Lepidocrocite-like TiO 2 and TiO 2 (110)–(1 × 2) supported on W(100)

Abstract

Ultrathin films of TiO₂ were grown on a W(100)–O(2 × 1) substrate and characterised with a combination of scanning tunneling microscopy (STM) and low energy electron diffraction. In addition to islands of rutile TiO₂(110) with (1 × 1) termination that were reported previously, we also observed rutile TiO₂(110) islands with a (1 × 2) film termination. A lepidocrocite-like TiO₂ nanosheet was also observed on the W(100) surface. High resolution STM images show that the nanosheet grows in the principal orthogonal directions of the W(100) substrate and forms a commensurate (1 × 7) coincident cell.

Keywords

STM Thin films W(100)Nanosheet Growth

Get full access to this article

View all access options for this article.

References

Henrich

V. E.

and Cox

P. A.

: ‘The surface science of metal oxides’, 1994, Cambridge, Cambridge University Press.

Kuhlenbeck

, Shaikhutdinov

and Freund

H-J.

: ‘Well-ordered transition metal oxide layers in model catalysis—a series of case studies’, Chem. Rev., 2013, 113, 3986–4034. doi: 10.1021/cr300312n

Grinter

D. C.

, Yim

C. M.

, Pang

C. L.

, Santos

, Mentes

T. O.

, Locatelli

and Thornton

Geoff

: ‘Oxidation state imaging of ceria island growth on Re(0001)’, J. Phys. Chem. C, 2013, 117, 16509–16514. doi: 10.1021/jp405887h

Freund

H-J.

and Pacchioni

: ‘Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts’, Chem. Soc. Rev., 2008, 37, 2224–2242. doi: 10.1039/b718768h

Luches

, Pagliuca

and Valeri

: ‘Morphology, stoichiometry, and interface structure of CeO₂ ultrathin films on Pt(111)’, J. Phys. Chem. C, 2011, 115, 10718–10726. doi: 10.1021/jp201139y

Franchy

: ‘Growth of thin, crystalline oxide, nitride and oxynitride films on metal and metal alloy surfaces’, Surf. Sci. Rep., 2000, 38, 195–294. doi: 10.1016/S0167-5729(99)00013-8

Guo

, Oh

W. S.

and Goodman

D. W.

: ‘Titanium oxide films grown on Mo(110)’, Surf. Sci., 1999, 437, 49–60. doi: 10.1016/S0039-6028(99)00678-0

Ashworth

T. V.

and Thornton

: ‘Thin film TiO₂ on nickel(110): an STM study’, Thin Solid Films, 2001, 400, 43–45. doi: 10.1016/S0040-6090(01)01445-6

Xia

, Zhu

, Kaspar

T. C.

, Du

, Birmingham

, Park

K. T.

and Zhang

: ‘Atomic structure of the anatase TiO₂(001) surface’, J. Phys. Chem. Lett., 2013, 4, 2958–2963. doi: 10.1021/jz401284u

10.

Silly

and Castell

M. R.

: ‘Formation of single-domain anatase TiO₂(001)–(1 × 4) islands on SrTiO3(001) after thermal annealing’, Appl. Phys. Lett., 2004, 85, 3223. doi: 10.1063/1.1805177

11.

, Kim

D. J.

, Kaspar

T. C.

, Chamberlin

S. E.

, Lyubinetsky

and Chmabers

S. A.

: ‘In-situ imaging of the nucleation and growth of epitaxial anatase TiO₂(001) films on SrTiO3(001)’, Surf. Sci., 2012, 606, 1443–1449. doi: 10.1016/j.susc.2012.05.010

12.

Diebold

, Ruzycki

, Herman

G. S.

and Selloni

: ‘One step towards bridging the materials gap: surface studies of TiO₂ anatase’, Catal. Today, 2003, 85, 93–100. doi: 10.1016/S0920-5861(03)00378-X

13.

Pang

C. L.

, Lindsay

and Thornton

: ‘Structure of clean and adsorbate-covered single-crystal rutile TiO₂ surfaces’, Chem. Rev., 2013, 113, 3887–3948. doi: 10.1021/cr300409r

14.

Diebold

: ‘The surface science of titanium dioxide’, Surf. Sci. Rep., 2003, 48, 53–229. doi: 10.1016/S0167-5729(02)00100-0

15.

Papageorgiou

A. C.

, Cabailh

, Chen

, Resta

, Lundgren

, Anderson

J. N.

and Thornton

: ‘Growth and reactivity of titanium oxide ultrathin films on Ni(110)’, J. Phys. Chem. C, 2007, 111, 7704–7710. doi: 10.1021/jp067802m

16.

Papageorgiou

A. C.

, Pang

C. L.

, Chen

and Thornton

: ‘Low-dimensional, reduced phases of ultrathin TiO₂’, ACS Nano, 2007, 1, 409–414. doi: 10.1021/nn700158s

17.

Atrei

, Cortigiani

and Ferrari

A. M.

: ‘Epitaxial growth of TiO₂ films with the rutile (110) structure on Ag (100)’, J. Phys.: Condens. Mattter, 2012, 24, 445005. doi: 10.1088/0953-8984/24/44/445005

18.

Atrei

, Ferrari

A. M.

, Szieberth

, Cortigiani

and Rovida

: ‘Lepidocrocite-like structure of the TiO₂ monolayer grown on Ag (100)’, Phys. Chem. Chem. Phys., 2010, 12, 11587–11595. doi: 10.1039/c0cp00173b

19.

Pang

C. L.

, Grinter

D. C.

, Matharu

and Thornton

: ‘A scanning tunneling microscopy study of ultrathin film rutile TiO₂(110) supported on W(100)–O(2 × 1)’, J. Phys. Chem. C, 2013, 117, 25622–25627. doi: 10.1021/jp409948u

20.

Bennett

R. A.

, Mulley

J. S.

, Newton

M. A.

and Surman

: ‘Spectroscopy of ultrathin epitaxial rutile TiO₂(110) films grown on W(100)’, J. Chem. Phys., 2007, 127, 084707. doi: 10.1063/1.2756842

21.

McCavish

N. D.

and Bennett

R. A.

: ‘Ultra-thin film growth of titanium dioxide on W(100)’, Surf. Sci., 2003, 546, 47–56. doi: 10.1016/j.susc.2003.09.015

22.

Bennett

R. A.

and McCavish

N. D.

: ‘Non-stoichiometric oxide surfaces and ultra-thin films: characterisation of TiO₂’, Top. Catal., 2005, 36, 11–19. doi: 10.1007/s11244-005-7858-2

23.

Ashworth

T. V.

, Muryn

C. A.

and Thornton

: ‘Nanodots and other low-dimensional structures of titanium oxides’, Nanotechnology, 2005, 16, 3041–3044. doi: 10.1088/0957-4484/16/12/052

24.

Hengerer

, Bolliger

, Erbudak

and Grätzel

: ‘Structure and stability of the anatase TiO₂ (101) and (001) surfaces’, Surf. Sci., 2000, 460, 162–169. doi: 10.1016/S0039-6028(00)00527-6

25.

Thomas

A. G.

, Flavell

W. R.

, Kumarasinghe

A. R.

, Mallick

A. K.

, Tsoutsou

, Smith

G. C.

, Stockbauer

, Patel

, Grätzel

and Hengerer

: ‘Resonant photoemission of anatase TiO₂ (101) and (001) single crystals’, Phys. Rev. B, 2003, 67, 035110. doi: 10.1103/PhysRevB.67.035110

26.

Atrei

, Bardi

and Rovida

: ‘Structure and composition of the titanium oxide layers formed by low-pressure oxidation of the Ni₉₄Ti₆(110) surface’, Surf. Sci., 1997, 391, 216–225. doi: 10.1016/S0039-6028(97)00485-8

27.

Agnoli

, Mentes

T. O.

, Niño

M. A.

, Locatelli

and Granozzi

: ‘A LEEM/μ-LEED investigation of phase transformations in TiOx/Pt(111) ultrathin films’, Phys. Chem. Chem. Phys., 2009, 11, 3727–3732. doi: 10.1039/b821339a

28.

Barcaro

, Agnoli

, Sedona

, Rizzi

G. A.

, Fortunelli

and Granozzi

: ‘Structure of reduced ultrathin TiOx polar films on Pt(111)’, J. Phys. Chem. C, 2009, 113, 5721–5729. doi: 10.1021/jp811020s

29.

Dulub

, Hebenstreit

and Diebold

: ‘Imaging cluster surfaces with atomic resolution: the strong metal-support interaction state of Pt supported on TiO₂(110)’, Phys. Rev. Lett., 2000, 84, 3646–3649. doi: 10.1103/PhysRevLett.84.3646

30.

Bennett

R. A.

, Pang

C. L.

, Perkins

, Smith

R. D.

, Morrall

, Kvon

R. I.

and Bowker

: ‘Surface structures in the SMSI state; Pd on (1 × 2) reconstructed TiO₂(110)’, J. Phys. Chem. B, 2002, 106, 4688–4696. doi: 10.1021/jp0138328

31.

Orzali

, Casarin

, Granozzi

, Sambi

and Vittadini

: ‘Bottom-up assembly of single-domain titania nanosheets on (1 × 2)-Pt(110)’, Phys. Rev. Lett., 2006, 97, 156101. doi: 10.1103/PhysRevLett.97.156101

32.

Breinlich

, Buchholz

, Moors

, Le Moal

, Becker

and Wandelt

: ‘Scanning tunneling microscopy investigation of ultrathin titanium oxide films grown on Pt₃Ti(111)’, J. Phys. Chem. C, 2014, 118, 6186–6192. doi: 10.1021/jp4105213

33.

Zhukhlistov

A. P.

: ‘Crystal structure of lepidocrocite FeO(OH) from the electron-diffractometry data’, Cryst. Rep., 2001, 46, 730–733. doi: 10.1134/1.1405857

34.

Vittadini

and Casarin

: ‘Ab initio modeling of TiO₂ nanosheets’, Theor. Chem. Acc., 2008, 120, 551–556. doi: 10.1007/s00214-008-0425-8

35.

Agnoli

, Orzali

, Sambi

, Vittadini

, Casarin

and Granozzi

: ‘Ultrathin TiO₂ films on (1 × 2)-Pt(110): a LEED, photoemission, STM, and theoretical investigation’, J. Phys. Chem. C, 2008, 112, 20038–20049. doi: 10.1021/jp807694r

36.

Walle

L. E.

, Agnoli

, Svenum

I.-H.

, Borg

, Artiglia

, Krüger

, Sandell

and Granozzi

: ‘High resolution photoemission and x-ray absorption spectroscopy of a lepidocrocite-like TiO₂ nanosheet on Pt (110) (1 × 2).’, J. Chem. Phys., 2011, 135, 054706. doi: 10.1063/1.3623271

37.

Yamazaki

, Kamisawa

, Kokubun

, Haga

, Kamimizu

and Sakamoto

: ‘Structure analysis of oxygen-adsorbed tungsten (001) surface’, Surf. Sci., 2001, 477, 174–178. doi: 10.1016/S0039-6028(01)00768-3

38.

Pang

C. L.

, Haycock

S. A.

, Raza

, Murray

P. W.

, Thornton

, Gülseren

, James

and Bullett

D. W.

: ‘Added row model of TiO₂(110) 1 × 2’, Phys. Rev. B, 1998, 58, 1586–1589. doi: 10.1103/PhysRevB.58.1586

39.

Elliott

S. D.

and Bates

S. P.

: ‘Assigning the (1 × 2) surface reconstruction on reduced rutile by first-principles energetics’, Phys. Rev. B, 2002, 65, 245145. doi: 10.1103/PhysRevB.65.245415

40.

Elliott

S. D.

and Bates

S. P.

: ‘Assignment of the (1 × 2) surface of rutile TiO₂(110) from first principles’, Phys. Rev. B, 2003, 67, 035421. doi: 10.1103/PhysRevB.67.035421

41.

Asari

and Souda

: ‘Atomic structure of TiO₂(110)-p(1 × 2) and p(1 × 3) surfaces studied by impact collision ion-scattering spectroscopy’, Phys. Rev. B, 1999, 60, 10719–10722. doi: 10.1103/PhysRevB.60.10719

42.

Onishi

and Iwasawa

: ‘Dynamic visualization of a metal-oxide-surface/gas-phase reaction: time-resolved observation by scanning tunneling microscopy at 800 K’, Phys. Rev. Lett., 1996, 76, 791–794. doi: 10.1103/PhysRevLett.76.791

43.

Murray

P. W.

, Condon

N. G.

and Thornton

: ‘Effect of stoichiometry on the structure of TiO₂(110)’, Phys. Rev. B, 1995, 51, 10989–10997. doi: 10.1103/PhysRevB.51.10989

44.

Blanco-Rey

, Abad

, Rogero

, Méndez

, López

M. F.

, Román

, Martín-Gago

J. A.

and de Andrés

P. L.

: ‘LEED-IV study of the rutile TiO₂(110)-1 × 2 surface with a Ti-interstitial added-row reconstruction’, Phys. Rev. B, 2007, 75.

45.

Onishi

and Iwasawa

: ‘Reconstruction of TiO₂(110) surface: STM study with atomic-scale resolution’, Surf. Sci., 1994, 313, L783–L789. doi: 10.1016/0039-6028(94)91146-0

46.

Takakusagi

, Fukui

K-I.

, Nariyuki

and Iwasawa

: ‘STM study on structures of two kinds of wide strands formed on TiO₂(110)’, Surf. Sci., 2003, 523, L41–L46. doi: 10.1016/S0039-6028(02)02353-1

47.

Blanco-Rey

, Abad

, Rogero

, Méndez

, López

M. F.

, Martin-Gago

J. A.

and de Andres

P. L.

: ‘Structure of rutile TiO₂(110)–(1 × 2): formation of Ti₂O₃ quasi-1D metallic chains’, Phys. Rev. Lett., 2006, 96. 055502 doi: 10.1103/PhysRevLett.96.055502

48.

Guo

, Cocks

and Williams

: ‘Surface Structure of (1 × 2) Reconstructed TiO₂(110) studied using electron stimulated desorption ion angular distribution’, Phys. Rev. Lett., 1996, 77, 3851–3854. doi: 10.1103/PhysRevLett.77.3851

49.

Bowker

and Bennett

R. A.

: ‘The role of Ti³⁺ interstitials in TiO₂(110) reduction and oxidation’, J. Phys.: Condens. Matter, 2009, 21, 474224. doi: 10.1088/0953-8984/22/5/059801

50.

Bennett

R. A.

, Stone

, Price

N. J.

and Bowker

: ‘Two (1 × 2) reconstructions of TiO₂(110): surface rearrangement and reactivity studied using elevated temperature scanning tunneling microscopy’, Phys. Rev. Lett., 1999, 82, 3831–3834. doi: 10.1103/PhysRevLett.82.3831

51.

Pieper

H. H.

, Venkataramani

, Torbrügge

, Bahr

, Lauritsen

J. V.

, Besenbacher

, Kühnle

and Reichling

: ‘Unravelling the atomic structure of cross-linked (1 × 2) TiO₂(110)’, Phys. Chem. Chem. Phys., 2010, 12, 12436–12441. doi: 10.1039/c0cp00160k

52.

Fukuda

, Sasaki

, Watanabe

, Nakai

, Inaba

and Omote

: ‘Novel crystal growth from a two-dimensionally bound nanoscopic system. Formation of oriented anatase nanocrystals from titania nanosheets’, Cryst. Growth Des., 2003, 3, 281–283. doi: 10.1021/cg025619m