Very sharp platinum tips for scanning tunneling microscopy

L. Libioulle, Y. Houbion, and J.M. Gilles Citation: Rev. Sci. Instrum. 66, 97 (1995); doi: 10.1063/1.1146153 View online: http://dx.doi.org/10.1063/1.1146153 View Table of Contents: http://rsi.aip.org/resource/1/RSINAK/v66/i1 Published by the American Institute of Physics.

Related Articles
Refined tip preparation by electrochemical etching and ultrahigh vacuum treatment to obtain atomically sharp tips for scanning tunneling microscope and atomic force microscope Rev. Sci. Instrum. 82, 113903 (2011) A compact sub-Kelvin ultrahigh vacuum scanning tunneling microscope with high energy resolution and high stability Rev. Sci. Instrum. 82, 103702 (2011) Compact device for cleaning scanner-mounted scanning tunneling microscope tips using electron bombardment Rev. Sci. Instrum. 82, 083701 (2011) Fabrication of silver tips for scanning tunneling microscope induced luminescence Rev. Sci. Instrum. 82, 083101 (2011) Scanning tunneling spectroscopy under large current flow through the sample Rev. Sci. Instrum. 82, 073710 (2011)

Additional information on Rev. Sci. Instrum.

Journal Homepage: http://rsi.aip.org Journal Information: http://rsi.aip.org/about/about_the_journal Top downloads: http://rsi.aip.org/features/most_downloaded Information for Authors: http://rsi.aip.org/authors

Downloaded 09 Dec 2011 to 158.144.59.155. Redistribution subject to AIP license or copyright; see http://rsi.aip.org/about/rights_and_permissions

Very sharp platinum

tips for scanning

tunneling

microscopy

L. Libioulle Laboratoire de Spectroscopic Moleculaire de Surface, Institute for Shrdies in Interface Sciences, Fact&s Universitaires N.D. de la Paix, Rue de Bruxelles 61, B-5000 Namur; Belgium Y. Houbion Unite Znterfacultaire de Microscopic Electronique, Institute for Shtdies in Interface Sciences, Fact&s Universitaires N.D. de la Paix, Rue de Bruxelles 61, B-5000 Namul; Belgium J.-M. Gilles Laboratoire de Spectroscopic Moleculaire de Surface, Institute for Studies in Interface Sciences, Facultes Universitaires N.D. de la Paix, Rue de Bruxelles 61, B-5000 Namu< Belgium

(Received 10 May 1994; accepted for publication 22 September 1994) To achieve both high stability for scanning tunneling microscopy (STM) measurements and well-defined tunnel current localization even on very rough surfaces, we have developed a new electrochemical procedure using CaCI, etching and HaSO, micro polishing technique to obtain a very reproducible tip geometry. The mean curvature radius is about 50 A. The contamination-free platinum tips are usable for a long time as well in air as in ultrahigh vacuum. The tip quality has been tested by STM measurements on gold (111) surfaces and on liquid-crystal films. Tips are stable and provide good STM image in far less time than commonly used tips. 0 1995AmericanInstitute

of Physics.

I. INTRODUCTION Since the invention of the scanning tunneling microscope (STM) and related scanning probe techniques,- tip fabrication has been a very active field of work. Standard STM tips used in ultrahigh vacuum (UHV) conditions are made of tungsten.spYThe well-known etching technique has been developed first for field ion microscopy measurements. O The curvature radius of tungsten tips, etched in NaOH solution, is generally in the order of 100 w.12-r4 Unfortunately, the etching dissolution of tungsten wire involves the surface oxidation during the process.r5 This oxide layer16 can be eliminated through evaporation by heating the tip at around 950 C in UHV conditions.17Y18 or can be removed chemically in a concentrated HF solution. Y However, once the tip has been cleaned, the presence of oxygen or water has to be avoided in order to keep the metal surface clean. From our experience of air STM measurements with tungsten tips, we have nearly always obtained evidence of contact between the sample surface and the tip.* In best cases, the quality of STM images is progressively degraded to reach the situation where the tunnel gap is the oxide layer which has grown around the tip apex. The spikes technique consisting of a sudden increase of tunnel current has been reported to restore the STM resolution but it can be considered to be an unpredictable procedure. The tip is modified but its geometry after the treatment is unknown and often subject to change while scanning. For this reason, tips used for air STM are very often made by simply mechanically cutting platinum wire. The tip shape obtained in this way cannot, however, be predicted. In this paper we describe a new etching technique for preparing very sharp platinum or platinum/iridium tips.22123 Our preparation procedure allows us to obtain a well-defined tip geometry, ended by a unique apex which decreases the probability of multiple tip images.4,25 Moreover, we use
Ftev. Sci. Instrum. 66 (l), January 1995

CaC1.JH,0/acetone26 and H2SOdjHz027 electrochemical solutions rather than highly toxic cyanideaam3or molten salt etchants. II. EXPERIMENTAL A. Tip preparation The tip is formed in a four-step process from a O.Emmdiam platinum or 9O:lO platinum/iridium wire.32 The tirst step is the coarse electrochemical etching of the wire in a fresh solution of CaCl,/H,O/acetone. We prepare the solution by adding 3 g of calcium chloride dihydrate powder to 40 ml of a mixture of water and acetone (1:l in volume). We obtain a solution saturated in acetone with a floating pure acetone layer on top. The saturated solution is removed from below the floating layer. The Pt or Pt/lr wire is vertically dipped 1 mm deep in that solution. The use of an acetone saturated solution comes from the need to control the gas bubbles generated at the interface between the wire and the solution. In aqueous solutions, the bubbles stream disturbs the material dissolution33 and even modifies locally the level of the solution so that the macroscopic tip shape fluctuates from one tip to another. In an acetone saturated solution, the bubbles regime is controlled in such a way that they stay very small (around 0.1 mm in diameter), they are radially extracted away from the tip region, giving a horizontal, constantly spreading out and stable, stream and they disappear individually without increasing in size. A sinusoidal polarization of 20 V at 40 Hz is applied between the wire and a carbon counter electrode until the current intensity falls below 30 mA. This alternating voltage is generated by a current ampIifier34 rather than by a transformer in order to avoid the sparking effect of the Ha gas bubbles and a local fusion of the tip apex.a3 The tips in this way always present the same shape: Avery rigid structure with an emerging small wire of a few microns diameter.% Figure 1 presents transmission
0 1995 American Institute of Physics 97

METHOD AND RESULTS

0034-6748/95/66(1)/97/4/$6.00

Downloaded 09 Dec 2011 to 158.144.59.155. Redistribution subject to AIP license or copyright; see http://rsi.aip.org/about/rights_and_permissions

b
Binocular * microscope

Horizontal glass tube

Positive pulses

Ground

d
FIG. 2. Schematic view of the experimental micropolishing setup. The H2SO&0 solution is held in a horizontal glass tube of 5 mm diameter. 15 V positive pulses (16 HISat 4 kHz) are applied on the tip against a carbon counter electrode.

FIG. 1. TEM images of the same Pt tip: (a) ahd (b) after the CaCl,/HzO/acetone etching step; (c) after the heating step; (d)-(f), after the H2SO&20 micropolishing step.

electron microscopy (TEM) views of a platinum tip. The length .of the microwire is in the order of 50 ,um [Fig. l(a)]. The curvature radius at that apex is less than 1 ,um and the tip surface is irregular [Fig. i(b)]. We will follow the transformation of the same ti@ throughout the three remaining steps of our etching method. In the second step, one heats the wire to red in a Bunsen flame. This is crucial for reducing the amount of dislocations and thus increasing the size of the microcrystals in the etched wire. The result of this annealing is shown in Fig. l(c). The curvature radius has been slightly increased and the microwire surface is now perfectly smooth. The third step proceeds with a precision micro polishing35 of the tip in a diluted H,SO, solution. The solution is contained in a horizontal glass tube (Fig. 2) and is in contact with the microwire. We observe the tip and the meniscus through a binocular microscope. The position of the wire is adjusted so that only the microwire is within the solution. The carbon counter electrode is put to ground. 15 V positive pulses of 16 ,us duration at.a repeating frequency of 4 kHz are applied on the tip. Positive pulses instead of an alternating voltage are used in order to obtain a slow etching rate and, thus, to have an optimal control of the tip polishing. Froni our experience, the pulse length has to be long enough to start the electrochemical reaction, and short enough to slowly remove the metal from the tip apex. 16 @ at 4 kHz is found to be an adequate experimental condition. The pulses are usually applied for lo-20 s. Figures l(d)-l(f) present the result of this micropolishing step. The microwire has been polished in such a way that it has been sharpened and its length has been slightly reduced. The resulting curvature
96 Rev. Sci. Instrum., Vol. 66, No.

radius is less than 100 ,A in all cases (generally between 30 and 100 A). The tip surface is very smooth and reproducible from one tip to another. Figure 3 presents another platinum tip. The geometrical characteristics are the same. However, the dissolution in diluted HzS04 solution involves the oxidation of the platinum surface. The oxide layer has to be removed in the last step of the tip preparation process. The first possibility is to heat the tip at 200 C under hydrogen flow at 10-l Torr for 2 h.36 This very long treatment can be easily replaced by an electrochemical step. Just after the micropolishing step, a reverse voltage of - 1.1 V dc is applied for 1 or 2 min to the tip while it is still in contact with the HZS04 solution.37 The applied voltage has to be chosen in such a way that the oxide layer is reduced without etching the tip: A slightly negative voltage is adequate. We stop the reverse voltage when the flowing current is in the order of few PA. B. STM measurements To test the quality of the etched platinum tips we have imaged, in air, a gold (111) surface evaporated on mica3s and a 4 -n-alkyl-4-cyanobiphenyl liquid-crystal (8CB) film on graphite? The very large gold (111) terraces are visible in Fig. 4. The tunnel current was very stable. We can distin-

FIG. 3. TEM views of a typical Pt tip after the four steps of electrochemical etching procedure. Curvature radius is in the order of 30-100 A. Sharp STM tips

1, January 1995

Downloaded 09 Dec 2011 to 158.144.59.155. Redistribution subject to AIP license or copyright; see http://rsi.aip.org/about/rights_and_permissions

1730 nm

642 nm

FIG. 4. STM image of gold (111) surface grown on mica [(a: 10 mV, 100 PA, 1730X1730 nm, 2 range: 9.6 nm) and (b: 10 mV, 100 PA, 642X642 nm, 2 range: 14 nm)] and TBM view of the used Pt tip (c). Slight accidental touch of the sample surface has probably modified the tip apex. The cmvature radius is still in the order of 100 A.

guish in Fig. 4(b) the presence of deep holes (90 A). Due to the sharpness of the platinum tip, lateral tunnel current is less probable, small structures on the surface are clearly visible,40 and the edges of the holes are abrupt. We can also notice that terraces edges are very indented. This feature is rarely visible when using gold tips with 1 pm mean curvature radius.t Figure 4(c) presents the platinum tip after the STM measurement. We see clearly the modification of the tip end, probably due to a small accidental contact with the sample. However, the tip radius is still in the order of 100 A which thus represents the worst tip geometry for the whole STM measurement. The persistence of a good tip shape is also the proof of the quality of the tip-to-sample approach at the start of the measurement as well as a check of the performance of the feedback loop. Figure 5 shows results on an 8CB liquid-crystal (LC) film. A drop of LC has been spread out at 40 C on a freshly cleaved graphite sample. After slow crystallization of the film, the STM measurements have been performed at 18 C. The crystalline periodicity of the film is clearly visible at large scale [Fig. S(a)] and molecular resolution is achieved as demonstrated in Fig. 5(b). This last image has been slightly filtered in order to remove high-frequency noise. The unit cells, composed of eight molecules, form zig-zag rows. The cyanobiphenyl molecular heads are clearly distinguished. We can also notice that the LC molecules are visible even at very

low bias voltage and small current (40 mV and 5 PA, respectively). The stability of the tunnel tip was confirmed throughout the three day measurement period, always keeping the molecular resolution. This represents a significant improvement with respect to the stability observed with gold tips. Of course, to keep the quality of the tip, it is necessary to control the scanning speed in order to avoid any unwanted contact with the sample. In conclusion, platinum or platinum/iridium tips can be prepared easily with a standard electrochemical etching procedure. The tips are very sharp (curvature radius about 50 A), reproducible and inert to oxidation. During STM measurements, the tips are very stable and no mechanical vibration was observed. The best STM resolution is routinely obtained and long period STM stability is also achieved. It is thus possible to obtain good STM images in far less time than by using standard gold tips. The use of a STM tip which has a reproducible shape will also probably decrease the number of tip artifacts. ACKNOWLEDGMENTS Our thanks and appreciation go to Dr. U. Diirig and Dr. H. Salemink from IBM Zurich for their helpful discussions, to Dr. W. He& from the University of Miinchen for advice on sample preparation, to Dr. A. Ronda for active collaboration, and to Dr. A. Walcarius, Dr. R. Miiller, and Dr. A. Peremans for assistance in resolving electrochemical problems. This work was supported by the InterUniversity Attraction Pole in Interface Sciences (Ifs).

FIG. 5. STM image of 4 -n-alkyl-4-cyanobiphenyl (8CB) liquid-crystal film on graphite: (a: 40 my 5 pA, 750X750 A, 2 range: 6 A) and (b: 40 mV, 5 pA, 133X133 A, Z range: 4 A). Rev. Sci. Instrum., Vol. 66, No. 1, January 1995

G. Binnig and H. Rohrer, Surf. Sci. 126, 236 (1983). G. Binnig, C. E Quate, and Ch. Gerber, Phys. Rev. Lett. 56, 930 (1986). U. Diirig, 0. Ziiger, and D. W. Pohl, J. Microsc. 152, 259 (1988). 4J. H. Coombs, J. K. Gimzewski, B. Reihl, and J. K. Sass, J. Microsc. 152, 325 (1988). M. Specht, J. D. Pedamig, W. M. He&, and T. W. Hansch, Phys. Rev. L&t. 68, 476 (1992). D. W. Pohl, U. Ch. Fischer, and U. Diirig, J. Microsc. 152, 853 (1988). R. Wiesendanger, D. Biirgler, G. Tarrach, A. Wadas, P. Brodbeck, H.-J. Ciintherodt, G. Gintherodt, R. J. Gambino, and R. Ruf, J. Vat. Sci. Technol. B 9, 519 (1991), s W. M. Heck& Tips Manufacturing-Protocols Substrates-Characteristics, Workshop, Foundation Formentin-Guilbert (Noisy Le Grand, 1991). 9 J. P. Ibe, P. P. Bey, S. L. Brandow, R A. Brizzolara, N. 4. Burnham, D. P. DiLella, K. P. Lee, C. R. Marrian, and R. J. Colton, J. Vat. Sci. Technol. A 8, 3570 (1990). E. W. Miiller and T. T. lhong, Field Ion Microscopy, Principles and Applications (Elvesier, New York, 1969). I M. K. Miller and G. D. Smith, Atome Probe Microanalysis: Principles and Applications to Materials Problems (Materials Research Society, Pittsburgh, PA, W89). P J Bryant, H. S. Kim, Y. C. Zheng, and R Yang, Rev. Sci. Instrum. 58, 1115 (1987). 13M. Fotino, Rev. Sci. Instrum. 64, 159 (1993). r4D K. Biegelsen, F. A. Ponce and J. C. Tramontana, Appl. Phys. Lett. 54, 1223 (1989). J. P. Song, N. H. Pryds, K. Glejbol, K. A. March, A. R. Tholen, and L. N. Christensen, Rev. Sci. Instrum. 64. 900 (1993). t6J. E. Fasth, B. Loberg, and H. Norden, J. Sci. Instrum. 44, 1044 (1967). r7U. Diirig, 0. Ziiger, B. Michel, L. Haussling, and H. Ringsdorf, Phys. Rev. B 48, 1711 (1993). so, Albrektsen, H. W. Salemink, K. A. March, and A. R. Thblen, J. Vat. Sci. Technol. B (in press). L. A. Hackett and S. E. Creager, Rev. Sci. Instrum. 64, 263 (1993). Sharp STM tips 99

Downloaded 09 Dec 2011 to 158.144.59.155. Redistribution subject to AIP license or copyright; see http://rsi.aip.org/about/rights_and_permissions

* J. Garnaes, F. Kragh, K. A. March, and A. R. Tholen, J. Vat. Sci. Technol. A 8, 441 (1990). a*H. J. Mamin, P. H. Guethner, and D. Rugar, Phys. Rev. Lett. 65, 2418 (1990). A. A. Gewirth, D. H. Craston, and A. J. Bard, J. Electroanal. Chem. 261, 477 (1989). A. J. Melmed, J. Vat. Sci. Technol. B 9, 601 (1991). %L. Libioulle and J. M. Gilles, Abstract of the 14th General Conference on Condensed Matter Division, EPS, Madrid, March 1994. L. Libioulle, Y. Houbion, and J. M. Gilles, Physicalia Mag. (in press). %I. H. Musselman and P. E. Russell, J. Vat. Sci. Technol. A 83558 (1990). 27H Angerstein-Kozlowska, B. E. Conway, and W. B.A. Sharp, Electronan. Chem. Interf. Electrochem. 43, 9 (1973). *M J Heben, M. M. Dovek, N. S. Lewis, R. M. Penner, and C. F. Quate, J. Microsc. 152, 651 (1988). 9R M. Penner, M. J. Heben, and N. S. Lewis, Anal. Chem. 61, 1630 (1989).

30H Lemke T. Goddenhenrich, H. P. Bochem, U. Hartmann, and C. Heiden, Rev. Sci. ~nstrum. 61, 2538 (1990). aS. P. Kounaves, Platinum Metals Rev. 34, 131 (1990). *Goodfellow Metals Ltd., Cambridge Science Park, England. M. Fotino, Appl. Phys. L&t. 60, 2935 (1992). 34H. Morikawa and K. Goto, Rev. Sci. Instrum. 59, 2195 (1988). A. J. Melmed and J. J. Carroll, J. Vat Sci. Technol. A 2, 1388 (1984). a6J.-P.Delve, Ph.D. thesis, Universite de I Etat, Mons (1978). A. Peremans, LURE Orsay France (private communication). 38S. Buchholz, H. Fuchs, and J. P. Rabe, J. Vat. Sci. Technol. B 9, 857 (1991). j9D. P. E. Smith, J. Vat. Sci. Technol. B 9, 1119 (1991). 4oM. Stedman, J. Microsc. 152, 611 (19883. H. J. Mamin, S. Chiang, H. Birk, P. H. Guethner, and D. Rugar, J. Vat. Sci. Technol. B 9, 1398 (1991). *D. P. E. Smith, W. M. He&l, and H. A. Klagges, Surf. Sci. 278, 166 (1992).

100

Rev. Sci. Instrum.,

Vol. 66, No. 1, January

1995

Sharp STM tips

Downloaded 09 Dec 2011 to 158.144.59.155. Redistribution subject to AIP license or copyright; see http://rsi.aip.org/about/rights_and_permissions