Chemically etched fiber tips for near-field optical microscopy: a process for smoother tips

Patrick Lambelet, Abdeljalil Sayah, Michael Pfeffer, Claude Philipona, and Fabienne Marquis-Weible

An improved method for producing ber tips for scanning near-eld optical microscopy is presented. The improvement consists of chemically etching quartz optical bers through their acrylate jacket. This new method is compared with the previous one in which bare bers were etched. With the new process the meniscus formed by the acid along the ber does not move during etching, leading to a much smoother surface of the tip cone. Subsequent metallization is thus improved, resulting in better coverage of the tip with an aluminum opaque layer. Our results show that leakage can be avoided along the cone, and light transmission through the tip is spatially limited to an optical aperture of a 100-nm dimension. 1998 Optical Society of America OCIS codes: 050.1220, 060.2370, 180.5810, 240.6700, 350.5730.

In scanning near-eld optical microscopy SNOM a sharp probe tip of submicrometer dimension picks up optical information in the near eld by sending, collecting, or diffracting light at the surface of a sample.1 The near eld that is the source of subwavelength optical information is inuenced as much by the shape and optical properties of the sample surface as it is by the tip itself.2 Reliable results thus critically depend on the ability to work with well-dened tips whose geometrical and optical properties are characterized and controlled. Most of the SNOM probes used today are based on tapered optical bers. Tips are obtained either by heating and pulling3,4 or by chemical etching5,6,7 in aqueous solution of uorhydric acid HF, producing a conical tip. To yield a subwavelength optical probe, the conical tip is coated with an aluminum layer, leaving a nanometer-size aperture at the tip apex. The ideal tip is characterized by high optical transmission through a single hole with dimension of a few tens of nanometers. The optical resolution is of the
When this research was performed, the authors were with the Institut dOptique Applique e, Ecole Polytechnique Fe de rale, 1015 Lausanne, Switzerland. A. Sayah is now with the Institut de Microsyste ` mes, Ecole Polytechnique Fe de rale, 1015 Lausanne, Switzerland. The e-mail address for P. Lambelet is patrick. lambelet@ep.ch. Received 20 April 1998; revised manuscript received 3 August 1998. 0003-693598317289-04$15.000 1998 Optical Society of America

order of the size of the aperture.8 Furthermore, sharp tips characterized by a small radius of curvature are more appropriate, since they allow the tip to come quite close to the sample surface when this surface is not perfectly at. The heating and pulling process produces long tips 1 mm, with smooth surfaces, allowing good and uniform metallization with aluminum and leading to well-dened apertures. Compromises between optical transmission and aperture diameter lead, for that type of tip, to typical transmissions of 108104 for aperture sizes between 30 and 100 nm.4 The rather low transmission is due to the strong attenuation of the light along the taper as well as to the very small cone angle of the tip typically a few degrees. Chemical etching, on the other hand, allows one to produce ber tips with much shorter cones 200 m and thus much larger cone angles. This leads to higher transmission, with the light being guided in the intact core of the ber down to a few micrometers from the tip apex. Typical transmissions of 103 have been reported.9 The main drawback of chemical etching is the roughness of the surface obtained after etching with HF, which decreases the quality of the aluminum coating.10 Such tips often show leakage of light along the conical taper. In this paper we propose a new etching technique that allows one to produce much smoother surfaces and thus tips of higher quality. Applying this new technique, we have been able to obtain tips with a smooth metal coating and no leakage along the taper. The high transmission ratio of chemically etched tips can then
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Fig. 1. An optical ber is dipped, with its acrylate jacket, in aqueous hydrouorydric acid covered by oil as a protective layer. The acid diffuses through the acrylate and etches the quartz ber. After 35 min a sharp tip is formed. Fig. 2. SNOM tips obtained by chemical etching of a a ber with its acrylate jacket, b a bare ber; c and d, corresponding axial views after metallization.

be combined with some of the advantages of pulled tips, such as smooth cone surfaces and opaque metal coatings. The new mechanism for fabrication of the tips is based on the chemical etching of a glass ber through its acrylate jacket, as opposed to the standard chemical etching that is usually performed on bare bers after removal of the jacket. The etching setup is shown in Fig. 1. An optical ber, monomode at 633 nm FS-SN-3221 from 3M, is dipped with its acrylate jacket into an aqueous 40% HF solution. The HF solution is covered by oil to protect the ber against acid vapor and is heated to 60 C to accelerate the procedure. The acid does not dissolve the acrylate jacket but rather diffuses through it to etch the quartz ber. After 35 min the ber is removed and rinsed successively with water, trichlorethylene, and acetone. At this point a tip has been formed inside the acrylate jacket. To remove the jacket, an incision is made a few millimeters above the tip, and the jacket, softened by acetone, can then be pulled by being seized in front of the tip. The jacket is thus removed without damage to the ber tip after the tip is formed. This method is similar to a previous technique used to make ber tips by chemical etching.7 However, although the mechanism of chemical etching of the glass is the same, etching through the jacket leads to a different tip formation process. When etching is performed on a bare ber, the meniscus formed by the acid along the ber is determined by the acid oil quartz interface. As the ber is etched, its diameter decreases and following the laws of supercial tension; the meniscus height decreases until the tip is fully formed. In the present method acid does not etch the jacket but rather diffuses through it to etch the glass. The meniscus height is determined by the acid oilacrylate interface and remains constant during tip formation. The formation of the tip is thus essentially due to a diffusion process. As the ions of acid react with the quartz, new ions have to diffuse from the liquid to the surface of the quartz. In the upper part of the meniscus the layer of liquid is very thin, and thus the ions saturate more rapidly,
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slowing down the etching rate. In the deeper liquid the concentration of ions close to the ber remains higher owing to more efcient diffusion from the large reservoir. This explains why a tip is formed, although the height of the meniscus does not change. Note that the diffusion through the acrylate is very efcient. With the same acid concentration and temperature, forming a tip across the acrylate jacket takes only 5 min longer than on bare bers. In Fig. 2 scanning electron microscopy with a eld emission electron microscope JEOL, F 6300 is used to give an image of a tip obtained by this new technique Fig. 2a and to compare it with a tip produced under the same conditions but by etching a bare ber Fig. 2b. These gures show that the surface of the tip etched through the jacket is very smooth comparable to pulled bers and does not suffer from the surface irregularities clearly visible in Fig. 2b, which are usually encountered in chemically etched tips. Here the radius of curvature of the tip apex is 15 nm in Fig. 2a and 30 nm in Fig. 2b. This improvement of the quality of the surface shows that the movement of the meniscus along the tip when a bare ber is etched is the main effect responsible for the irregularities observed on the surface. Keeping the jacket on the ber stabilizes the meniscus and produces a smoother surface, with etching being governed essentially by diffusion. Although the global shape of the tip, viewed on a larger scale, is symmetric, asymmetries can occur in the last few micrometers of the tip in the form of elongated depressions along the axial direction. This effect, as can be seen in Figs. 2a and 2b, however, is less pronounced in bers etched through the jacket. The ber tips are metallized with a 100-nm-thick layer of aluminum deposited at 10 nms, at a pressure P 5 106 mbar. Axial views of the tip apex after metallization are displayed in Figs. 2c and 2d. A smoother surface is observed on the tip etched through the jacket, although aluminum grains

Fig. 3. Angular light distribution from a tip chemically etched a with the acrylate jacket, b without the acrylate jacket. The scale is in numerical apertures, NA.

are still present. The aperture is not clearly dened for either type of tip. We attribute the difculty of obtaining clear circular apertures in the metal layer to the very small radius of curvature typically 15 nm characterizing the quartz tip of etched bers. In contrast, pulled tips are characterized by a at end, for which much better dened apertures have been observed. We measured a transmission of logT 3.3 0.8 26 samples for the tips etched through the jacket and logT 2.8 0.8 13 samples for the tips made from bare bers. This means that the transmission varies between 8 105 T 3 102 for tips made with the new etching process and 2 104 T 102 for the other kind of tip. The higher transmission of the latter tips is attributed to leakage of light along the cone resulting from the greater roughness of the surface. To check the effect of roughness, we completely closed the aperture at the tip apex by successively evaporating the aluminum from the side and from the front of the tip. The transmission of the tips etched with the jacket decreased to our detection limit of Tclosed 107, but the transmission of the other tips decreased only by a factor of 10 and was still Tclosed 7 104. This result shows the importance of the quality of the surface of the quartz tip for guaranteeing efcient metallization without leakage of light along the cone of the tip. Note that quantitative information on the transmission of the tip is not sufcient to determine its quality; information on leakage along the cone and aperture size are important parameters as well. To further analyze light leakage along the cone, we measured the angular emission of both types of tip in the far eld. Figure 3 displays this far-eld prole for tips with a 100-nm-thick coating of aluminum, obtained with a water-immersion microscope objective numerical aperture NA 1.2 by placing the tip apex at the object focal plane of the objective and imaging its back pupil on a CCD camera. Figure 3a corresponds to the ber etched with the jacket and shows a uniform and wide light distribution, which is the ngerprint of a single, small 300 nm aperture. The low-contrast features appearing on this image are due to leaking light along the cone but with a total power much lower than the light emitted by the small aperture. On the other hand, Fig. 3b,

Fig. 4. Near-eld line scan of a 1:1 chromium grating of period 372 nm. Solid curve, topography; dotted curve, near-eld optical transmission. Optical resolution, x 100 10 nm.

which corresponds to etching a bare ber, shows a structure containing many speckles, which is due essentially to the light leaking along the cone of the tip. Note that this far-eld pattern is highly sensitive to leaking light because the interference contrast of the leaking light with the light coming from the tip depends on their relative total power, not on their actual intensity at the tip surface. Fifty percent of the bers etched with the acrylate jacket show a far-eld distribution similar to Fig. 3a, but none of the bers etched without the jacket can produce such a uniform prole. These results show that the problem of light leakage encountered until now with most etched bers can be solved by etching through the jacket. The resulting smoother surface of the tip allows one to obtain better aluminum coverage without leakage. This observation also shows that the difculty encountered until now in obtaining a good coating on chemically etched tips in comparison to that on pulled tips is due not to a different chemical state of the surface but to a higher surface roughness. The problem of light leakage along the cone of the tip is not necessarily critical for imaging in the neareld, since this leaking light has a poor lateral connement and just adds a background to the near-eld image. But for applications based on photochemical reactions11 this leaking light must absolutely be avoided, since it induces a reaction far from the targeted positions. For such applications it is critical to have only one optical aperture on the SNOM tip. To test the performance of the tip in a near-eld optical measurement, a transmission SNOM image of a 1:1 chromium grating period 372 nm, chromium thickness 21 nm deposited on glass is taken with a tip etched through the acrylate jacket. Figure 4 shows a cut through such an image. The prole of the light transmission shows a contrast of 0.28. Measured on the same grating with four tips of each type, the contrast in the optical prole is improved by a factor of 2 jacket 0.17 0.1 versus bare 0.08
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0.07 for tips etched through the jacket. This difference can be explained by the more prominent background signal resulting from light leakage along imperfectly coated tips obtained by etching bare bers. From the slope of the sides of the grating, in Fig. 4, a resolution of x 100 10 nm is measured 10%90% of the intensity. In conclusion, we have presented a modied etching technique for producing SNOM tips. The ber is dipped with its acrylate jacket in an HF solution covered by a protective oil layer. In this way the formation of the tip is governed only by diffusion and results in smoother tips compared with those on chemically etched bare bers. This smoother surface, comparable with the surface of a pulled ber, allows one to obtain a high-quality aluminum coating on the tip, leading to minimum light leakage along the cone. The authors are grateful to B. Senior Centre Interde partmental de Microscopie Electronique, Ecole Polytechnique Fe de ral Lausanne for taking the electron micrographs and to M. Gale Centre Suisse dElectronique et de Microtechnologie SA, Zu rich for fabricating the test grating. Financial support from the Swiss National Fund for Scientic Research is acknowledged.
References
1. M. A. Paesler and P. J. Moyer, eds. Near Field Optics, J. Wiley, New York, 1996.

2. B. Hecht, H. Bielefeldt, Y. Inouye, D. W. Pohl, and L. Novotny, Facts and artifacts in near-eld optical microscopy, J. Appl. Phys. 81, 24922498, 1997. 3. E. Betzig and J. K. Trautman, Near-eld optics: microscopy, spectroscopy, and surface modication beyond the diffraction limit, Science 257, 189 195 1992. 4. G. A. Valaskovic, M. Holton, and G. H. Morrison, Parameter control, characterization, and optimization in the fabrication of optical-ber near-eld probes, Appl. Opt. 34, 12151228 1995. 5. D. R. Turner, Etch procedure for optical bers, U.S. Patent. 4,469,554 5 April 1983. 6. T. Pangaribuan, K. Yamada, S. Jiang, H. Ohsawa, and M. Ohtsu, Reproducible fabrication technique of nanometric tip diameter ber probe for photon scanning tunneling microscope, Jpn. J. Appl. Phys. 31, L1302L1304 1992. 7. P. Hoffman, B. Dutoit, and R.-P. Salathe , Comparison of mechanically drawn and protection layer chemically etched optical-ber tips, Ultramicroscopy 61, 165170 1995. 8. L. Novotny, D. W. Pohl, and B. Hect, Scanning near-eld optical probe with ultrasmall spot size, Opt. Lett. 20, 970 971 1995. 9. D. Zeisel, S. Nettesheim, B. Dutoit, and R. Zenobi, Pulsed laser-induced desorption and optical imaging on a nanometer scale with scanning near-eld microscopy using chemically etched ber tips, Appl. Phys. Lett. 68, 24912492 1996. 10. A. Sayah, C. Philipona, P. Lambelet, M. Pfeffer, and F. Marquis-Weible, Fiber tips for scanning near-eld optical microscopy fabricated by normal and reverse etching, Ultramicroscopy 71, 59 63 1998. 11. J. Aizenberg, J. A. Rogers, K. E. Paul, and G. M. Whitesides, Imaging the irradiance distribution in the optical near-eld, Appl. Phys. Lett. 71, 37733775 1997.

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