Langmuir 1987,3, 1025-1027
(2) Adsorbed boron does not inhibit adsorption or dissociation of ethene, propene, or 3,3,34rifluoropropene on the Mo(100)surface. This is in contrast to carbon and oxygen adatoms, which do inhibit dissociation of these molecules. (3) Boron adatoms, unlike carbon and oxygen, may not be located in 4-fold hollow sites on the Mo(100) surface. Acknowledgment. We wish to thank Joan Deffeyes and Anne Horlacher Smith for performing the diborane
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thermal desorption measurement. This research was supported by the National Science Foundation under Grant CHE-8505723. The measurements were carried out in the Surface Science Facility of Northwestern University's Materials Research Center, supported in part under the NSF-MRL program (Grant DMR-8520280). Registry No. B,7440-42-8;Mo, 7439-98-7;BzH6,19287-45-7; MoBz, 12007-27-1;carbon monoxide, 630-08-0;ethene, 74-85-1; propene, 115-07-1;3,3,3-trifluoropropene,677-21-4.
Scanning Tunneling Microscopy and Lithography of Solid Surfaces Covered with Nonpolar Liquids J. Schneir" and P.K. Hansma* Department of Physics, University of California, Santa Barbara, California 93106 Received March 20, 1987. I n Final Form: May 11, 1987 We show that atomic-resolution tunneling microscopy can be done under nonpolar liquids. Two possible areas of application are explored lithography and imagin air-sensitivematerials. The lithography was demonstrated by writing a hole 20 i% X 40 A (wide) X 20 (deep) onto a gold surface. The imaging of air-sensitive materials was demonstrated by imaging GaAs.
1
Introduction
As electrochemists have known for a long time, there are really only two ways in which a surface can be maintained clean: (1)under ultrahigh vacuum and (2) under a clean liquid. Despite the importance of the liquid+lid interface in technology and biology, the vacuum-solid interface has had much more attention in science. There are very good reasons for this: (1)it is simpler to understand theoretically and (2) there are more available analytical tools. Fortunately, however, the scanning tunneling microscopel (STM), which has been shown to be a powerful analytical tool,2 will work a t a liquid-solid interface. Atomic-resolution images have been obtained for solids covered with liquid n i t r ~ g e nliquid ,~ helium$6 water: and conductive solutions.' Here we show that atomic-resolution tunneling microscopy can be done under nonpolar liquids. We demonstrate two possible areas of application: lithography and imaging air-sensitive materials. Important work has already been done in both of these areas. Lithography has been done with STMs under vacuum.g11 An air-sensitive compound, GaAs, has been imaged not only under vacuum12-14but also under a KOH (1)Binnig, G.; Rohrer, H.; Gerber, Ch.; Weibel, E. Phys. Rev. Lett., 1982,49,57. (2)Two recent reviews are: Quate, C. F. Phys. Today 1986,39,26. Hansma, P. K.;Tersoff, J. J . AppZ. Phys. 1987,61,R1. (3)Drake, B.; Sonnenfeld, R.; Schneir, J.; Hansma, P. K.; Slough, G.; Coleman, R. V. Rev. Sci. Instrum. 1986,55,441. (4)Binnig, G.; Smith, D. P. E. Rev. Sci. Instrum. 1986,57(8),1688, 1689. (5)Marti, 0."Scanning Tunneling Microscope at Low Temperatures", Ph.D. Dissertation No. 8095,ETH, Ziirich, Switzerland, 1986. (6)Sonnenfeld, R.; Hansma, P. K. Science (Washington, DC) 1986, 232,211. (7)Sonnenfeld, R.; Schardt, B. Appl. Phys. Lett. 1986,49, 1172. (8)Rmgger, M.; Hidber, H. R.; Schlijgl, R.; Oelhafen, P.; Gtintherodt, H. J. Appl. Phys. Lett. 1985,46,832. (9)Abraham, D. W.; Mamin, H. J.; Ganz, E.; Clarke, J. IBM J.Res. Deu. 1986,30,492. (10)Becker, R. S.;Golovchenko, J. A.; Swartzentruber, B. S. Nature (London) 1987,325,419. (11)Staufer, U.;Wiesendanger, R.; Eng, L.; Rosenthaler, L.; Hidber, H. R.; GCmtherodt, H.-3.; Garcia, N., manuscript in preparation. (12)Stroscio, J. A.; Feenstra, R. M.; Fein, A. P. Phys. Rev. B Condens. Matter 1985,32,1394. (13)Feenstra, R. M.; Fein, A. P. ZBM J. Res. Dev. 1986, 30, 466.
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solution.16 Advantages of working under nonpolar liquids in this report rather than polar solutions include simplicity, lack of ionic conduction, and low volatility.
Experimental Section Figure 1shows the microscope used for this study. The springs firmly hold the scanner mount against a tripod of coarse tipadjustment screws. Fine mechanical adjustment is achieved by a 101reducing lever arrangement similar to that previously used by Demuthls and by Kaiser and Jacklevic." The piezoelectric scanning element itself is of the single-tube design developed by Binnig and Smith4 The transverse calibration constant, 2.6 nm/V, was established by imaging the well-known surface structure of graphite.18i1g The vertical calibration constant, also 2.6 nm/V, was obtained from a simple calculation using the manufacturer's data, dB1= 0.135 nm/V, for the Channel 5400 material used for the element.*O Images were recorded by photographing a storage oscilloscope screen. The lines are z vs. x plots separated by Ay. Scanning was done right to left and top to bottom. The tunneling tips used were commercially available etched PtIr microelectrodes.21 AU images were obtained with the sample at +0.1 V with respect to the tip and 3-nA tunneling current. The tunneling current was determined by measuring the voltage drop across a 2 X 108Q shunt resistor in series with the junction. The shunt resistor limited the tunneling current, even in the case of a short, to 50 nA. Results and Discussion Figure 2 shows atomic-resolution images taken under various nonpolar fluids. The sample was highly oriented pyrolytic graphite.22 Fresh surfaces were exposed by (14)Feenstra, R. M.; Stroscio, J. A.; Tersoff, J.; Fein, A. P. Phys. Reu. Lett. 1987.58. 1192. (15)Sohenfeld, R.; Schneir, J.; Drake, B.; Hansma, P. K.; Aspnea, D. Appl. Phys. Lett. 1987,50, 1742. (16)Tromp, R. M.; Hamers, R. J.; Demuth, J. E. Phys. Rev.Lett. 1985, 55. 1909. --I
(17)Kaiser, W. J.; Jacklevic, R. C. Surf. Sci. 1987,181,55. (18)Binnig, G.; et al. Europhys. Lett. 1986,1, 31. (19)Schneir, J.; Sonnenfeld, R.; Hansma, P. K. Phys. Reu. B Condens. Matter 1986,34,4979. (20)Data book from Channel Industries, Inc., Santa Barbara, CA 93106. (21)Part No. 197201A from Frederick Haer and Co., Brunswick, ME. (22)Moore, A. W. In Chemistry and Physics of Carbon; Walker, P. L., Jr., Thrower, P. A., Eds.; Marcel Dekker: New York, 1973;Vol. 11, p 69. Moore, A. W. In Chemistry and Physics of Carbon; Walker, P. L., Jr., Thrower, P. A., Eds.; Marcel Dekker: New York, 1981;Vol. 17,p 233.
0 1987 American Chemical Society
Schneir and Hansma
1026 Langmuir, Vol. 3, No. 6, 1987
PARAFFIN O I L
SlLlCONE OIL
TIP
SAMPLE
FLdOROCARHON GREASE
H
NICROSCOPE IUMERSION OIL
100 A
Figure 1. Constructionof this STM was simplified by the use of a single-tub The largest area which can he imaged is 1r m X 1rm.
Figure 3. Images of the surfaceof GaAs taken under different oils and greases. To ensure that there was no residual film on the tip or sample we used a new tunneling tip and a different GaAs sample (cut from the same wafer) for each fluid. GaAs is difficult to image in air because of the formation of a surface oxide. The small features visible under the silicone oil indicate a vertical resolution of better than 10 A.
SILICONE OIL
PARAFFIN O I L
t =0sec
FLUOROCARBON GREASE
2
t = 3 0 set
SILICONE VACUUM GREASE
Figure 2. Images of atoms on a graphite surface that was wered with different oils and greases. To ensure that there was no residual film on the tip or sample, we used a new tunneling tip and a freshly cleaved graphite surface for each fluid. Note that the spacing of the atoms is comparable in all images, suggesting that viscous drag is a negligible factor-even for grease.
cleaving the graphite with a razor blade. Atoms were imaged under paraffin oil, silicone oil (Dow Coming 705 diffusion oil), silicone vacuum grease (DOWComing highvacuum grease), and fluorocarbon grease (Research Organic/Inorganic Chemical Corp. Poly-Fluor Laen grease). Graphite has previously been imaged with atomic resolution in UHV,’s and water! Figure 3 shows images of the GaAs(001) surface taken under various nonpolar fluids. The GaAs was p type Zn doped with carrier concentrations of 1.6 X l0l9cms. It was submerged in 1:l NHIOH solution and placed in an ultrasonic cleaner for -5 min. The W O H dissolved the native surface oxide.” The sample was then dipped in (23) Park. Sang-Il.; Quate, C. F. Appl. Phys. Lett. 1986.48.112. (24) Aspnee, D.E.;Studna, A. A. Appl. P h p . Lett. 1981, 39, 316.
t-60sec
H
20 i
1-90sec
Figure 4. Images of the same area of a gold surface covered with fluomcarhon grease taken before (at t = 0 and t = 30 s) and after (at t = 60 and t = 90 s) positioning the tip in the center of the frame and raising the bias voltage up to ==3V. The hole rcduced in this way is approximately 20 A X 40 A (wide) X 20 (deep).
fi
methanol and immediately placed in the nonpolar liquid. Some shaking was necessary to knock the methanol drops off the surface while under the nonpolar liquid. These images are similar to Gaks images previously obtained in KOH?4 In our experience, images taken in air occasionally are as good as those under fluids, but more often they are noisy and not reproducible. Figure 4 shows two images of a gold snrface taken before lithography (at t = 0 and t = 30 s) and two images of the same area after lithography (at t = 60 and t = 90 s). These images taken before lithography are consistent with published images of gold films under oil? air; and aqueous s o l ~ t i o n that s ~ ~have ~ ~ appeared previously. Specifically, the present images are higher magnification views of the top of a “rolling hill” similar to those in the earlier images.
Langmuir 1987, 3, 1027-1034 The lithography was done under fluorocarbon grease (Research Organic/Inorganic Chemical Corp. Poly-Fluor Laen grease). The lithography method was similar to that used by Becker et al. to write on germanium.1° To start, two images of a gold surface with a characteristic feature were taken to determine the drift rate. In this case, from the small mound in the lower left corner the drift rate could be seen to be ~ 0 . A/s. 5 Next the tip was positioned in the center of the scan area and scanning stopped. The bias voltage was increased from the 0.1 V used for imaging until the feedback voltage, which was applied to the z-piezo to keep the tunneling current constant, jumped suddenly. This usually occured at 53 V with the sample positive with respect to the tip. After this lithography, which took about 20 s, the bias voltage was reduced back to 0.1 V and the same area was imaged twice more. We were able to produce similar holes in five out of five trials. Using a nonpolar imaging fluid was the key to doing lithography out of a vacuum chamber. Our previous trials under air, water, and aqueous solutions were unsuccessful in producing nanometer-scale features. In these trials we were unable to turn the bias voltage above 2 V. At these low-bias voltages the tunneling electrons do not have enough energy to break chemical bonds. Images obtained under different fluids are of varying quality. In an attempt to determine if images are effected by the fluid used, we imaged both a thin gold film on a
1027
glass substrate and a GaAs sample 5 times under each fluid. These results indicated that most, if not all, of the variation between images is due to variations in tunneling tips and differences between different regions on the sample. We did not observe any systematic variation in images obtained with different oils and greases.
Conclusions In summary, a STM operated with its sample and tip covered with nonpolar fluids can (1)achieve atomic resolution, (2) provide images of air-sensitive materials, and (3) be operated with a high enough tip-to-sample voltage to do lithography. Acknowledgment. We thank R. Sonnenfeld for providing and helping us prepare the G d s surfaces, B. Drake for helping design and build our STM, R. Becker, J. Golovchenka, and B. Swartzentruber for their inspiration on lithography, and W. Kaska for suggesting and supplying the fluorocarbon grease. This work was supported by the National Science Foundation Solid State Physics Division under Grant No. DMR 86-13486. The STM imaging system was built, in part, with support from the Office of Naval Research. Registry No. GaAs, 1303-00-0; An, 7440-57-5; graphite, 7782-42-5.
Associated Complex Formation in the Liquid-Vapor Interface: The Water-Ethanol and Water-tert -Butyl Alcohol Systems E. Tronel-Peyroz,* J. M. Douillard, L. Tenebre, R. Bennes, and M. Privat U A 330 "Physicochimie des SystGmes PolyphasW, CNRS, 34033 Montpellier, Cedex, France Received January 14, 1987. In Final Form: April 17, 1987 The Gibbs surface excess rzland the ellipticity coefficient p were measured at the liquid-vapor interfaces for two binary mixtures: water-ethanol and water-tert-butyl alcohol. The surface composition fluctuations were deduced and explained by assuming the existence of an associated complex in the transition layer. These associated complexes are correlated in a crude manner with the contact angle measured at the triple contact line of liquid-glass-vapor.
I. Introduction The transition layer between a binary liquid mixture and its vapor has been the object of many experimental studies; many of which are based mainly on measurement of the surface tension.14 More recently, it appeared that the description of this transition layer deduced from these results can be improved upon by use of ellipsometric measurements.&1° (1) Randles, J. E. B.; Behr, B. J. Electround Chem. 1972,35, 389.
(2)Eriksson, J. C.Ark. Kemi 1966,26,49. (3)Guggenheim, E. A.; Adam, N. K. Proc. SOC.London, A 1933,139, 218. (4)Ter-Minassian-Saraga, L. J. Chim. Phys. (Paris) 1960,57, 10. (5)Rusanov, A. I. In Progress in Surface and Membrane Science; Danielli, J. F., Ed.; Academic: New York, 1971; Vol. 4,p 57. (6)Tenebre, L. J. Phys. (Les Ulis, Fr.) 1977,38C5,123. (7)Tenebre, L.; Lize, A. C. R . Seances Acad. Sci., Ser. C 1976,282, 995. (8)Lize, A.; Tenebre, L. C. R . Seances Acad. Sci., Ser. C 1973,276, 975.
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Different approaches"J2 have shown how it is possible to correlate the relative surface excess determined from the Gibbs relation and adsorption studies, with the ellipticity coefficient p if one assumes, as in Drude's the0ry,I3that the surface phase heterogeneity, normal to the surface, is entirely responsible for p . However, the ellipticity coefficient cannot be reduced to the Drude component alone. It also includes the following two contributions: The first is a contribution PTM due to surface roughness14116caused by the thermal motions of the adsorbed (9)Engelsen, D. D.;de Koning, B. J. Chem. SOC.,Faraday Trans. 1 1974,70, 1603. (10)Mang, H.; Findenegg, G. H. Colloid Polym. Sic. 1980,258,428. (11) Beaglehole, D. J. Chem. Phys. 1980,73,3366. (12) Tronel-Pepoz, E.;Bennes, R.; Douillard, J. M.; Privat, M. C. R . Seances Acad. Sci., Ser. 2 1984,299,1313. (13)Drude, P. Pr6cis d'optique; Gauthier-Villars: Paris, 1912;Vol. 2, p 43. (14)Beaglehole, D. Physica B+C (Amsterdam) 1982, 112B, 320.
0 1987 American Chemical Society
