Zurich, January 22, 2006. Chemists working with ETH professor Renato Zenobi have developed a new analytical procedure with extremely high sensitivity and precision. It allows the reliable identification of single molecules on surfaces. The ETH researchers present their new method in the Journal of Physical Chemistry.
Researchers at ETH Zurich have developed an analytical procedure that should be of special interest for applications in nanotechnology. As reported by ETH professor Renato Zenobi's research group in the Journal of Physical Chemistry (1), they have succeeded in localizing and precisely determining the chemical na-ture of individual molecules on a surface. Chemical analysis thus advances to new dimensions. Identification on a scale of just 10 nanometres is made possi-ble by this method.
In order to detect single molecules, scientists previously relied on the fluorescence method. This method, however, does not permit identification of the substances found. The method newly developed by the ETH researchers, on the other hand, is based on Raman spectroscopy, which supplies a true fingerprint of the molecule. In this procedure, the sample to be investigated is irradiated with laser light. The majority of the light is immediately scattered, but a part is absorbed by the molecules and then re-emitted as clearly defined Raman radiation. If this emitted radiation is measured, it is possible to determine which substances are present on the surface of the sample.
Amplification factor of several millions
The principle of this method of analysis has actually been known for some time, but a limitation has been that individual molecules emit a signal that is too weak to be measured. The ETH researchers, however, have now succeeded in enor-mously amplifying the signal with a special experimental set-up. For some time it has been known that Raman radiation is more intense when the sample is placed on a silver or gold substrate. A comparable effect is obtained, but with considerably smaller spatial dimensions, if a silver or gold tip is scanned over the sample during the measurement.
By combining the two principles, Zenobi has now succeeded in developing a high-resolution analytical method. The sample is deposited on a gold surface. During measurement, a silver tip of roughly the size used in a scanning tunnel-ing microscope is moved over the sample. Between the tip and the gold sub-strate, over an area of approximately 10 by 10 nanometres, a strong electrical field is generated that amplifies the Raman signal by a factor of 107.
By performing measurements on two different substances, the researchers were able to show that in principle, all compounds may be determined by this method. They are also sure that they can actually detect individual molecules by this procedure. For example, if the sample substance on the gold surface is more dilute, signals of the same intensity as before are measured, but at fewer loca-tions where molecules are still present. The precision of the procedure is also demonstrated by the fact that the signals measured fluctuate when observed over a period of a few seconds. The researchers consider this to arise from mo-lecular motion. If the Raman signals measured were to originate from a cluster of molecules, one would not expect such fluctuation. Finally, a third indication that adds confidence to this interpretation is the observation that for some molecules, the Raman signal disappears suddenly and does not return. According to the researchers, this occurs when the molecules are decomposed by the laser light.
The researchers envisage numerous applications for their new method. In prin-ciple, it is now possible to determine with high precision on thin samples of a material which substances are present and where. Such measurements could supply useful information in biology, environmental analysis, and also in the preparation of new materials.
(1) Weihua Zhang, Boon Siang Yeo, Thomas Schmid, Renato Zenobi: Single Molecule Tip-Enhanced Raman Spectroscopy with Silver Tips, Journal of Physical Chemistry (2007).
Prof. Renato Zenobi
Laboratory of Organic Chemistry
Tel.: +41 44 632 43 76
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