wavelength of 514 nm. In addition, enhanced electric elds between nanoparticles could contribute to more efcient energy deposition mechanism.12 Besides the efcient energy deposition, the deposited energy is more conned to the laser focal spot due to reduced thermal diffusion in the nanoparticle thin lm. The low thermal conductivity of nanostructured materials is well known in the thermoelectric energy conversion area.13 The nanosystem thermal conductivity is determined by the presence of the interface that induces phonon reection Kapitza resistance or phonon scattering. It is reported that AuPd nanoparticles stabilized by alkanethiol have very small thermal conductance 5 MW/ m2 K due to the huge vibrational mismatch

FIG. 3. Color online Dark eld microscope image of laser ablation ejecta captured from a sintered gold thin lm and b nonsintered gold nanoparticle lm. Ejecta from sintered gold lm showed several micron size ejecta while ejecta from unsintered nanoparticle lm were aggregates of 5 50 nm agglomerate nanoparticles. The inset is a SEM image of nanoparticles aggregates. Downloaded 28 Feb 2008 to 129.132.68.243. Redistribution subject to AIP license or copyright; see http://apl.aip.org/apl/copyright.jsp

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FIG. 4. Color online 20 innite corrected laser ablation with 50 lower ablation energy.

AFM depth and cross sectional images of gold positive line features made from a nonsintered nanoparticle lm laser ablation with long working lens, b sintered nanoparticle lm bulk gold lm laser ablation with 20 lens, and c nonsintered nanoparticle lm lens. Note that the positive features are always cleaner and well dened in a nonsintered nanoparticle lm laser ablation with much FWHM of positive feature in c was 400 800 nm.

between the nanoparticle solid core and the surface monolayer.14 The efciently deposited energy that experiences lower conduction loss induces nanoparticle melting at very low energy level due to thermodynamic size effect. Heat is then transferred to the SAM or residual solvent inducing evaporation. The melting temperature depression enables ablation driven by material melting and vaporization at much lower laser energy than bulk. Upon reaching the nanoparticle sintering temperature 130 140 C , the SAM desorbs and becomes volatile. At this stage, molten nanoparticles agglomerate to bigger molten particles that are expelled by the pressure built-up from the volatile species expansion such as desorbed SAM, residual organic solvent, and trapped air gas. In addition, due to the presence of SAM, nanoparticles are held together by weak physical van der Waals force15 compared with the strong polycrystalline metal bonding in sintered nanoparticle lm material. These combined effects contribute to the low ablation threshold and clean ablation prole. Scanning electron microscopy SEM and dark eld optical microscope images of laser ablation ejecta collected on a quartz substrate placed at 1 mm gap above the ablation surface are shown in Fig. 3. The ejecta from sintered nanoparticle lm consisted of big molten drops approximately in micrometers and exfoliated lm fragments. On the contrary, the laser ablation of unsintered nanoparticle lm produced 5 50 nm aggregates, including the agglomerates that grew at the expense of smaller molten nanoparticles. The brightness of this deposit changed upon heating above the sintering temperature of 130 140 C, signifying that the ejecta from contain not only molten nanoparticles but also unsintered nanoparticles with SAM. Based on the nanoparticle lm laser ablation, Au positive lines were fabricated. Figure 4 shows how this technique can be applied to improve the quality of ablation features. Laser ablation of sintered lm Fig. 4 b predictably showed elevated rim prole due to melt expulsion while laser ablation of unsintered nanoparticle lm Fig. 4 a yielded clean features. Figure 4 c shows submicron lines full width at half maximum FWHM : 400 800 nm with 3 m pitch. The conductor lines were sintered after ablation and found highly electrically conductive and isolated from each other. Note that the ink-jet printing resolution is 50 100 m, while such small features would require a photolithographic process. The size of the conductive positive features can be reduced signicantly by utilizing higher magnication focusing lens. Even sub-100- m features will be possible with

near eld scanning optical microscope-based ablation scheme.16 To summarize, by ablating unsintered nanoparticle lms, clean and precise patterning characterized by low ablation threshold could be obtained. This could be explained by considering the combined effects of melting temperature depression, lower conductive heat transfer loss, strong absorption of the incident laser beam, and relatively weak bonding between nanoparticles during laser irradiation. The possibility of utilizing high frequency nanosecond laser and a fast x-y galvanometer system could make this method attractive in exible electronics manufacturing. Financial support from the University of California, Berkeley by the U.S. NSF CTS-0417563 , from the Swiss Federal Institute of Technology in Zurich by the Swiss National Science Foundation 2000-063580.00 , and from Korea University by Basic Research Program of the Korea Science and Engineering Foundation R01-2005-000-11036-0 is gratefully acknowledged.
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