Ru(0001) Nanomesh on the Nano- and

Jun 21, 2008 - URL: http://www.uni-giessen.de/cms/fbz/fb08/chemie/physchem/ag-prof-dr- ... Li Jin , Qiang Fu , Hui Zhang , Rentao Mu , Yanhong Zhang ,...
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J. Phys. Chem. C 2008, 112, 10423–10427

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Oxygen-Etching of h-BN/Ru(0001) Nanomesh on the Nano- and Mesoscopic Scale A. Goriachko,† A. A. Zakharov,‡ and H. Over*,† Physikalisch-Chemisches Institut, Justus-Liebig-UniVersita¨t, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany, and Department of Synchrotron Radiation Research, UniVersity of Lund, So¨lVegatan 14, S-22362 Lund, Sweden ReceiVed: March 18, 2008; ReVised Manuscript ReceiVed: April 28, 2008

The stability of the recently discovered h-BN/Ru(0001) nanomesh is of crucial importance for potential applications as a nanotemplate. In particular, thermal stability in oxygen environment is important for nanocatalysis applications. We report here on the etching experiments of the h-BN layer by molecular oxygen exposure at elevated temperatures. This process is studied both by scanning tunneling microscopy (STM) on a microscopic scale and with in situ low energy electron microscopy (LEEM) on the mesoscopic scale. Temperature thresholds are determined for the microscopic (600 °C) and the mesoscopic (750 °C) etching processes for O2 pressures up to 1 × 10-6 mbar. Submonolayer amounts of Au deposited on the h-BN/ Ru(0001) nanomesh improve considerably the stability of the h-BN nanomesh against etching by O2. 2. Experimental Details

1. Introduction Only recently a particularly intriguing h-BN nanomesh on Rh(111) has been discovered by Corso et al.,1 which promises various potential applications, including a sturdy oxygen- and carbon-free template for the production of nanocatalysts, nanomagnets, and functionalized surfaces. In the meanwhile, a very similar h-BN nanomesh has been identified on Ru(0001) with structural and electronic characteristics similar to those of h-BN/Rh(111).2 In order to allow for potential applications of the h-BN nanomesh as a sturdy template for instance in nanocatalysis, one has to demonstrate that the h-BN nanomesh is both thermally and chemically stable. If degradation of the nanomesh takes place by chemical etching, one has to identify means to improve the stability of the nanomesh against harsh reaction conditions. In this paper we present experimental data which demonstrate that the h-BN nanomesh on Ru(0001) is thermally stable up to 1000 °C under UHV conditions. The threshold for mesoscopic etching of the nanomesh in oxygen (P(O2) ) 5 × 10-8 mbar) is roughly 750 °C as shown with low energy electron microscopy (LEEM). The etching process starts at macroscopic defects and propagates then in the form of radial reaction fronts across the surface. The mesoscopic etching reveals a sharp border, which separates the areas with and without the h-BN nanomesh. We have also studied the microscopic etching process by means of scanning tunneling microscopy (STM), showing the etching at nanometer scale uniformly over the entire surface. At 600 °C and P(O2) ) 1 × 10-6 mbar already the exposure to 10L of molecular oxygen suffices to produce microscopic defects in the h-BN nanomesh visible in STM, while an O2 dose of 600L removes completely the h-BN/Ru(0001) nanomesh. The deposition of up to 0.5 monolayer (ML) of Au improves significantly the chemical stability of the nanomesh against O2 etching. * Corresponding author. E-mail: [email protected]. Fax: ++49-641-9934559. URL: http://www.uni-giessen.de/cms/fbz/ fb08/chemie/physchem/ag-prof-dr-herbert-over. † Justus-Liebig-Universita ¨ t. ‡ University of Lund.

The microscopic aspects of O2 etching of the h-BN nanomesh were investigated in two separate ultrahigh vacuum (UHV) chambers. Both chambers offer facilities for annealing and ion sputtering of the sample as well as for gold evaporation. One chamber houses a scanning tunneling microscope (STM), and the second chamber was equipped with an Auger Electron spectrometer (AES) and a mass spectrometer to perform thermal desorption experiments. The process of mesoscopic etching was studied in real time with the help of low energy electron microscopy (LEEM) and X-ray photoelectron microscopy (XPEEM). The LEEM and XPEEM experiments were performed using a commercial Elmitec SPELEEM system at MAXlaboratory installed as the second experimental station connected to the undulator based soft X-ray beamline I311 at the MAX-II storage ring. The LEEM could be operated also in a microprobe low energy electron diffraction (µLEED) mode, revealing the local diffraction pattern from a surface area of several dozens µm2. Also XPEEM could be used in the energy analyzer mode, thus enabling microprobe X-ray photoelectron spectroscopy (µXPS) on the areas of similar sizes. During substrate preparation, the single crystalline Ru(0001) sample was held at 800 °C and cleaned by Ar+ (1.5 keV) ion sputtering. Subsequently the sample was annealed to 700 °C in O2 (p ∼ 2 × 10-7 mbar) to remove segregating C contamination via oxidation to CO. To produce the h-BN nanomesh the well-prepared Ru(0001) surface was exposed to ∼3 × 10-7 mbar of borazine (BHNH)3 for 180s at a sample temperature of 800 °C. The high-quality borazine was supplied by H. Sachdev.3 After the borazine flux was switched off, the substrate temperature was still kept at 800 °C for several minutes. This preparation recipe resulted in a Ru(0001) surface that was uniformly covered by the h-BN nanomesh. 3. Results and Discussion 3.1. Structural Characteristics of the h-BN/Ru(0001) Nanomesh. The high resolution STM image (Figure 1a) reveals the real space structure of the nanomesh, consisting of a periodic array of pores (depressed regions) and wires (elevated regions). The average distance between the centers of neighboring pores is 3.25 nm (i.e., 12 unit cells of Ru substrate), and the pore

10.1021/jp802359u CCC: $40.75  2008 American Chemical Society Published on Web 06/21/2008

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Figure 1. Pure h-BN/Ru(0001) nanomesh. (a) High-resolution STM image 8 nm × 8 nm, Usample ) 0.1 V, Itunnelling ) 8 nA; the h-BN atomic lattice is distinguishable, the white rhombus indicates the surface unit cell. (b) Atomistic model of the h-BN/Ru(0001) nanomesh: topmost layer of Ru atoms (large open circles), N atoms (small filled circles), B atoms (dots). Grey colored BN regions correspond to the wires of the nanomesh, dark colored BN regions correspond to the nanomesh pores. Dark rhombus indicates the surface unit cell, dark hexagons designate the apertures perimeters. (c) 38.1 eV µLEED, the nanomesh spots are visible in the vicinity of the 0th order spot and the 1st order Ru(0001) spots. The inset (white box) displays the vicinity of the 0th order spot at 3.5 eV. (d-f) µXPS spectra of the Ru 3d, B1s, and N1s emissions, excited by hν ) 340 (d), 240 (e), 450 eV (f). The N1s emission is low and noisy due to low photon flux in the higher energy region.

size is 2 nm across. The atomic lattice is discernible on both wires and pores, with a periodicity of 0.25 nm. According to recent ab initio calculations, only the nitrogen atoms in the h-BN nanomesh are imaged in STM.4 The observed wire/pore height difference of 0.1 nm together with additional experimental evidence presented in refs 2 and 5. favors clearly a single h-BN layer model for the h-BN/Ru(0001) nanomesh. A single h-BN basal plane is periodically modulated due to the varying strength of interaction of the BN layer with the Ru(0001) substrate surface across the (12 × 12) unit cell (Figure 1b). The interaction of the basal h-BN plane and the Ru(0001) is strongest in those regions where N atoms sit on-top of Ru atoms and the B atoms reside in hcp hollow positions.4 Accordingly the pores of the h-BN nanomesh correspond to regions where nitrogen and boron atoms can form strong bonds to the Ru(0001) substrate, while the wires of the h-BN nanomesh are attributed to regions with weak cohesion of h-BN basal plane to the Ru(0001) surface. The produced h-BN/Ru(0001) nanomesh covers uniformly the Ru(0001) as demonstrated with representative µLEED patterns at 3.5 eV and 38.1 eV (cf. Figure 1c), revealing many diffraction superstructure spots and thus a high quality of the h-BN nanomesh on Ru(0001). The µLEED patterns are consistent with corresponding normal LEED patterns reported in

Goriachko et al.

Figure 2. LEEM images obtained in the mirror mode with 0.8 eV kinetic energy of the electrons. The circular field of view is 50 µm in diameter: (a) typical representative image of the pure h-BN/Ru(0001) surface obtained at room temperature on a freshly prepared nanomesh; (b-f) images of the area near some macroscopic defect in the upper right corner, obtained at ∼750 °C and P(O2) ) 5 × 10-8 mbar. (b) Start with the oxygen supply, (c) after 100 s, (d) after 200 s, (e) after 300 s, and (f) after 400 s of O2 etching.

the literature.2,6 In Figure 2d-f, we show photoemission spectra of Ru3d (d), B1s (e), and N1s (f) of a freshly prepared h-BN/ Ru(0001) nanomesh. These spectra clearly demonstrate the presence of B and N on the Ru(0001) substrate surface and are used as reference spectra for the O2 etching experiments. The lower sensitivity toward N1s is related to the low photon flux at hν ) 450 eV. Beyond hν ) 500 eV practically no photon flux is available, preventing the measurement of O1s core level data. 3.2. Etching the h-BN/Ru(0001) Nanomesh in Oxygen: Mesoscopic Scale. In Figure 2a we show a typical mirror mode LEEM image of the homogeneous area on the freshly prepared h-BN/Ru(0001) surface. No chemical contrast is discernible in the LEEM image, all features originate solely from the surface topography. The high quality of the h-BN nanomesh is also reconciled with the LEED pattern (cf. Figure 1c) in various regions of the sample. With the LEEM technique we investigated on the scale of some 10 micron the dynamic processes of h-BN removal by etching with O2. For instrumental reasons we could not apply higher O2 pressure than 5 × 10-8 mbar. As a consequence, we had to increase the oxidation temperature. We found the onset temperature of h-BN etching at about 750 °C. At this temperature the etching process started at some rare macroscopic defects (those could be mechanical scratches due to handling or imperfections of the surface polishing). In Figure

O2 Interaction with h-BN/Ru(0001) Nanomesh

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Figure 3. Frozen-in state of the O2 etching front on h-BN/Ru(0001). The data have been taken after turning off the oxygen flow and cooling the sample to RT. (a) XPEEM image excited by 240 eV photons, electrons kinetic energy is 0.6 eV. The circular field of view is 50 µm in diameter. (b) µXPS spectra of the B1s emission, excited by hν ) 240 eV obtained on the left- and right- hand sides of the reaction front. (c) 38.1 eV µLEED pattern obtained in front of (left) the reaction front. (d) 38.1 eV µLEED pattern obtained behind (right) the reaction front.

2, we show a selection of frames from a real time LEEM movie during the O2 etching process of h-BN/Ru(0001). The edging process starts at a macroscopic defect (partially visible in the upper right corner of the field of view), where presumably metallic Ru is not fully covered by the h-BN nanomesh so that oxygen can easily dissociate and attack the h-BN layer. Although the pressure is quite low, the reaction takes place quite fast due to high reaction temperature. Frame 2b was obtained just at the beginning of oxygen supply and when the sample temperature has reached 750 °C. Further LEEM frames Figure 2c-f were taken in time intervals of 100 s. After 200 s the reaction front (forming a white radial line around the defect) becomes visible and propagates toward the bottom left corner of the LEEM image. After 400s the reaction front has already passed ∼90% of the field of view, indicating a self-acceleration of the etching process. The reaction front in Figure 2d-f separates regions with different texture and brightness. These differences are stemming from chemical contrast as described below. The propagation of the reaction front could be stopped at any stage just by switching off the oxygen supply. A corresponding XPEEM image is shown in Figure 3. Figure 3a shows the XPEEM image of the region containing the frozen-in reaction front. Similar to the LEEM frames in Figure 2d-f, a strong brightness variation is observed which is separated by the reaction front. With µ-XPS, we observe a clear B1s signal (Figure 3b) in front of the reaction wave, but no B1s signal or a signal at a noise level behind the reaction front. This leads us to the conclusion that no h-BN exists in the regions of the surface, through which the front has passed (these regions appear darker in XPEEM and brighter in LEEM). The µLEED patterns in Figure 3c,d corroborate this conclusion, indicating a pattern similar in contrast and quality as for the freshly prepared h-BN nanomesh on the left side of the XPEEM image,

Figure 4. Observation of the h-BN etching in 5 × 10-8 mbar O2 at 750 °C far away from the initial macroscopic defect. (a-e) Mirror mode LEEM images at 1.2 eV electron energy: certain frames out of the real time LEEM movie. The circular field of view is 50 µm in diameter: (a) At time t when the etching front is far away from the initial macroscopic defect. (b) Frame taken at t + 50 s; (c) t + 100 s; (d) t + 150 s; (e) t + 200s. Black arrow designates the actual reaction front, white arrow points to the oxygen diffusion front. (f) 38.1 eV µLEED pattern obtained in the homogeneous area behind the diffusion front after turning off the oxygen flow and cooling down to RT.

and a 1 × 1 pattern corresponding to Ru(0001) substrate on the right side of the reaction front. Thus the propagation of the front seen in the LEEM sequence of Figure 2 visualizes the gradual etching process of the h-BN layer in oxygen environment. Since adsorbed nitrogen atoms desorb already in the temperature range of 500-850 K in the form of dinitrogen molecules from the Ru(0001) surface,7 this finding indicates that also no or only little nitrogen should be left behind the reaction front. This conclusion is fully consistent with corresponding (1 × 1) µ-LEED pattern in Figure 3d. Figures 2 and 3 reveal the initial stages of h-BN etching in molecular oxygen on a mesocopic scale. The etching process starts at some macroscopic defects (e.g., mechanical scratch). As the front propagates, its curvature becomes small so that it appears almost as a straight line in the 50 µm field of view of the LEEM. Such a situation is caught in Figure 4a. A notable feature in Figure 4a is the presence of the second front (marked by white arrow) moving behind the main etching front (marked by black arrow). The concerted movement of both fronts is clearly visible from consecutive frames (cf Figure 4a-e) selected in 50 s time intervals of the real time LEEM movie. After the second front passes out of the field of view (Figure 4e), a homogeneous surface area is left behind, on which a 2 × 2

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Figure 5. Differentiated AES spectra excited by 3 keV primary electrons. The curves from top to bottom: pure as-prepared h-BN/ Ru(0001) nanomesh, pure h-BN/Ru(0001) subjected to 600 L O2 at 600 °C, h-BN/Ru(0001) precovered with ∼0.3-0.4 ML Au subjected to 600 L O2 at 800, 900, and 1000 °C.

µLEED pattern was observed (Figure 4f). Unfortunately, the photon energy of µXPS is limited to energies below 500 eV (the photon flux above hν ) 500 eV is negligibly low). Therefore no local O1s photoemission spectra could be acquired. We presume that the O-coverage between the two fronts is significantly lower than behind the second wavefront. Oxygen is obviously consumed in the process of etching the h-BN, e.g., by forming some volatile BOx and NOy compounds. Thus, its concentration in the immediate vicinity of the first (etching, reaction) front must be very low. Far behind the etching front, oxygen can adsorb but is not consumed by the etching process, thus forming some stable overlayer on top of the Ru(0001) substrate. For example, the 2 × 2 µLEED pattern in Figure 4f may be explained by O(2 × 2)/Ru(0001) or O(2 × 1)/Ru(0001) structures.8 Naturally surface diffusion of oxygen atoms will take place from the high concentration region into a low concentration region. Hence the second front (marked by white arrows in Figure 4) may be identified with an oxygen diffusion front. 3.3. Etching the h-BN/Ru(0001) Nanomesh in Oxygen: Microscopic Scale. In the following we have performed a combined Auger electron spectroscopy (AES) and scanning tunneling microscopy (STM) investigation revealing some microscopic aspects of h-BN layer etching process in oxygen, as well as ways to improve the h-BN nanomesh stability in reactive environments. The threshold for etching the nanomesh in 1 × 10-6 mbar O2 environment was found to be ∼600 °C. At this temperature an O2 exposure of 600 L is just enough to remove the BN from the surface completely. This is clearly seen by comparison of the corresponding AES spectra in Figure 5. After the given O2 exposure, the KLL peaks of B and N disappeared, while the KLL peak of oxygen arises. This finding is reconciled with the half-order spots seen by LEED after the exposure, suggesting the evolution of a O(2 × 2)/Ru(0001) structure. Smaller oxygen exposures at ∼600 °C 1 × 10-6 mbar has led to partial reduction of the B and N KLL peak intensities as compared to the pure freshly deposited h-BN/Ru(0001). Such kind of etching is qualitatively different from the one investigated by LEEM

Figure 6. STM images 43 nm × 43 nm of the h-BN/Ru(0001) nanomesh before and after various oxygen exposures. (a) Pure h-BN/ Ru(0001), Usample ) 1.05 V, Itunnelling ) 1 nA; (b) Pure h-BN/Ru(0001) exposed to 10 L of 1 × 10-7 mbar O2 at 600 °C, 1.55 V, 3 pA; (c) Pure h-BN/Ru(0001) exposed to 100 L of 1 × 10-6 mbar O2 at 600 °C, 1.45 V 1 nA; (d) Pure h-BN/Ru(0001) exposed to 600 L of 1 × 10-6 mbar O2 at 600 °C, 0.5 V, 1 nA; (e) h-BN/Ru(0001) precovered with 0.5 ML Au and annealed at 800 °C, 0.9 V, 0.5 nA; (f) h-BN/ Ru(0001) precovered with 0.5 ML Au and exposed to 300 L of 1 × 10-6 mbar O2 at 800 °C, 2.5 V, 1 pA.

above. A sequence of STM images is shown in Figure 6a-d, starting from a pure h-BN/Ru(0001) nanomesh and exposed to progressively higher O2 exposures at 600 °C up to the 600 L. With increasing O2 exposure the number and the size of defect regions grow. In the defect region no h-BN nanomesh is visible in STM. Such patches appear uniformly distributed across the entire surface and there are fuzzy boundaries between the areas with and without the nanomesh. The STM image taking after 600 L O2 exposure at 1 × 10-6 mbar and 600 °C shows no signs of the nanomesh in full agreement with complete absence of B and N peaks in the corresponding AES spectrum in Figure 5. If the h-BN/Ru(0001) is covered with the sub-ML Au film, prior to oxygen exposure, than the threshold temperature for etching was substantially increased. As can be seen from the corresponding AE spectrum in Figure 5, an Au coverage of 0.3-0.4 ML fully protects the nanomesh against an 600 L of O2 exposure at 1 × 10-6 mbar and 800 °C. A similar exposure but at 900 °C leads to a barely noticeable loss of B and N in the AE spectrum. At 1000 °C, an O2 exposure of 600 L leads to complete removal of the h-BN layer. Figure 6e shows the 0.5 ML Au/h-BN/Ru(0001) after annealing at 800 °C in UHV. As thoroughly discussed in our previous paper,9 Au diffuses under the h-BN layer at elevated temperatures, forming some islands of an extra layer of the metal atoms (cf. Figure 6e,f). The h-BN nanomesh covers the Au related layer. Some rare

O2 Interaction with h-BN/Ru(0001) Nanomesh Au nanoparticles, also visible in Figure 6e,f, are on top of the nanomesh. Exposing this surface to 300 L of O2 at 1 × 10-6 mbar and 800 °C, causes no observable damage of the nanomesh (cf. Figure 6f), fully compatible with corresponding AE spectra at 800 °C shown in Figure 5. The microscopic mechanism of the etching process is suggested to proceed as follows: In order to oxidize the pure h-BN nanomesh, atomic oxygen must be present on the surface. However, a perfect h-BN nanomesh inhibits the dissociation of oxygen. Rather d-states from the Ru(0001) surface have to be accessible to the incident O2 molecule in order to cause its dissociation. The only places on the h-BN nanomesh coated Ru(0001) surface where O2 dissociation is possible are defects (vacancies or group of vacancies as visible in STM: Figures 1a and 6a). Molecular O2 can slip through such defects and dissociate on the Ru(0001) surface, thereby forming adsorbed atomic oxygen. This chemisorbed oxygen is very mobile at 600 °C and attacks the h-BN nanomesh at the defects, where not all sp2 bonds of B or N are saturated. The initial etching process is self-accelerated as with progressing etching the defects on the h-BN nanomesh grow in size so that in turn the supply of atomic oxygen is accelerated. Indeed this self-acceleration is observed in the STM images of Figure 6. While at the beginning the etching process is quite slow, producing only a few nanometer sized defects, the final step of removal of the h-BN nanomesh proceeds quite quickly. If O2 etching of the h-BN nanomesh proceeds via defects then their blocking should retard the etching process. This is the main role of predeposited Au, as demonstrated by data in Figures 5 and 6. As shown above, Au coverages of θ e 0.5 ML shift the onset of h-BN etching at 1 × 10-6 mbar of O2 to 1000 °C. This is not far from the 1030 °C threshold of BN evaporation from the Ru(0001) surface in UHV, as established by temperature programmed desorption (TPD). It is worth noting that smaller Au coverages (∼0.1 - 0.2 ML) also provided a certain yet lower degree of protection against oxygen etching: at 1 × 10-6 mbar O2 the etching threshold was shifted from 600 to 700 °C. The vacancy-type defects are always observed in abundance on the pure h-BN/Ru(0001) nanomesh. In STM images they can be discerned especially clear on the wires of the nanomesh (in the form of small black dots, e.g., Figure 6a). However, when sufficient Au was present on the surface, the nanomesh wires appeared mostly uniform (Figure 6e,f). This holds true for various Au coverages, but not for θAu e 0.1 ML.9

J. Phys. Chem. C, Vol. 112, No. 28, 2008 10427 These STM observations are in nice agreement with the assumption of Au blocking the defects. 4. Summary Molecular oxygen is able to etch the h-BN/Ru(0001) nanomesh in two different regimes: Above 600 °C nucleation and growth of defects are observed by STM with progressing O2 treatment. An O2 exposure of 600 L at 1 × 10-6 mbar removes completely the entire h-BN layer. At 750 °C the etching process starts from macroscopic defects, although at much lower oxygen partial pressure of 5 × 10-8 mbar. In LEEM we observed how the reaction fronts evolve and propagate away from the macroscopic defects upon O2 exposure time. Submonolyaer amounts of Au (θ e 0.5 ML) are able to suppress efficiently the etching process of the h-BN nanomesh with molecular oxygen. This simple recipe improves the chemical stability of the h-BN nanomesh, which may be important for potential applications of the h-BN nanomesh in nanocatalysis or in electrochemical environment. Acknowledgment. We gratefully acknowledge the financial support from the European Union under contract no. NMP4CT-2004-013817 (Nanomesh). We acknowledge Edvin Lundgren to encourage us to perform the LEEM experiments at Max II, beamline I311. We express special thanks to Alexei Preobrajensky for various technical help and inspiring discussions. References and Notes (1) Corso, M.; Auw ¨ arter, W.; Muntwiler, M.; Tamai, A.; Greber, T.; Osterwalder, J. Science 2004, 303, 217. (2) Goriachko, A.; He, Y.; Knapp, M.; Over, H.; Corso, M.; Brugger, T.; Berner, S.; Osterwalder, J.; Greber, T. Langmuir 2007, 23, 2928. (3) Sachdev, H. Anorganische Chemie; Universita¨t des Saarlandes: Saarbru¨cken, Germany. (4) Laskowski, R.; Blaha, P.; Gallauner, T.; Schwarz, K. Phys. ReV. Lett. 2007, 98, 106802. (5) Berner, S.; Corso, M.; Widmer, R.; Groening, O.; Laskowski, R.; Blaha, P.; Schwarz, K.; Goriachko, A.; Over, H.; Gsell, S.; Schreck, M.; Sachdev, H.; Greber, T.; Osterwalder, J. Angew. Chem., Int. Ed. 2007, 46, 5115. (6) Paffett, M. T.; Simonson, R. J.; Papin, P.; Paine, R. T. Surf. Sci. 1990, 232, 286. (7) Schwegmann, S.; Seitsonen, A. P.; Dietrich, H.; Bludau, H.; Over, H.; Jacobi, K.; Ertl, G. Chem. Phys. Lett. 1997, 264, 680. (8) Pfnur, H.; Held, G.; Lindroos, M.; Menzel, D. Surf. Sci. 1989, 220, 43. (9) Goriachko, A.; He, Y. B.; Over, H. J. Phys. Chem. C 2008, 112, 8147.

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