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Structure and Stability of The Anatase Tio 2 (101) and (001) Surfaces
Structure and Stability of The Anatase Tio 2 (101) and (001) Surfaces
www.elsevier.nl/locate/susc
Abstract
Well-defined (101) and (001) surfaces of anatase TiO were studied for the first time by secondary-electron imaging
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and low-energy electron diffraction. Initially, both surfaces show a crystalline structure corresponding to the bulk
anatase phase, buried under an atomically thin contamination layer. After mild sputtering with 500 eV Ne+ ions, we
have observed a surface phase transition from tetragonal anatase to face-centered cubic titanium monoxide TiO.
Subsequent annealing at 900 K restores the (1×1) anatase structure at the (101) surface. On the (001) surface,
however, a (1×4) reconstruction appears. The unreconstructed structure can be recovered by exposing the surface to
oxygen. These observations demonstrate the stability of the anatase surfaces and illustrate the feasibility of preparing
and investigating clean surfaces of this technological important form of TiO . © 2000 Elsevier Science B.V. All
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rights reserved.
Keywords: Electron–solid interactions; Low energy electron diffraction (LEED); Secondary electron emission measurements;
Sputtering; Surface relaxation and reconstruction; Surface structure, morphology, roughness, and topography; Titanium oxide
0039-6028/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S0 0 39 - 6 0 28 ( 00 ) 0 05 2 7 -6
R. Hengerer et al. / Surface Science 460 (2000) 162–169 163
making the assumption of a perfect surface ter- found out that, due to the high electron mobility
mination of the bulk anatase lattice. In this paper, in the conduction band, anatase samples appa-
we report the first successful imaging of the surface rently do not need to be doped. We therefore used
lattice of TiO single crystals in the anatase struc- undoped samples in our subsequent work in order
2
ture by secondary-electron imaging (SEI ) and low- to preserve the high degree of stoichiometry of the
energy electron diffraction (LEED)1. The measure- crystals. Heating up to 900 K in UHV did not
ments were made on samples that were prepared dope the anatase crystal either, contrary to rutile,
by a chemical transport reaction [10,11], which which generally seems to be more easily doped
proved to be an appropriate method by which to than anatase2.
obtain high-quality anatase single crystals. The The experiments were performed in an ultra-
crystals exhibited mm2-sized (101) and (001) sur- high-vacuum chamber with a total pressure in the
faces; these are also the main surfaces in nanocrys- lower 10−10 Torr range. Chemical information
talline films [14]. On both faces, we have observed about the surface was obtained by Auger electron
reversible structural transitions, induced by sput- spectroscopy (AES ). The electron energy was
tering and subsequent annealing. These cycles can 2 keV for SEI as well as for AES. The same device,
be repeated reproducibly, demonstrating the sta- a display-type, retarding-grid spherical collector
bility of the anatase structure, which could per- system, is used for LEED and SEI, the only
fectly be recovered even after its complete difference being the energy of the primary
destruction at the surface. The sharp LEED pat- electrons [16 ].
terns presented here for both surfaces are, to our SEI records the backscattered (secondary)
knowledge, the first patterns reported for anatase electrons generated with primary electrons having
TiO . Earlier attempts to investigate naturally an energy in the keV range. SEI carries real-space
2
grown anatase using LEED have failed due to information about the local geometric arrangement
surface contaminations [15]. of atoms near a surface and is therefore comple-
mentary to the reciprocal-space information acces-
sible in LEED. Direct-projection imaging of the
2. Experimental interatomic directions, produced by the forward-
focusing effect in electron-atom scattering, is
Anatase single crystals were grown from the responsible for the formation of the SEI pattern.
gas phase by a chemical transport reaction as In the patterns presented here, the polar angle, h,
described previously [10]. The transparent and is defined by the direction of the primary-electron
colorless crystals ordinarily have a truncated bipyr- incidence and the particular direction of the
amidal habitus exhibiting mainly the (101) and secondary electrons. h can be determined within
(001) faces, as confirmed by Laue X-ray diffrac- an accuracy of ±1°, and its maximum value is
tion. They have surface areas of 1–4 mm2, and limited by approximately 52°, which corresponds
atomic-force microscopy revealed that the corruga- to the outer rim of the collector screen. Images
tion of the working surfaces was typically below can be recorded while the sample is rotated, which
1 nm. Prior to insertion into a vacuum, all crystals provides three-dimensional views of the structure.
were rinsed in water, ethanol, and acetone and For a structural transition, as reported here, SEI
contacted with silver glue to a copper plate in allows the correspondence of the high-symmetry
direct contact with an oven. Initially, we investi- axes of these structures to be identified, from which
gated a crystal that was reductively doped in pure the relative orientation of the initial and final
hydrogen at 800 K for 24 h in order to prevent structures can be readily determined [17]. While
electrostatic charging of the samples. However, we LEED is extremely sensitive to changes in the
surface atomic structure owing to the short mean
1 During the revision of this paper, another publication
appeared in Ref. [13] on X-ray photoelectron diffraction of an 2 This is also evident by the fact that reductive doping takes
anatase (001) thin film. much longer for anatase than for rutile.
164 R. Hengerer et al. / Surface Science 460 (2000) 162–169
free path of the 30–400 eV electrons, SEI provides tilting the (101) surface normal from the display
information on the first 10–20 atomic layers of the axis by 23°. The twofold symmetry of the (100)
surface. Thus successful imaging is possible with surface of the tetragonal anatase is clearly detecta-
SEI even when the surface atomic layer is disor- ble. The horizontal bright band corresponds to the
dered or contaminated [15]. (010) lattice plane of the anatase structure. The
central vertical band contains directions in the
(001) plane that are above or below the (010)
3. Results plane at a distance of approximately ±27 and
±45° from [100]. They can be identified as belong-
3.1. The (101) surface ing to the
210 and the
110 directions, respec-
tively. The bright spot, 23° to the left of the
Fig. 1a shows a secondary-electron pattern of electron gun, corresponds to the (101) surface
the (101) surface of an anatase crystal recorded normal of the crystal. Other salient features can
directly before any treatment of the surface. The be assigned to different symmetry directions of the
primary-electron beam is incident along the [100] anatase lattice. These results are in good agreement
direction of the crystal, which coincides with the with earlier investigations [15] and imply that the
center of the display unit. This is achieved by positions of the atoms in a near-surface region do
not deviate from the bulk values, i.e. the crystalline
structure is flawless and not reconstructed within
the inelastic mean free path of 2 keV electrons.
Note that this untreated surface is still covered by
a thin layer of contamination and/or disordered
atoms so that no LEED observation could be
made.
Attempts to produce clean and atomically
ordered surfaces on naturally grown anatase by
only sputtering (500 eV He+ ions for 15 min) failed
in a previous experiment due to the destruction of
the surface atomic order [15]. The SEI patterns
smeared out and could not be restored even after
a heat treatment at 500 K and exposure of the
surface to oxygen up to 10−3 Torr · s. A similar
problem was encountered with the present vapor-
phase-grown anatase already after sputtering for
only 30 s with 500 eV Ne+ ions. The SEI pattern
became diffuse, but still showed twofold symmetry
around the (010) plane. However, after continuing
the sputtering for 5 min, this symmetry changed
to fourfold (cf. Fig. 1b). Viewed along the [100]
direction, one recognizes a highly symmetrical
cross with the horizontal band still being the (010)
plane and the vertical band the (001) plane. Two
Fig. 1. Secondary-electron patterns obtained from the (101) other bands corresponding to the (011) and (011: )
anatase surface: (a) before and (b) after sputtering with 500 eV planes can now be identified at 45° to these bands.
Ne+ ions. The sample is tilted by 23° so that the primary
electrons are incident along the [100] direction. The central
Tilting the crystal around the [010] direction, one
portion of the pattern (polar angle h=0°) is covered by the detects bright patches at angles of 45 and 90°
shadow of the electron gun used for the excitation. relative to the [100] direction, signalling the
101
R. Hengerer et al. / Surface Science 460 (2000) 162–169 165
to be bulk-terminated, i.e. the surface is obviously this surface is clearly detectable. The horizontal
not reconstructed3. The surface lattice constants, bright band corresponds to the (010) lattice plane
calculated from the LEED pattern, correspond to and the vertical band to the (100) plane of the
the bulk values within an error limit of ≤1%. The anatase structure. The bright spots, approximately
(101) surface is thus undistorted, similar to (110), 38.5° to the left and right of the electron gun (as
the most stable face of rutile [18]. well as above and below it), all marked with a
cross, correspond to the
201 directions. Other
3.2. (001) surface symmetry directions of the anatase lattice produce
the remaining salient features observed in the
The next common surface of anatase is the pattern. These results show again that the atoms
(001) face, for which a secondary-electron pattern near the surface have positions given by their bulk
is presented in Fig. 4a, recorded before any surface values. It is remarkable that, similar to the (101)
treatment. The primary-electron beam is incident surface, the crystal structure of the untreated (001)
along the [001] direction of the crystal. The quasi- surface has an excellent quality, observed using
fourfold symmetry in the atomic arrangement at SEI.
An electron-diffraction pattern obtained from
the (001) surface at an energy of 191 eV is pre-
sented in Fig. 5a. This pattern is observed after
heating the sample to 900 K. Apparently, sputter-
3 It should be mentioned, however, that a (1×1) symmetry Fig. 5. LEED pattern of (001) surface of anatase recorded after
found by LEED cannot exclude a surface unit cell with a sym- annealing the surface at 900 K (a) without and (b) with
metric defect. sputtering.
R. Hengerer et al. / Surface Science 460 (2000) 162–169 167
face [24] predict a small relaxation of the (101) are due to H. Berger for technical help during the
and the (001) surfaces. These shifts in the atomic crystal growth.
positions are, however, only in the order of pm
and therefore beyond the resolution limit of the
LEED measurements. Strictly speaking, our state- References
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