Enhancement-Factor Measurement of TERS Tips: An Imaging and a Spectroscopic Approach

Naresh Kumar1, Ali Rae1 and Debdulal Roy1*

1

National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK *debdulal.roy@npl.co.uk

Introduction
The enhancement factor in tip-enhanced Raman spectroscopy (TERS) is a complex parameter to measure. It depends on the measurement condition of the instrument, sample properties as well as the TERS tip characteristics. Therefore, variation of the enhancement factor reported in TERS literature ranges from 30 to an astounding value of 1013(1, 2). Such a high degree of variability makes the comparison of performance of a TERS tip difficult (3). In this poster, we propose two approaches to measure enhancement factor of a tip. (a) An imaging method using a 1-dimensional nanostructure such as a single wall carbon nanotube (SWCNT). This method is verified using tip-enhanced Raman images from our laboratory, and an image from another group published before (4). (b) a spectroscopic approach that involves TERS measurements on a bi-layer thin-film consisting of polyacrylonitrile (PAN) as the bottom layer and 4-aminothiophenol (4-ATP) molecules embedded in polymethylmethacrylate (PMMA) as the top layer. This method utilises a normalisation technique using the far-field Raman signal from the bottom layer of the sample, and eliminates the most significant source of error arising due to far-field contribution during the TERS measurements.

Imaging Approach

Spectroscopic Approach a) b)

Figure 3a). Schematic diagram of the bilayer sample.

Figure 3b). Schematic diagram showing the principle of spectroscopic approach.

Methodology
Figure 1. Schematic diagram of the imaging approach..

(NF + FF1) R = FF2

(NF1 + 1) = K FF2

(1)

Methodology
To calculate the enhancement factor using this approach we perform TERS on a SWCNT. 1.  The far-field illumination produces a Raman image of the one dimensional structure where the width of the image is equal to the far-field spatial resolution. 2.  The far-field and the near-field profiles are then fitted with a Gaussian+Lorentzian fit. The full width half maxima of the fits provide a measure of probed length of the structure and the intensity heights corresponds to the near-field and the far-field intensities. 3.  The near-field and far-field intensities per unit length of the structure are then calculated; the ratio of the two intensities gives the value of actual enhancement factor. A similar methodology has been used in the fields of x-ray photoelectron spectroscopy and Auger electron spectroscopy (5).

FF1 K = FF for total thickness of the layers confocal depth, 2 EF = R K 1

(2)

Where ASpot and ATip are the areas of the laser spot-size and TERS tip respectively.

Results a)

Results a)

Figure 4a). Confocal Raman Spectrum of a pure PAN film, 4-ATP molecules embedded in PMMA layer, bilayer sample and the near-field spectrum from the bilayer.

b)

b)
Figure 4b). K-value histogram from 500 far-field measurements. Figure 4c). Enhancement factors of three TERS tips.

Figure 2a) Results of imaging approach on SWCNT sample from our lab with Au tip and 633 nm laser. 2b) Analysis of SWCNT image published by Hartschuh et al.

Conclusions
Enhancement factor
4.25 4.9 4.1 7.35
Queens Printer and Controller of HMSO, 2013. 10561/0713

Images
Hartschuh et al. Profile 1 Profile 2 Profile 3

Intensity Peak width (a.u.) (nm) Near field

0.54 384 244 270 53 74 76 84

Intensity Peak width (a.u.) (nm) Far field

0.75 556 478 346 313 531 613 795

We have demonstrated two approaches to the enhancement factor calculation of TERS tips. The first approach uses an imaging method of a 1-dimensional material such as SWCNT and the second method uses a bilayer thin-film sample to measure the enhancement factor. Both the approaches give consistent values of enhancement factor unlike those reported in the literature. These methods can be employed for comparing the enhancement factors of different tips in a laboratory, results obtained in different laboratories and different tips prepared by commercial manufacturers. These can also be powerful methods to compare the results obtained from different commercial TERS instruments.

Acknowledgements
The authors gratefully acknowledge the Innovation, Research and Development (IRD) programme of the National Measurement Office (NMO), UK for funding this research work.

References

1. T. A. Yano, Y. Inouye, and S. Kawata, Nano Lett. 6, 1269 (2006). 2.  M. D. Sonntag, J. M. Klingsporn, L. K. Garibay, J. M. Roberts, J. A. Dieringer, T. Seideman, K. A. Scheidt, L. Jensen, G. C. Schatz and R. P. Van Duyne, J. Phys. Chem. C 116 (1), 478-483 (2012). 3. D. Roy, J. Wang and C. Williams, Journal of Applied Physics 105, 013530-013531 (2009). 4. A. Hartschuh, N. Anderson, and L. Novotny, J. Microsc.210, 234 (2003). 5.  M. P. Seah, in Practical Surface Analysis, edited by D. Briggs and M. P. Seah John Wiley and Sons, 1, 201 (1990)

ASpot ATip

(3)

c)

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