NANO LETTERS

Laser-controlled Growth of Needle-shaped Organic Nanoaggregates

Frank Balzer
Humboldt-UniVersitat zu Berlin, Institut fur Physik/ASP, InValidenstr. 110, D-10115 Berlin, Germany

2002 Vol. 2, No. 7 747-750

Horst-Gunter Rubahn* 1
Fysisk Institut, Syddansk UniVersitet, CampusVej 55, DK-5230 Odense M, Denmark
Received April 6, 2002; Revised Manuscript Received May 2, 2002

ABSTRACT
Arrays of mutually parallel oriented, single-crystalline, needle-like structures of light-emitting p-hexaphenyl molecules are generated in the focus of an argon ion laser. The cross sectional dimensions of the needles are of the order of 100 to 200 nm with lengths up to several hundred micrometers. While the orientation of the individual molecules in the needles is defined by the direction of surface dipoles, the localization on the surface, the length distribution as well as mutual distances can be adjusted via size and position of the laser focus spot.

1. Introduction. A pronounced dichroism and efficient blue light emission following electric or optical excitation make para-hexaphenyl (p-6P) thin films well-suited candidates as the optically active elements in polarized organic lightemitting diodes, full color displays, or organic semiconductor lasers.1 Adsorbed on dielectric surfaces, their molecular axes are aligned either parallel to or normal to the surface. The alignment can be altered by the growth conditions (adsorption rate, surface temperature) in combination with the choice of the underlying substrate.2-4 Light absorption, emission, and electrical properties of p-6P thin films depend strongly on the molecular orientation.5-7 For example, the threshold voltage for electroluminescence is significantly lower for molecules aligned parallel to the surface as compared to that of normal oriented molecules.8 Hence, growth conditions that favor the generation of films with parallel oriented molecules are of special interest. Due to their large luminescence quantum yield (up to 0.39) p-6P molecules might serve as versatile optoelectronic components not only if they form an ultrathin film but also if lower dimensional nanoscaled aggregates such as quantum dots or quantum wires are generated. For that purpose the formation of mutually and, with respect to the substrate surface, well-oriented aggregates with large aspect ratios would be most useful. Recently we have demonstrated that growth of p-6P on a mica surface at elevated surface temperatures results in these kind of nanostructures, namely single crystalline needles with their (111) face parallel to hh
* Corresponding author. E-mail: rubahn@fysik.sdu.dk. 10.1021/nl0255707 CCC: $22.00 Published on Web 05/10/2002 2002 American Chemical Society

the surface plane.10 The needles consist of parallel stacks of laying molecules, which are oriented along the direction of microscopic dipoles on the mica surface. They have submicrometer cross sectional dimensions and lengths as large as millimeters. Moreover, due to the strong dipole confinement of individual molecules, the needles form large domains with parallel oriented entities. In the present article we show that the growth of needlelike structures on mica substrates occurs in a rather narrow surface temperature range T 25 K at a small adsorption rate of 0.025 nm/s. This observation can be used to locally influence needle growth via laser-induced surface heating. The direction of the needles is still given by the direction of surface dipoles and they are mutually well aligned. Their length distribution and their mutual distances can be varied by changing the ratio between global and local heating. With this laser-controlled growth mechanism a significant step has been achieved toward the generation of nanostructured connecting elements between optically active surface areas. 2. Experimental. Growth of p-6P thin films on muscovite mica is performed in high vacuum (10-7 mbar). p-Hexaphenyl (TCI America) is evaporated onto the mica surface at variable surface temperatures with a deposition rate of 0.025 nm/s from a resistively heated oven with a nozzle of 0.5 mm diameter. The flux of p-6P molecules is monitored by a water cooled quartz microbalance. Low energy electron diffraction measurements ensure the single-crystallinity of the generated films and nanostructures. Thin sheets of mica (thickness L ) 120 m) are cleaved in air and are transferred immediately after cleavage into the high vacuum chamber.

Figure 1. Fluorescence micrographs of p-6P films (mass thickness 5 nm) grown at substrate temperatures of (a) 340 K, (b) 356 K, and (c) 368 K.

They are mounted on a copper plate which allows homogeneous heating via a tungsten filament. During film growth, radiation from an argon ion laser (multiline 456-514 nm) is focused onto the mica substrate. The measured Gaussian focus diameter is 2w ) 0.9 mm. Following growth of films with 5 nm mass thickness, the substrates are investigated in a fluorescence microscope in air. Excitation is performed with a mercury lamp centered at 365 nm. The emission is observed behind a 420 nm long pass filter with a high-resolution digital camera. 3. Results and Discussion. In Figure 1 fluorescence micrographs of p-6P films, grown on mica with 5 nm mass thickness and at various substrate temperatures of (a) 340 K, (b) 356 K, and (c) 368 K are shown. Obviously, the growth of long needles takes place only for the sample held at 356 K, whereas for slightly higher or lower surface temperatures continuous films (on a micrometer scale11) are grown. Note that in ref 10 we have reported needle growth of p-6P on mica at surface temperatures between 360 and 460 K. However, for these measurements the sample heating was not uniform, resulting in strong temperature gradients on the surface. As shown in the present paper with an
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Figure 2. Influence of laser irradiation on the growth of p-6P thin films (mass thickness 5 nm) on mica at room temperature. Argon ion laser power 0.55 W (a), 0.72 W (b), and 0.9 W (c). The Gaussian focus diameter of the laser at the substrate surface is 0.9 mm.

improved sample holder, needle growth is observed whenever the correct temperature is obtained, hence even on sections of samples that are partially too hot. Because of the use of a polarizer in front of the camera, two domains of differently aligned molecules are visible in Figure 1c.10 In Figure 2 fluorescence micrographs are shown for 5 nm thick p-6P films, grown at room temperature on mica, but under the influence of irradiation from the Argon ion laser. From (a) to (c) the laser power has been increased from 550 mW to 720 mW and 900 mW. In Figure 2a a pronounced needle growth is observed solely inside the laser focus, probably induced by laser heating. For Figures 2b and 2c the temperature increase in the center of the laser focus is too high to allow needle growth. The area in which needle growth is allowed is successively shifted outward. Before rationalizing these observations we note that the copper plate that underlies the sample will be heated only marginally.12 In this way it will act as a heat sink, ensuring that the heating is roughly restricted to the illuminated area. Unfortunately the presence of the copper plate also makes it difficult to quantitatively estimate the laser-induced temNano Lett., Vol. 2, No. 7, 2002

Figure 3. Normalized reciprocal laser intensity vs radii rN, where needle growth is observed. The solid line is the expected increase of the distance, where a certain temperature rise occurs, with increasing laser intensity (Gaussian radius w ) 450 m).

perature increase in the center of the focus. If we neglect the heat sink and assume a free-standing mica, then with an irradiation time of 200 s, an absorption coefficient R ) 5.8 10-4 m-1,15 thermal diffusivity of mica ) 1.6 10-6 m2/s, and thermal conductivity of Kmica ) 3.1 W/Km, we calculate12 a temperature rise in the center of the laser spot of T ) 69 K for PL ) 550 mW. This agrees well with the temperature of T ) 356 K for the thermally heated sample, where needle growth is observed (Figure 1b). However, due to the presence of the copper plate, at least a two-dimensional numerical simulation (perpendicular to and radial on the surface) of heat transport through the mica is necessary. This FTCS (forward time, central space14) calculation results in a temperature increase of 11 K on the mica surface within the focus center. This value very much depends on the thermal constants of mica. If we apply instead of the average values used up to now the minimum conductivity values from ref 13, then we find a temperature increase of more than 50 K, which might be even higher if we take into account a finite thermal resistance between mica sheet and copper plate. From that we conclude that it is very likely that the needle growth is directly related to the laserinduced temperature increase on the mica surface. If the laser irradiance is too high, needle growth is not observed within the center of the laser focus, but in a ring around that spot (Figures 2b and 2c). The ring has a radius rN and width rN that both increase with increasing laser irradiance (Figure 2b and Figure 2c). Figure 3 shows that this increase is directly related to the temperature profile within the laser focus. The radial range rN is represented as horizontal bars. Because of the direct relation between the Gaussian laser beam profile and the temperature rise on the mica surface, r2 depends exponentially on PL, N PL,0 r2 N ) exp - 2 PL w

Figure 4. (a) Growth of well-separated needles within the laser irradiated spot on a p-6P film grown at 356 K. Laser power 0.5 W. (b) Growth 150 m outside the center of the focus. (c) Typical force microscopy image (3 3 m2) of parallel needles, revealing their characteristic dimensions. Height of the central needle 84 nm, width 217 nm.

( )

(1)

with PL,0 denoting the minimal laser power suitable for needle growth (i.e., rN ) 0 for PL ) PL,0). In Figure 3 this relation
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is plotted as a solid line. It agrees very well with the measured radii. So far we have investigated the effect of laser irradiation on needle growth on an otherwise structureless film. Now we investigate conditions where needle growth occurs already without laser irradiation. The sample grown at 356 K (Figure 1b) shows long, densely packed needles. If we irradiate this sample during growth with 0.5 W laser power, we find within the laser focus well separated needles with nearly constant length of 16 ( 3 m (Figure 4a). At the border of the laser focus the length and density of the needles are increasing (Figure 4b), until the density reaches that of the rest of the sample (Figure 1b). The true dimensions of the needles that have been generated that way (width 200 nm, height 100 nm) are shown in Figure 4c with the help of atomic force microscopy.16 Obviously, behind a simple heating of the sample, laser irradiation also leads to a more complex manipulation of aggregate dimensions in terms of thermal or even nonthermal
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laser desorption and growth inhibition. Size-dependent desorption characteristics are well investigated for metallic aggregates on dielectrics,17 and they can be used to control also the growth of metallic nanoparticles.18 In summary, we have demonstrated that irradiation with an argon ion laser during growth of p-6P films allows one to stimulate and to manipulate the generation of nanometer scaled, needle-shaped aggregates. Since it is also possible to modify the mutual distances between the needles, it will be possible to locally induce needle growth on predefined areas of a substrate that contains an optoelectronically active pattern. The minimum structure size achievable with this method is given by (a) the intrinsic restrictions in width and height of the needles that depend on adjustable growth conditions and allow the laser-induced formation of aggregates with submicrometer dimensions; and (b) the focus diameter (a few micrometers) and the thermal diffusion length. The latter factors, however, concern the length of the needles. This length is mainly determined by the size of the surface dipole domains and the size of the uncovered mica substrate. Acknowledgment. We are grateful to the Danish Research Foundation SNF for financial support and to E. J. Kintzel, Jr. for atomic force microscopy on our samples. We also like to thank one of the referees for pointing out the complex thermal behavior of our system.

References
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