Eur. Phys. J. E 12, 443448 (2003) DOI: 10.

1140/epje/e2004-00014-7

THE EUROPEAN PHYSICAL JOURNAL E

Inuence of surface cleaning on dewetting of thin polystyrene lms

P. M ller-Buschbauma u
TU Mnchen, Phy.-Dept. E13, James-Franck-Str.1, 85748 Garching, Germany u Received 1st August 2003 Published online 20 January 2004 c EDP Sciences, Societ` Italiana di Fisica, Springer-Verlag 2004 a Abstract. Thin polystyrene (PS) lms on top of silicon substrates are a frequently investigated model system in the framework of unstable lms. However, with respect to stability the various experiments yielded contradictory results. Focussing on the inuence of preparation conditions such as the surface cleaning solves these contradictions. By applying dierent surface cleans the PS lm can be changed from a stable homogeneous one into a completely dewetted one. In addition to the type of clean applied, the time between cleaning the surface and spin-coating the polymeric layer on top turned out to be an important experimental parameter. PACS. 68.55.-a Thin lm structure and morphology 68.15.+e Liquid thin lms 68.47.Mn Polymer surfaces

1 Introduction
Thin polymer lms are of growing importance with respect to an increasing number of high-tech applications. Caused by the progressive miniaturization, typical spatial sizes have to be decreased. With reducing lm thickness the long- and short-range interactions between the polymer and the solid [1,2] become important. While macroscopically thick lms are stable, thin lms can be unstable or metastable. A relaxation towards the thermodynamical equilibrium can occur, e.g. caused by heat load exposed on the polymeric layer. The corresponding destabilization process destroys the initially homogeneous polymer lm. The lm dewets from the substrate and rearranges into an assembly of polymeric drops replacing the continuous layer. Because the assembly of drops has inferior properties with respect to typical application characteristics such as dielectric constant or resistance a prediction of the dewetting is highly demanded. Therefore unstable thin polymer lms are interesting from a basic research as well as from an applied science point of view. The model system polystyrene (PS) on top of silicon substrates (Si) covered with an oxide layer (SiOx ) turned out to be preferentially examined [323]. With respect to the long-ranged part of the eective interface potential as long as only van der Waals contributions are taken into account, PS is stable on Si and unstable on SiOx . For Si covered with a thin oxide layer of thickness d, PS lms with thicknesses smaller than a critical thickness hc are unstable and with a thickness h > hc are expected to be stable. However, experimental results on the destabia

e-mail: muellerb@ph.tum.de

lization and the related dewetting mechanism (spinodal dewetting versus nucleation) partly yielded contradictory results. In contrast, the model system (PS on SiOx /Si) itself seems well dened. PS is widely used in applications, easily synthesized with a narrow molecular weight distribution and readily purchased from suppliers. Soluble in many standard solvents such as toluene or tetrahydrofurane PS is well suited for thin lm preparation via the spin-coating technique. The applicability of the spin-coating technique is of great importance since spin-coating enables the preparation of thin homogeneous polymer lms also on non-wetting surfaces [24,25]. As a consequence the lm thickness is tuneable from values below the radius of gyration of the unperturbed molecule up to many micrometers and thus covers the interesting range with respect to dewetting. PS is glassy at room temperature, but has a moderate glass transition temperature, which can be achieved with standard heating set-ups. In atactic PS no complications due to crystallization occur. PS is chemically inert and has a low vapor pressure in the melt like most polymers. Also Si is extremely important for industrial applications and readily purchased from suppliers with very high purity. Its crystallographic orientation, doping (p- or ntype), resistivity, thickness and diameter can be chosen. The polished surface exhibits a very small surface roughness typically below 1 nm. Thus as compared to typical feature heights resulting from the dewetting of a thin polymer lms, the Si surface can be assumed to be at and smooth. However, the surface of Si is commonly covered with a native oxide layer. This native oxide layer results from the manufacturing of the substrates and has a typical thickness of 12 nm. To increase the oxide layer thickness

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the substrates are thermally oxidized which typically resulted in values on the order of 200 nm [35,17,18]. Within this commentary the inuence of preparation conditions on the dewetting of thin PS lms is focused. The inuence of surface cleaning in the thin lm preparation is discussed and turned out to be a central part with respect to dewetting.

2 Surface cleaning
After exposure to air the bare Si surface is usually covered with a thin native oxide layer and various impurities, such as particulates, organic residues, metal residues and ionic species. For Si based device fabrication a variety of dierent cleaning procedures has been established to remove these impurities. With each new device generation, the cleaning requirements become more stringent, and the number of cleaning steps increases. For example, for 64 Mb 0.25 m dynamic random access memory (DRAM) fabrication, 60 to 70 cleaning steps are usually required [26]. Common cleaning procedures can be grouped in aqueous cleaning, dry wafer cleaning, ultraviolet-ozone cleaning, vapor phase wafer cleaning and plasma cleaning processes [27]. Prominent examples of aqueous cleaning processes are RCA-1 clean (based on 5 parts deionized water, 1 part 27% ammonium hydroxide and 1 part 30% hydrogen peroxide), RCA-2 clean (based on 6 parts deionized water, 1 part 27% hydrochloric acid and 1 part 30% hydrogen peroxide), piranha clean (based on 1 part deionized water, 3 parts 98% sulfuric acid and 1 part 30% hydrogen peroxide) or BOE clean (based on 1 part deionized water, 1 part hydrouoric acid and 1 part ammonium uoride) [28]. A typical example of dry wafer cleaning is cryogenic cleaning using either a CO2 or an argon/nitrogen gas source (frequently called snow-jet). RCA-1 and piranha are used as a procedure for removing organic residues and certain metals, RCA-2 for removing atomic and ionic contaminants and BOE for stripping the oxide. If wrongly applied, cleaning is replaced by etching and from the aqueous cleaning processes a surface roughening can result. CO2 cleaning removes micron and submicron particulates and hydrocarbon-based contamination. It is nondestructive, nonabrasive and residue-free and mainly used for specic spot cleans. Limiting problems with recontamination are overcome by special ultra-clean environmental control [26]. In contrast to multiple-step cleaning, most likely investigations concerning the dewetting of thin polymer lms make use of one single cleaning step only. In addition, in dierent experimental groups, dierent cleaning procedures have established, e.g. [6,18,29,30]. As a consequence, although the systems under investigation are nominately equal, by dierent surface cleaning small differences can be introduced. Having a closer look on the inuence of the dierent cleaning processes with respect to the resulting oxide layer, X-ray reectivity measurements turned out to be very eective [3135]. Native oxides formed by aqueous cleaning processes were reported to have a lower mass

density as compared to Si (Si = 2.33 g/cm3 ). From ammonium hydroxide (SiOx = 2.11 g/cm3 ) and hydrochloric acid (SiOx = 2.07 g/cm3 ) based cleaning even lower densities result as compared to oxides formed by sulfuric acid (SiOx = 2.23 g/cm3 ) [31,34]. In contrast thermally oxidized SiOx typically exhibited densities larger than bulk Si (SiOx = 2.41 g/cm3 ) [32]. In addition the density depends on the oxidation temperature applied. Some measurements even showed evidence for the presence of a density gradient through the thick oxide layer, which was attributed to a possible temperature gradient within the sample during the oxidation process [35]. The density decreased from the surface to the Si/SiOx interface. The structure of the amorphous SiOx (a-SiO2 ) is similar to that of a quartz, which consists of tetrahedral SiO4 units [36]. The macroscopic density variation of the native oxides was gured out not to result from the densication of a-SiO2 , but to be originated by inhomogeneities of the layer. Si hydrides and hydroxyl was considered to be present, depending on the cleaning process chosen. Native oxides prepared in presence of hydrochloric acid had a large amount of Ox Si-Hy and Si-Hz imperfections, prepared with ammonium hydroxide had little Ox Si-Hy but large Si-Hz contributions and prepared with sulfuric acid only very little of both [34]. As a consequence native oxide and thermally induced oxide dier in their chemical composition and a deviation in the short and long-ranged part of the interface potential might be expectable. With respect to the wettability of the surface the contact angle is of interest. On silicon substrates, as received from the manufacturer, the top oxide layer is hydrophilic or hydrophobic, depending on the chemicals used during the polishing of the surface. In principle, after polishing the wafers were demounted and subjected to a nal clean. However, the surface chemistry is uncontrolled due to this unknown cleaning, which explains the rather large scatter of contact angle values reported (e.g. contact angle against water up to 31 [37]). After application of the RCA-1 clean the surface is rather hydrophilic with a typical contact angle against water of = 2 . The subsequent application of RCA-2 does not modify this value [37]. An additional storage time of 5 days increases the value up to = 16 . Applying only RCA-2 creates a hydrophilic surface with = 0 which is less stable. A storage under vacuum for 1 hour only results in a surface modication yielding = 36 [38]. Replacing water by a Langmuir lipid monolayers such as L--dimyristoylphosphatidyl-ethanolamone DMPE [39] results in higher sensitivity and dierences of the contact angle between the application of the RCA-1 clean and a subsequent RCA-2 clean. The value of the contact angle in the liquid-expanded phase increases from 11.5 to 26 if the second cleaning step was added. Using a sequence of RCA-1, RCA-2, RCA-1 clean results in values equal to the single RCA-1 clean which underlines the reproducibility of the surface chemistry introduced by the chosen clean [40]. During aging by storage in the Langmuir trough slight changes of the contact angle value were detected after one hour already.

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Fig. 1. Optical micrographs of the surface of a 30 nm 8.9 k PS lm after annealing for 24 h at 140 C. The substrates were cleaned by a) piranha, b) piranha + 12 h storage, c) RCA-1, d) RCA-1 + 12 h storage, e) RCA-2, f) RCA-2 + 12 h storage, g) 24 h storage in Milli-Q water and h) wiping with a toluene soaked wipe immediately before spin-coating the PS layer. While the PS lm looks gray, the Si surface reects more light and is looking white. Each micrograph shows a surface size of 625 469 m2 .

3 Thin polystyrene lms

To picture the inuence of dierent cleaning processes on the dewetting, the model system PS (Mw = 8.9 k, Mw /Mn = 1.05) on top of Si with a native oxide layer (thickness 1 nm) is revisited. Figure 1 shows the example of 8 dierent surface cleans applied immediately before spin-coating a 30 nm PS layer out of a toluene solution on top. Frequently applied cleaning procedures such as (a) the piranha clean, (c) the RCA-1 clean and (e) the RCA-2 clean are compared with more exotic techniques such as (g) 24 h storage in ultra pure water (Milli-Q water) and (h) wiping with a toluene soaked kimwipe. In addition the inuence of 12 h storage between cleaning and spin-coating (b, d, f) is demonstrated, to gure out the inuence of aging on the common cleans. After spin-coating homogeneous PS lms resulted, as determined by X-ray reectivity and atomic force microscopy (AFM). Subsequently, the samples were stored in a vacuum furnace for 24 h at a temperature (T = 140 C) well above the glass transition temperature of PS. From the spinodal dewetting model within this time no destabilization from an, if applicable spinodal process is expected. After quenching down to room temperature the resulting structures were viewed with optical microscopy. From the piranha, RCA-1, aged RCA-1 and RCA-2 clean homogeneous and defect free surfaces resulted, as expected from the long-ranged part of the interface potential. In contrast, the 4 other cleans yielded a destabilization. The aged piranha, aged RCA-2 and the Milli-Q water clean caused micrometer sized holes in the PS layer and after a kimwipe usage a complete decay into isolated drops was observed. The deposition of polydimethylsiloxane (PDMS) grains solved in toluene from the kimwipe and by the wiping spread over the complete surface destabilizes the PS lm, because PS dewets on PDMS. The ultra pure water aggressively attacked the oxide surface by a partial dissolving. Being a local process similar to etching, the storage under Milli-Q water gives rise to an increase in the surface roughness by a factor of 2. The modied surface

areas act as nucleation sites for a dewetting of the PS lm. The dierent stages of the dewetting which were reached by a modied surface treatment can be transformed into a time span after the onset of destabilization. Indicating the density and strength of the nucleation sites, obviously PDMS, usually used as a dewetting agent, is most eective. The acid piranha clean is sensitive to aging similar to the acid RCA-2 clean. Small holes of uniform diameter are visible. The short-ranged part of the interaction is modied resulting in a strong change of the contact angle by more than 30 . Causing a deep minimum in the eective interface potential close to the wall the short ranged interaction can introduce dewetting. The comparison with dewetting experiments of other research groups is restricted to examples which provided a detailed description of the surface cleaning by the authors. Reiter [14] used native oxide covered Si substrates as obtained by the supplier and observed dewetting pattern similar to Figure 1h. Stange et al. [20] used Si wafers as received from the manufacturer to keep a contamination layer of airborne hydrocarbons as detected with X-ray photoelectron spectroscopy. Removing the contaminations by ozone or acid cleaning virtually eliminated dewetting. Subsequently to cleaning contaminated wafers exhibited the same process of nucleation and dewetting as the received wafers, although the rate of hole growth diered [20]. An acid cleaning based on sulfuric acid with varying details of the applied solution was performed by several groups [6,12,13,17,18,21]. Dewetting of a 30 nm 4k PS lm was observed by Feng et al. [6] after storage of the cleaned substrates in a vacuum furnace for approximately 30 min at room temperature. Xie et al. [21] stored the cleaned surface for 24 h under vacuum at room temperature. After 25 h annealing of the 35 nm 4k PS lm holes comparable to the ones shown in gure 1b were reported. Seemann and coworkers [17,18] applied the acid cleaning step prior to coating of the PS layer. PS lms in the lm thickness regime on the order of 30 nm were stable. Thus the observed behavior is well explainable within the applied surface clean.

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4 Ultra-thin polystyrene lms

Decreasing the PS lm thickness at heights comparable to the radius of gyration Rg results in an instability of the initial homogeneous PS lm irrespective of the applied surface clean. Ultra-thin PS lms are spin-coated from highly diluted toluene solutions on pre-cleaned Si substrates. The lm thicknesses were determined with X-ray reectivity measurements and with the AFM scratch test resulting in the required high precision on the order of angstrms. o In contrast to the thin lm regime, the resulting PS lms can exhibit surface structures without an additional annealing. These structures result either directly from the spin-coating or develop during storage of the spin-coated PS lm at room temperature. Figure 2a shows the surface of a 207k PS (Rg = 4.5 nm) lm on a piranha cleaned, non pre-stored Si as measured with AFM. After spin-coating, the PS lm was stored at room temperature for approximately 2 months before the AFM were taken. The initially homogeneous 2.5 nm thick lm had decayed, exhibiting a surface structure with one dominant in-plane length as visualized by the Fourier transform (Fig. 2b). The dewetting of highly elastic thin PS lms with even larger lm thickness was reported by Reiter previously [41]. Decreasing the PS concentration of the spin-coated solution even further as compared to the one used to obtain initially 2.5 nm thick PS lms, yields non homogeneous lms immediately after spin-coating. Figure 2c shows an example of a non homogeneous surface probed with AFM directly after the spin-coating. Comparable surface structures had been observed in earlier work as well [19]. PS forms polygonal pattern (similar to Voronoi tessellations [42]) on the Si surface which resemble the polygons commonly observed in the dewetting of thicker PS lms [14] but scaled-down in their lateral size. In contrast, increasing the PS concentration of the spin-coated solution as compared to the one used to obtain initially 2.5 nm thick PS lms, gives rise to homogeneous lms. For a large variety of molecular weights such as 8.9 k, 27.5 k, 207 k and 1530 k lms with thicknesses 3 nm remain stable at room temperature during months of storage after the spin-coating. As compared to the radius of gyration (e.g. Rg = 2.5 nm for 8.9k PS up to 33.2 nm for 1530k PS) the degree of connement diers for these lms. Nevertheless, a destabilization as pictured in Figure 2a was not observed without annealing and therefore the starting conditions of a common dewetting experiment, as performed in the thin lm regime, are fullled. Destabilization of homogeneous, ultra-thin PS lms which were stable during storage at room temperature occurred during annealing. However, since the surface chemistry is strongly inuenced by the applied clean, the time constants of the instability dier. Figure 2 shows two extreme cases resulting from the applied cleaning procedures such as (d) the piranha clean and (e) wiping with a toluene soaked kimwipe. A 3 nm thick 27.5k PS lm was annealed for 20 min at 130 C. AFM data were taken directly after the annealing was nished. On the piranha cleaned surface rst small holes in the elsewhere continuous but modu-

Fig. 2. AFM pictures and related Fourier transforms of ultrathin PS lms on ad) piranha cleaned Si and on e, f) toluene soaked wipe cleaned Si. The initial lm thicknesses were a) 2.5 nm and d, e) 3 nm. In c) no initial homogeneous lm was obtained. The used molecular weights were a, c) 207 k and d,e) 27.5 k. Scan size (2 2 m2 for a, c, d and 8 8 m2 for e) and height scaling (color bar covers approximately a) 4, c) 2, d) 2, e) 4 nm) are individually adapted to emphasize on the resulting topography. High surface regions are shown in white, low ones in black. AFM measurements were performed in non-contact mode to minimize a tip induced surface modication.

lated lm are visible. RCA-1 and RCA-2 cleaned surfaces exhibit comparable features with slightly modied density of holes whereas the toluene soaked wipe cleaned surface is spangled with holes. Transferring the two shown snap shots into a time dependence yields dierent characteristic rupture times. In the framework of the spinodal dewetting model the dierent rupture times = 48h5 /A2 would correspond to changes in the Hamaker constant A, because the other parameters such as surface tension , viscosity and lm thickness h are constant. Unfortunately, the exact detection of a rupture time by AFM is rather dicult and inconvenient. In Fourier space the rst small holes do not give rise to a ring-like intensity distribution as it is present for the wipe cleaned Si (Fig. 2f). Consequently, the pattern is described by one characteristic wavelength qmax obtained from the position of the intensity maximum. Typical spinodal like surface pattern evolve during further annealing. A similar observation was reported by Xie et al. [21] in case of 4k PS lms with thicknesses below 10 nm on acid cleaned Si. Due to the smaller molecular weight these lms

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were not that conned as compared to the ones presented in Figure 2. In contrast, Seemann et al. [17] restricted the spinodal regime to a PS layer thickness below 2 nm in case of a 1 nm oxide layer thickness. With increasing oxide layer thickness the value of the PS lm thickness being unstable against spinodal dewetting increases in their investigation. However, due to the small molecular weight chosen (Rg = 1.2 nm for 2k) the connement regime was not touched in the investigation of Seemann et al. [17]. Rehse et al. [43] observed an instability-stability transition of PS (molecular weights between 5.6k and 1000k) on corrugated as well as on at Si substrates at a critical thickness. The critical thickness was reported to scale with the radius of gyration of the unperturbed chain. Films with thicknesses larger than 0.55 Rg remained stable and ones with thicknesses smaller than 0.55 Rg dewetted [43]. Aubouy [44] identied one single process, namely the competition between the entropy of the set of loops, which favors a dense state of the polymer layer, and the repulsive loop-loop interaction, which favors a dilute state of this layer, to result in a critical lm thickness. As a consequence ultra-thin polymer lms dewet surfaces that thick lms wet [44]. With respect to the late stages the resulting droplet pattern of dewetted conned PS lms do not obey a polygonal assembly but are distributed with one most prominent nearest neighbor distances [12,45]. As a consequence, only the generally applied clean is not sucient to overcome the apparently dierent observations with respect to dewetting. Due to the extreme sensitivity of these ultra-thin PS lms on the short ranged part of the interface potential, additional work on this particular topic will be required to install a relation between cleaning and interface potential.

References
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5 Summary
In summary, the substrate surface cleaning marks a central step of the complete dewetting experiment. Cleaning changes the chemistry of the oxide layer. Due to the chosen cleaning the lm stability can be varied from a stable homogeneous lm into a dewetting of the polymer lm. In addition, the time between cleaning the surface and spin-coating the polymeric layer on top turned out to be an important parameter. Taking into account the dierent cleans applied, the contradictory experimental observations with respect to the stability of thin PS lms on Si with an oxide surface are explainable. For ultra-thin PS lms still discrepancies remain. As a consequence, a detailed description of the applied surface cleaning should be part of each experimental description related to dewetting.
This work had beneted from discussions with K. Graf, M. Mller, O. Wunnicke and M. Stamm and was supported by u the DFG in the framework of the priority program wetting and structure formation at interfaces (Sta324/8). A Gtzendorfer o and E. Bauer assisted with the AFM investigations.

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Discussion on contribution by P. Mller-Buschbaum u

U. Steiner comments on M ller-Buschbaums obseru vation the preparation of homogeneous lms thinner than about 2 nm by spin-coating seems to be impossible. We are able to make homogeneous lms in the 1-2 nm range. The ability to do this depends presumably on the molecular weight (we used 2 kg/mol, M-B. used 207 kg/mol), the spin-coating solvent and the substrate preparation. A. Sharma comments on the question if the instability of ultrathin lms may be caused by NONequilibrated conformations of the polymer chains. We have a theory (with J. Sarkar and V. Shenoy; to be published) that indeed predicts destabilization of soft elastic lms thinner than a few nanometers by the van der Waals force alone without invoking any non-equilibrium congurations. This is not to deny the importance of non-equilibrium eects in the form of residual stresses for example, which would cause further damage! Comment by H. Kaya and B. Jrme eo The observed transformation of a polystyrene lm at room temperature seem to point towards the concept of a cooperation distance in glasses [B. Jrme, J. eo Phys.: Condens. Matter 11, A189 (2001)]. When the lm thickness is lower than the cooperation distance, the relaxation time of the molecules is so low that the polymer behave as a liquid rather than a glass. It is dicult to make any absolute statements referring to the equilibrium conformations of the polymers in the thin lm. In a real-life experiment on spin-cast PS lms, the chains conformations will be distributed around the equilibrium value. Referring to solvent retention experiments performed in our group (J. Garcia Turiel and B. Jrme, in press), the measured eo amounts of retained toluene in the polystyrene lms always showed signicant error bars, especially at small thicknesses, although the overall physical trend was clear. The chain conformation averaged across the lm can deviate strongly from the equilibrium average conformation, again a small-system eect. Comment by U. Thiele I think, it is not necessary to invoke additional eects like non-equilibrated conformations of the polymer chains. In my understanding a ultrathin polystyrene lm on an oxide coated silicon substrate is energetically unstable independently of it being in glassy or liquid state. Thereby, I assume that the Hamaker constants depend only weakly on temperature or phase. However, this unstable situation is usually relaxed by dewetting (associated normally with viscous ow) above the glass transition temperature. But there exists in my opinion no reason why an energetically favourable rearrangement of the polystyrene layer should not happen below the glass transition temperature. A possible candidate for the mediating transport process could be surface diusion. Because the process is governed by the same energy functional as dewetting and also represents the evolution of a conserved order parameter (because of mass conservation) even the governing equation will have the form of the usual lm thickness evolution equation with the mobility replaced by a diusion constant (that itself may depend on concentration or lm thickness). This implies that there is a continuous transition between the spinodal length scales found in viscous dewetting and in diusional dewetting. However, the transition in the time scales will normally not be continuous because diusion is much slower than viscous ow. A discussion of possible kinetics can be found in [D. Srolovitz, S. Safran, J. Appl. Phys. 60, 255 (1986)].