METAL-ASSISTED CHEMICAL ETCHING OF SILICON: PREPARATION OF SILICON NANOWIRE ARRAYS

Elisabeth Galopin, Galle Piret, Yannick Coffinier, Sabine Szunerits and Rabah Boukherroub Institut de Recherche Interdisciplinaire (IRI) USR-3078 Institut dElectronique de Microlectronique et de Nanotechnologie (IEMN), CNRS-8520 Villeneuve dAscq, France. Rabah.boukherroub@iemn.univ-lille1.fr
etching of the clean substrate in HF/AgNO3 (5.25./0.02 M) solution at 50C for a given time. Fig. 1 displays a SEM image of the resulting surface. It consists of SiNW arrays wrapped by dendrites. The energy dispersive X-ray spectroscopy shows that these dendrites are composed of silver (Fig. 2).

Topic : Integration and synthesis of new materials

The paper reports on the preparation of SiNW arrays and patterns using the chemical etching method of crystalline silicon substrate. Electroless deposition of silver nanoparticles onto the silicon nanowires was further exploited for the preparation of highly sensitive Surface Enhanced Raman Spectroscopy (SERS) substrates.
I. INTRODUCTION

In recent years, a great deal of effort has been made to the fabrication of one-dimensional nanostructured materials owing to their submicron ultimate feature size and dimensionally dependent physical properties for future use in nanodevices [1]. Silicon is the basic material in microelectronics, and silicon nanowires (SiNW) and nanowire arrays have attracted much attention for their potential applications in the field of silicon nanoelectronics and use the SiNWs as nanocomponents to build nano circuits and nanobiosensors [2]. II. SILICON NANOWIRE FABRICATION

Figure 1. SEM image of branched silver dendrites formed on Si sample after etching in HF/AgNO3 aqueous solution at 50C for 10 min.

A. Metal Assisted Ckemical Etching Various methods have been developed to prepare onedimensional silicon nanostructures [1, 2]. Even though the techniques offer a good control over the nanostructures dimensions, most of the methods require high temperatures or a high vacuum, templates and complex equipment. Metal-assisted chemical etching of silicon has been used in the past for the preparation of porous silicon substrates [3]. The technique has successfully been applied for the fabrication of large-area aligned SiNW arrays on single crystal silicon wafers [4-6]. Silicon wafers with different doping levels were used in the study. The surface was first degreased in acetone and isopropanol, rinsed with Milli-Q water and then cleaned in a piranha solution (3:1 concentrated H2SO4/30% H2O2) for 15 min at 80C followed by copious rinsing with Milli-Q water. The SiNW arrays were prepared by chemical

Figure 2. Energy dispersive X-ray image of silver dendrites formed on Si sample by etching in HF/AgNO3 aqueous solution at 50 C for 10 min.

The electroless deposition of Ag and silicon etching in the fluoride solution containing Ag+ occurs according to the following equations:

Ag+ + 1eSi + 4h + 4HF SiF4 + 2HF

+

Ag SiF4 + 4H+ H2SiF6

Chemical removal of the silver deposits using a mixture of HCl/HNO3/H2O (1/1/1) at room temperature led to the formation of well-aligned SiNW arrays (Fig. 3).

III.

CONCLUSION

Figure 3. Cross-sectional SEM image of the silicon nanowire array formed by chemical etching of Si(100) in HF/AgNO3 aqueous solution at 50C for 10 min.

We successfully prepared silicon nanowire arrays using the chemical etching method for crystalline sililcon substrate. These surfaces were then covered by silver nanoparticles by electroless deposition. Finally, we investigated the surface-enhanced Raman Scattering (SERS) performances of the resulting structure. The performance of the substrate was demonstrated for Rh6G concentrations down to 1x10-9 M. ACKNOWLEDGMENT The authors would like to acknowledge FEDER (Fonds Europen de DEveloppement Rgional) who supported this work by equipment contribution. REFERENCES
[1] [2] [3] [4] [5] [6] Rao, C. N. R.; Deepak, F. L.; Gundiah, G.; Govindaraj, A. Prog. Solid State Chem. 2003, 31, 5147. Hu, J.; Odom, T. W.; Lieber, C.M. Acc. Chem. Res. 1999, 32, 435. Li, X.; Bohn, P. W. Appl. Phys. Lett. 2000, 77, 2572. Peng, K.; Wu, Y.; Fang, H.; Zhong, X.; Xu, Y.; Zhu, J. Angew. Chem.,Int. Ed. 2005, 44, 2737-2742. Peng, K.; Fang, H.; Hu, J.; Wu, Y.; Zhu, J.; Yan, Y.; Lee, S. T. Chem.-Eur. J. 2006, 12, 7942-7947. Piret, G.; Coffinier, Y.; Roux, C.; Melnyk, O.; Boukherroub, R. Langmuir 2008, 24, 1670-1672.

By combining optical lithography and chemical etching, we have successfully prepared SiNW patterns in a controllable fashion. The choice of the resist that is stable in HF/AgNO3 aqueous solution is the key step in this process. B. Silver nanoparticles deposition We then have used the electroless technique for the deposition of silver nanoparticles onto the silicon nanowire arrays. The nanoparticles were obtained by dipping the silicon nanowires 1min in HF/AgNO3 (0.26/5.10-4 M) at room temperature (Fig. 4).

Figure 4. Electroless technique for the deposition of silver nanoparticles onto the silicon nanowire arrays.