Scanning Near-Field Optical Microscopy and Spectroscopy as a Tool for Chemical Analysis

Research into the nanometer-scale region is currently of relevance in many branches of modern science and engineering, such as in microelectronics, supramolecular chemistry, and in a biological context. A great deal of attention is given to the design of molecular devices, usually towards understanding the function of existing "molecular machines". Central to this task are powerful diagnostic tools capable of recording chemical information with spatial resolution in the nanometer range. While elemental analysis of surfaces with a lateral resolution of a few dozen nanometers is almost routine, analysis of molecular species with a resolution of <1 µm is very difficult. Scanning-tunneling and atomic-force microscopies usually do not give any chemical information. By combining scanning near-field optical microscopy (SNOM)-the "optical member" of the family of scanning-probe microscopies-with optical spectroscopy, it is possible to obtain molecular information from sample areas as little as 50 nm in diameter. In SNOM, a light source is scanned above the object of interest at a distance of a few nanometers. In the optical near field, the illuminated area is not subject to the Abbé diffraction limit, but merely by the size of the illuminating source. High quality SNOM probes can be reproducibly prepared by a chemical-etching method. These etched probes have an optical transmission up to 1000-fold higher than commercial (pulled) SNOM tips and can withstand higher laser power. This last advantage allows not only high resolution optical imaging, but also localized spectroscopic investigations of surfaces and even optical "nanosampling" by pulsed-laser ablation. The ablated material can be transported over a considerable distance, which opens the possibility for its subsequent analysis with a complementary, highly sensitive analytical method, such as mass spectrometry.