NANO LETTERS

Direct Thermal Patterning of Self-Assembled Nanoparticles

Hendrik F. Hamann,* S. I. Woods, and Shouheng Sun
IBM T. J. Watson Research Center, Yorktown Heights, New York 10598
Received August 26, 2003; Revised Manuscript Received October 8, 2003

2003 Vol. 3, No. 12 1643-1645

ABSTRACT
A general methodology for direct thermal patterning of self-assembled nanoparticle films is presented. Specifically, using laser heating we have fabricated ferromagnetic FePt nanoparticle array patterns with 0.8 m pitch and an edge resolution of 100 nm. The nanoparticle arrays have been investigated by scanning SQUID microscopy and MFM. Finally, we have measured the patterning rate as a function of temperature by monitoring the change in optical reflectance.

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One of the most exciting prospects of nanoparticles is their implementation as building blocks for novel electronic, photonic, and magnetic devices.1-3 While major progress has been made in synthesizing nanoparticles and in controlling the self-assembly of thin films, a general method to pattern and modify these films is not available. Previous techniques to form patterned arrays relied on conventional photo or e-beam/ion beam lithography,4-7 which can be a complicated process. Recently, a simpler patterning technique using direct e-beam exposure has been demonstrated.8,9 While this direct patterning method has successfully reduced the number of process steps (i.e., from five to three), the required vacuum for the e-beam exposure is still costly and could potentially limit the throughput of such a technology. In this paper we present an even simpler patterning methodology, which utilizes localized heating. Our technique is generally applicable; it does not require vacuum conditions and is compatible with emerging contact printing techniques,10-12 micro/nanosphere lithography,13,14 and copolymer lithography.15,16 Depending on the choice for the heat source, the potential resolution may be similar to e-beam lithography. Specifically, using laser heating we demonstrate nanoparticle array patterns with 0.8 m pitch and an edge resolution of 100 nm. After further thermal annealing, the patterned FePt nanoparticle arrays are investigated by a SSM (scanning SQUID microscope) and a MFM (magnetic force microscope), demonstrating the ferromagnetism of the patterned islands. Finally, we investigate the rate of the patterning as a function of temperature by monitoring the change in optical reflectance. The patterning process is illustrated in Figure 1. As a first step nanoparticles with attached stabilizers are deposited on a substrate as described previously.3 The particle film
* Corresponding author. E-mail: hendrikh@us.ibm.com Present address: Neocera, 10000 Virgina Manor Road, Suite 300, Beltsville, MD 20705-4215. 10.1021/nl034706d CCC: $25.00 Published on Web 10/29/2003 2003 American Chemical Society

Figure 1. Process flow of the direct thermal patterning method.

thickness can be tuned readily using self-assembly deposition techniques. In this work we have patterned successfully on glass as well as on Si/SiO2 (50 nm) substrates. In a second step we expose regions of the film to a heat source, which carbonizes the surfactants.3 In a third and final step unexposed regions of the film are removed by an appropriate solvent such as hexane. In our experiments the heat treatment is realized with a pulsed and focused laser beam (@532 nm; NA 0.8; pulse width 10 s; absorbed laser power 4 mW), which is scanned with respect to the sample. The size of the islands can be tuned by either adjusting the laser pulse width or controlling the laser power. Larger patterns can be made by scanning the laser beam slowly with respect to the sample. The temperatures are estimated to be 550 C. The as-

Figure 3. SSM (A) and MFM (B) image of patterned FePt nanoparticle arrays.

Figure 2. Atomic force microscope (AFM) (A) and corresponding line scan (B) of patterned arrays of about four layers of 6 nm FePt nanoparticles, and high-resolution AFM images (C) showing the particle ordering within a patterned island.
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synthesized and patterned particles exhibit a chemically disordered face-centered cubic (fcc) phase and are superparamagnetic. Post-deposition annealing converts the particles to a ferromagnetic, ordered face-centered tetragonal (fct) phase, which has a high magnetic anisotropy (Ku 6 106 J/m3) at room temperature.3 Figure 2 shows respectively an atomic force microscope (AFM) image (A) and a corresponding line scan (B) of a pattern of 6 nm FePt nanoparticles. It demonstrates that the pattern has been developed cleanly and that the background (unexposed regions) is free of particles. The nanoparticle islands have a diameter of 0.8 m with fairly sharp edges (<100 nm). The thickness of the film is 24 to 30 nm, corresponding to about four layers of FePt particles. A closer look at the patterned nanoparticle islands in Figure 2C reveals clearly the individual particles, which suggests that particle sintering does not occur during the patterning process (550 C for less than 10 s). One of the open questions with such a thermal patterning method is whether the properties of the particles will be altered during the process. In our particular case, the pattern is generated under ambient conditions, and consequently the oxidation of the FePt nanoparticles is a concern. To test whether the ferromagnetism of the FePt particles is influenced by the process, we first generated a larger 10 10 m2 array pattern with 40 m pitch and 80 nm heights. After the patterning we annealed the sample under N2 at 580 C for 30 min to ensure that the particles in the pattern were converted to the hard magnetic fct phase. Then we aligned the magnetization direction of the pattern in horizontal direction with a 5 T magnet, removed the field, and scanned the arrays with an SSM. We repeated that experiment with 3 m diameter arrays and scanned the islands with an MFM. Figure 3 shows the respective SSM and MFM images of the nanoparticle islands. Both images demonstrate clearly the ferromagnetism of the patterned arrays; the SSM shows the in-plane magnetization direction. In fact, measuring the absolute magnetic field of the 3 m diameter islands by SSM, we find that the magnetization of the processed FePt
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Figure 4. (A) Calculated temperature distribution (for 3 mW absorbed laser power) in the nanoparticle films and the corresponding rate of patterning. The two scale bars show the fwhm of the heating and probe laser beams. (B) Corresponding reflectance-time profile for 3 mW absorbed laser power and 10 s laser pulse. The solid line represents a fit (see text for details).

nanoparticles is approximately 106 A/m, comparable to the value for unprocessed nanoparticles. This result indicates that the FePt particles were not oxidized during the patterning process. For future application, the patterning speed and its temperature dependence is of importance. For the FePt nanoparticle assemblies, along with the patterning, a change in optical reflectance of the assembly film occurs. We measured this reflectance change with a second probe laser (@650 nm (10 W)). The probe laser is aligned coaxially with respect to the heating laser. We defocus the heating laser beam slightly (full width half-maximum (fwhm) 1.1 m) so that the probe beam (fwhm 0.5 m) samples a smaller region of approximately constant temperature. The
Nano Lett., Vol. 3, No. 12, 2003

spot sizes of the heating and the probe laser beam are inferred from measuring the numerical apertures. In combination with the measured absorbed heating laser power (e.g., 12% for 15 nm thick films), we estimate the resulting steady-state temperatures using finite element (FE) modeling calculations assuming a thermal conductivity of the film and glass of 25 W/mK and 1.4 W/mK, respectively. The resulting temperature distribution for 3 mW absorbed laser power in a 15 nm thick film is shown in Figure 4A. Figure 4B shows the corresponding time profile of the reflectance, which reveals at least two time constants. After the laser beam is turned off, the reflectance increases suddenly, indicating a small thermoreflectance effect in the patterned film. Investigations with different film thicknesses did not show a thickness dependence on the patterning kinetics. Although the exact reaction mechanism of the patterning process is not known, we suggest that the thermal pattering process involves a carbonization of the stabilizers.3 This is supported by Rutherford backscattering experiments,3 where thermally annealed (560 C for 30 min) 4 nm FePt particle assemblies showed a high carbon content of 40 to 50%. In the absence of a more detailed kinetic model, we assume-simply for representation purposes-two consecutive first-order reaction steps and fit the profiles of Figure 4B to a double exponential association function. This gives two first-order rate constants, kfast and kslow. Using the estimated temperatures from the FE modeling and fitting the rate constants obtained at different temperatures to an Arrhenius equation, also shown in Figure 4B, we obtain kfast 108 exp(-14 000 K/T) s-1 and kslow 5 106 exp(-13 000 K/T) s-1. This yields small activation energies for both rate constants (1.6 kJ/mol). Although the measured rates for the process seem to be quite low, we believe that more reactive stabilizers could, in principle, accelerate the speed of the patterning process. From the temperature dependence of the rate constants we obtain the profile for the patterning rates, which is shown in Figure 4A. The lateral change of the patterning rate exceeds significantly the initial heating laser profile, which may explain the fairly sharp edges as observed in Figure 2. Although it has yet to be demonstrated, it is conceivable that the spatial resolution of this patterning technique can approach single-particle dimensions if nanoheat stamps or heated nanoprobes are used.17 In summary, we have presented a simple three-step general method for direct thermal patterning of nanoparticle films.

Using laser heating we have demonstrated the clean patterning of the FePt nanoparticle arrays with an edge resolution of less than 100 nm. We have investigated the patterned (and thermally annealed) FePt nanoparticle arrays by MFM and SSM, which demonstrates the ferromagnetism of the patterned islands. Finally, we have quantified the rate of the patterning process and its temperature dependence. Our patterning approach may be used to generate patterned magnetic media as a solution to the superparamagnetic limit.18,19 Further, it can be extended to attach a single or a few nanoparticles to the end of a sharp AFM tip for fabrication of a highly sensitive MFM probe. Supporting Information Available: Measured patterning rate constants as a function of temperature in an Arrhenius representation. This material is available free of charge via the Internet at http://pubs.acs.org. References
(1) Murray, C. B.; Kagan, C. R.; Bawendi, M. G. Science 1995, 270, 1335-1338. (2) Alivisatos, A. P. Science 1996, 271, 933-937. (3) Sun, S.; Murray, C. B.; Weller, D.; Folks, L.; Moser, A. Science 2000, 287, 1989-1992. (4) New, R. M. H.; Pease, R. F. W.; White, R. L. J. Vac. Sci. Technol. B 1995, 13, 1089-1094. (5) Toporov, A. Yu.; Langford, R. M.; Petford-Long, A. K. Appl. Phys. Lett. 2000, 77, 3063-3065. (6) Fischer, U. C.; Zingsheim, H. P. J. Vac. Sci. Technol. 1981, 19, 881. (7) Ross, C. A. Annu. ReV. Mater. Res. 2001, 31, 203. (8) Lin, X. M.; Parthasarathy, R.; Jaeger, H. M. Appl. Phys. Lett. 2001, 78, 1915-1917. (9) Bedson, T. R.; Palmer, R. E.; Jenkins, T. E.; Hayton, D. J.; Wilcoxon, J. P. Appl. Phys. Lett. 2001, 78, 1921-1923. (10) Chou, S. Y.; Krauss, P. R.; Renstrom, P. J. Science 1996, 272, 85-87. (11) Jacobs, H. O.; Whitesides, G. M. Science 2001, 291, 1763-1766. (12) Xia, Y.; Whitesides, G. M. Angew. Chem. Chem., Int. Ed. 1998, 37, 550. (13) Haynes, C. L.; VanDuyne, R. P. J. Phys. Chem. B 2001, 105, 55995611. (14) (14) Deckman, H. W.; Dunsmuir, J. H. Appl. Phys. Lett. 1982, 41, 377. (15) Park, M.; Harrison, C.; Chaikin, P. M.; Register, R. A.; Adamson, D. H. Science 1997, 276, 1401. (16) Wu, M.-H.; Whitesides, G. M. Appl. Phys. Lett. 2001, 78, 2273. (17) King, W. P.; Kenny, T. W.; Goodson, K. E.; Cross, G.; Despont, M.; Durig, U.; Rothuizen, H.; Binnig, G. K.; Vettiger, P. Appl. Phys. Lett. 2001, 78, 1300-1302. (18) Terris, B. D.; Weller, D.; Folks, L.; Baglin, J. E. E., Kellock, A. J.; Rothuizen, H.; Vettiger, P. J. Appl. Phys. 2000, 87, 7004-7006. (19) Chou, S. Y. Proc. IEEE 1997, 85, 652.

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NL034706D

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