Materials Letters 60 (2006) 1095 1098

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Laser-induced nanocomposite formation for printed nanoelectronics

F. Antolini a,, A. Ghezelbash b , C. Esposito c , E. Trave d , L. Tapfer c , B.A. Korgel b
b

C.R. ENEA Faenza, Via Ravegnana 186, 48018 Faenza, Italy Department of Chemical Engineering, Texas Materials Institute and the Center for Nano- and Molecular Science and Technology, The University of Texas at Austin, Austin, TX 78712, USA c C.R. ENEA Brindisi, S.S. 7 Appia km 714, 72100 Brindisi, Italy d Department of Physics, University of Padova, Via Marzolo 8 35131 Padova, Italy Received 29 July 2005; accepted 24 October 2005 Available online 17 November 2005

Abstract CdS nanocrystals are formed by regioselective thermal decomposition of metal alkanethiolates in a polymer matrix by selective heating of a polystyrene foil filled with the cadmium-(bis)-thiolate precursor using focused laser beam irradiation. CdS nanocrystal formation in the polymer was investigated by photoluminescence emission and excitation (PL and PLE) spectroscopy and transmission electron microscopy (TEM). The PLE spectra show a band edge at 420 nm for the irradiated area, indicating the presence of nanocrystalline CdS of size of about 23 nm. The PL exhibits an emission band at 535 nm that is also characteristic of nanometer-sized CdS. TEM images confirm the presence and size of CdS nanoparticles. The surface temperature was estimated theoretically considering the relationships between the temperature, time and power of the laser pulses. Nanoparticle formation via laser probe is also discussed in terms of possible utilization of other probes (e.g., electrons, etc.), inducing nanocrystal formation for the realization of conducting nanowires embedded in non-conductive matrix materials useful for nanoelectronic devices or conductive plastic. 2005 Elsevier B.V. All rights reserved.
Keywords: Nanomaterials; Laser processing; Semiconductor; TEM; Photoluminescence

1. Introduction In recent years, semiconductor nanoparticles, or quantum dots (QDs), have been attracting much attention because of their electronic, optical and catalytic properties resulting from the quantum size effect [15]. The main reason for the wide interest in QDs is that they are chemically stable [4] and the above-mentioned properties can be modulated just by varying their dimensions without changing their chemical composition [13]. An exciting application area of semiconductor quantum dots (QDs) is their incorporation in polymers because Polymer-QD composite-based devices can be easily processed in different

Corresponding author. Fax: +39 0546 678503. E-mail address: f.antolini@faenza.enea.it (F. Antolini). 0167-577X/$ - see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2005.10.093

geometries, morphologies and compositions with subsequent control over different electro-optical properties [6]. Semiconductor QDs can be dispersed in polymers by both ex situ and in situ methodologies and polystyrene has been used extensively as a nanocomposite polymer [712]. In the ex situ pathway, the nanoparticles are prepared and then incorporated into the polymer [79], while in situ dispersion utilizes the dispersion of a suitable precursor in the polymer, then the nanoparticle formation is induced by introducing gas, heating or irradiating the sample [1012]. Both methods are widely used to prepare nanocomposite materials and the choice depends on the desired properties of the final nanocomposite. The ex situ process has allowed better particle size control during synthesis, but faces the challenge of good dispersibility in the polymer [13,14]. The in situ methodology becomes particularly interesting when nanoparticles can be synthesized in selected spatial regions in the polymer driven by an appropriate probe.

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Recently, it was shown that the temperature can be used as a driving force to produce metal sulphide nanoparticles [15,16]. In particular, by filling the polymer matrix with metal-(bis)thiolate it was possible to obtain metal sulphide nanoparticles embedded in the polymer simply by heating the ample [1719]. The use of temperature to drive QD formation is a very interesting methodology for CdS synthesis, because the thermal treatment can be selectively induced in different regions by using an appropriate thermal probe. Here, we show that a laser pulse induces a thermal shock to provoke the regioselective formation of QDs in a polymer matrix. The effect of the laser pulse on the material properties was evaluated by photoluminescence spectroscopy and TEM. 2. Materials and methods The synthesis of cadmium-(bis)-thiolate and the preparation of polystyrene foil containing the precursor is carried out as reported in Antolini et al. [1719]. The laser treatment was performed using a 2000 W NdYAG laser (1.06 m wavelength). A foil (1 cm2) approximately 300 m thick was irradiated with the laser pulse. To avoid disintegration of the sample, the laser beam was defocused to a spot diameter of 4 mm. The laser power was set to 2000 W with a 10- to 50-ms pulse time. Photoluminescence emission (PL) and excitation (PLE) spectra were recorded with a FluoroMax spectrofluorometer (Jobin Yvon-SPEX) equipped with a 150 W Xe lamp, with continuous emission in the range of 235850 nm, using suitable interference and cut-off optical filters. Low-resolution TEM images were acquired using a Philips 208 TEM with 80 kV accelerating voltage with an AMT Advantage HR model CCD Camera. High-resolution TEM was performed using a JEOL 2010F TEM operating at 200 kV. Images were acquired digitally on a Gatan multipole scanning CCD camera. TEM samples were prepared by drop-casting nanocrystals from chloroform dispersions on 200-mesh carboncoated copper TEM grids (Ladd Research).
3. Results and discussion CdS nanoparticles were synthesized from the single-source precursor, cadmium-(bis)-thiolate, by thermal decomposition as previously reported [1719]. This is an advantageous method to produce CdS nanoparticles because it is relatively simple and has a low chemical impact. Another interesting advantage is that any spatially selective thermal probe can drive the chemical transformation of the precursor to CdS nanoparticles. Here, a laser source is used to form CdS nanoparticles by irradiating the desired portion of the polymer foil filled with the CdS nanoparticle precursor. The action of the laser pulse on the polystyrene foil filled with the cadmium-(bis)-thiolate is shown in Fig. 1. A circular region of yellow fluorescence appears under the UV lamp indicating the formation of CdS nanoparticles in the region of the polymer foil irradiated by the laser. It is also possible to observe a shadow area surrounding the yellow dot. This effect is due to laser, which burns the surface of the polystyrene. More detailed information about the CdS presence is derived from the PL and PLE spectra of the samples shown in Fig. 2. The PLE spectrum shows a band edge at 420 nm, indicating that the
Fig. 1. Photograph of 1 cm2 of polystyrene foil filled with precursor after irradiation with laser (yellow spot = 4 mm diameter). The colours are due to the UV lamp. The white region surrounding the yellow spot is the colour of the polymer foil before irradiation. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

energy gap is shifted to higher energy with respect to bulk CdS (bulk edge at 500 nm). This value of band edge that suggests the formation of nanostructured CdS can be utilised to make an estimation of particle size of about 23 nm [20]. Only the PL spectra of irradiated polymer foils with the precursor exhibited photoluminescence characteristic of CdS nanoparticles, while irradiated polymer foils without precursor did not show yellow luminescence. The emission centred at 535 also confirms the presence and the size of nanostructured CdS. The TEM images reveal the CdS nanocrystals formed in the polymer foil. It is difficult to resolve the CdS nanocrystals in the polymer composite by TEM because of the small size of the crystals, and the presence of the polystyrene that leads to charging under the microscope, which makes high-resolution TEM imaging difficult [19]. The low-resolution TEM images (Fig. 3a) show the presence of many small nanocrystals aggregated in different regions of the polymer. Particle aggregation could be due either to the presence of the polymer that acts as a bridging agent between the nanocrystals or to a polymer particle phase separation enhanced by entropic packing differences [19]. The HRTEM images also confirm the presence of the crystals because the measure of lattice spacings from Fast Fourier Transforms (FFT) of the CdS nanocrystals indicates a good agreement with the lattice spacings of CdS bulk. The size of the nanoparticles of about 3 nm is also in good agreement with the optical measurements. The laser-assisted synthesis of CdSe nanoparticles in solution recently reported by Lin et al. [21] shows that the nanoparticle formation is a function of the temperature and of the energy absorbed from the photons pumped in solution by the laser. Here the mechanism of CdS formation is due to the rise of temperature induced by laser pulse on the polymer. The temperature reached by the polymer foil can be estimated by considering the relationship reported below [22]:   4kt ePln 1 2 d T 1 4pKL where is the emissivity of the surface (this value is between 0 and 1 and represents the fraction of the laser pulse adsorbed by the polymer foil), P is the total power of the laser pulse (in W), k is the thermal conductivity (in W m 1 C 1), t is the pulse time (s), d is radius of the laser spot (in m), K is the thermal diffusivity (in m2 s 1) and L is the thickness of the polymer foil (in m).

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Fig. 2. (a) PL intensity of two replicas of irradiated samples (black and red lines, respectively). The green line is the PL signal of non-irradiated sample. The azure and blue lines are the polystyrene samples without precursor irradiated and not irradiated respectively. The PL was recorded using an excitation wavelength of 337 nm. (b) PLE spectrum of the two irradiated samples. The PLE was recorded at 535 nm, the maximum of the PL intensity. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 3. (a) Low-resolution TEM images of nanocomposite after thermal treatment and its dissolution in chloroform; (b) HRTEM of the same sample of CdS. The red ovals indicate three different particles. The crystal lattice parameters of CdS, reported in white, are in good agreement with the ones determined for the particles under study. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

The temperature rise predicted by this formula considering a laser pulse of power of 2000 W varying from 10 to 100 ms, = 0.01, K = 3, k = 0.17, d = 0.0025, L = 0.0003 is more than 104 C. At this temperature, the organic material will vaporize immediately provoking a hole in the sample. However, the real value of the temperature is difficult to determine exactly, because it is not trivial to determine all the thermal constants and the emissivity of the polystyrene foil filled with the precursor. In addition, it should be taken into account that the first layers of polymer foil have been burned by laser pulse; therefore, a high percentage of the laser energy was absorbed by the phase transition of the polymer and its disruption. It is possible to hypothesize that this temperature is reached only at the surface of the foil, then the laser power decreases enough to produce only a rise of temperature compatible with the particle formation and polystyrene resistance (200300 C). This condition is reached supposing only that a small part of the laser power (4050 W) is really utilized for the nanoparticles formation as reported in Fig. 4. This reported method of generating CdS by a laser probe is very interesting from an industrial point of view because it allows the

possibility of creating a semiconductor wire inside a non-conductive polymer by using a laser. While in this work the chemical transformation of the precursor inside the polymer is induced by a laser, it is possible to imagine that other energy sources (i.e. electrons) could be used to produce the chemical reaction of the precursor inside the polymer. In particular, the electrons can be used as a source of energy with the advantage that the generated path is of size of few tenths of a nanometre. Combining the use of nanometric probes with

Fig. 4. Temperature increase in the polymer foil as a function of laser pulse as obtained by Eq. (1) considering the effective laser power of 50 W.

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the fabrication of polymer films realised at molecular level by means of LangmuirBlodgett technology could also improve the formation of nanoparticles inside the film. This possibility could open new interesting applications for the formation of dense two-dimensional arrays of semiconductor dots useful for data storage or semiconductor wires formation.

Acknowledgements The authors would like to thank R. Lucente for his valuable technical assistance with NdYAG laser in ENEA center of Trisaia. This work was sponsored by the Ministero dell'Istruzione, dell'Universit e della Ricerca (MIUR, Rome, Italy) FISR project Synthesis of nanophases and nanostructured materials. A.G. and B.A.K. thank the National Science Foundation, the Welch Foundation and the Advanced Materials Research Center through collaboration with International SEMATECH for partial funding of this work. References
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