Surface electronic states in three-dimensional SnO2 nanostructures

Kucheyev, S. O.; Baumann, Theodore F.; Sterne, P. A.; Wang, Y.M.; Buuren, T. van; Hamza, A. V.; Terminello, Louis J.; Willey, Trevor M.

doi:10.1103/physrevb.72.035404

Cited by 105 publications

(87 citation statements)

References 34 publications

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“…Oxidation on the single crystal surfaces can be clearly detected by sXAS (Figure 1 c). [ 24,26 ] As elaborated later, this surface oxidation layer plays an important role in the SEI formation on different Sn surfaces. SEI formation on surfaces prepared under inert atmosphere exhibit different phenomena but is outside the scope of this work.…”

Section: Resultsmentioning

confidence: 98%

Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Qiao

Lucas

Karim

et al. 2014

Adv Materials Inter

103

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Soft X‐ray absorption spectroscopy with different probe depth was employed to characterize the solid electrolyte interphases (SEIs) formed on β‐Sn single crystals with two different surface orientations. Based on comparative studies of C‐K, O‐K, and F‐K absorption spectra between the SEIs and reference samples, SEI on Sn (100) mainly consists of porous Li2CO3 species with electrolyte uptake, while SEI on Sn (001) essentially consists of LiF and organic molecules, with a small amount of –CO3 and electrolyte buried inside. Theoretical calculation suggests that Sn (001) surface is more reactive than (100), especially after air exposure. The reactive (001) surface facilitates the decomposition of LiPF6 to form a LiF layer. In contrast, SEI on (100) surface is predominately from the typical decomposition of carbonate‐based electrolyte. While the LiF passivates Sn (001) electrode after one cycle, the porous carbonate layer on (100) surface does not prevent further decomposition of electrolyte after many cycles. This leads to drastically different electrochemical behavior and morphology of the two SEIs. The result is a direct proof that surface properties of active materials could strongly impact the SEI formation on electrodes even with the same electrolyte. Such effect could lead to distinct SEI formation and electrochemical performance.

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Section: Resultsmentioning

confidence: 98%

Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Qiao

Lucas

Karim

et al. 2014

Adv Materials Inter

103

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“…The small leading edge feature at 488.5 eV present in the M 5 band for TiO 2 -SnO 2 :F has been identified previously in SnO 2 aerogels 39 and nanoribbons. 41 It is suggested to be related to Sn p states that are created by oxygen vacancies and surface reconstruction.…”

Section: Tin 3d Soft X-ray Absorptionmentioning

confidence: 91%

“…The broadening and overall reduction in resolution of these peaks compared to those for bare SnO 2 :F has been found in X-ray absorption spectra for SnO. 39 Through consideration of high-surface-area SnO 2 aerogels, Kucheyev et al 39 assigned the distortion to the presence of under-coordinated surface atoms. Ahn et al 40 observed a similar broadening in their study of size-controlled SnO 2 nanoparticles, where increased broadening was found to be correlated with decreasing nanoparticle size.…”

Section: Tin 3d Soft X-ray Absorptionmentioning

confidence: 99%

“…Surface reconstruction of this type will alter the Fermi level position of the heterostructure. 39 The presence of additional Sn p states, which have been assigned to exist both below 42 and above 39 the conduction band minimum, potentially alters the electronic structure of the conduction band. In order to confirm the presence of SnO 2 surface reconstruction, which is only observed indirectly here, more detailed analyses are required, for example those involving high-resolution transmission electron microscopy.…”

Section: Tin 3d Soft X-ray Absorptionmentioning

confidence: 99%

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TiO2-SnO2:F interfacial electronic structure investigated by soft x-ray absorption spectroscopy

et al. 2012

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The electronic structure of the titanium dioxide (TiO 2 ) -fluorine-doped tin dioxide (FTO) interface is investigated by soft X-ray absorption spectroscopy using synchrotron radiation. The measurements probe the site-and symmetry-selected unoccupied density-of-states, and reflect a complex interaction between an early transition metal oxide (d 0 ) semiconductor and a post-transition metal oxide ( d 10 ) degenerate semiconductor. The distinct interfacial electronic structure of TiO 2 -FTO is established by contrasting spectra with those for anatase and rutile TiO 2 , FTO, and ZnO-FTO and CdO-FTO interfaces. Oxygen 1s absorption spectra, which relate to the O 2p partial density-of-states of the conduction band, indicate that the interface is associated with a reduction in Ti d -O p orbital hybridization and an alteration of the TiO 2 crystal field. These observations are consistent with measured titanium 2p absorption spectra, which in addition provide evidence for distortion of long-range order around the cation site in the interfacial TiO 2 . The TiO 2 -FTO interface is a functional component of a number of optoelectronic devices, perhaps most notably within the anode structure of solar cell architectures. In non-equilibrium conditions such as those found in operating solar cells interfacial electronic structure directly influences performance, for instance by modifying the quasi-Fermi level of electrons and the potential distribution at the transparent electrode.

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“…[1][2][3][4][5] However, their properties depend heavily on the nanostructure morphology as well as electronic structure, which is modified by intrinsic oxygen vacancies (OVs). 6,7 Development of optoelectronic encompassing bulk SnO 2 materials, for instance, has been hampered by its dipole forbidden nature.…”

Section: Introductionmentioning

confidence: 99%

Regulation of oxygen vacancy types on SnO2 (110) surface by external strain

et al. 2016

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In tin dioxide nanostructures, oxygen vacancies (OVs) play an important role in their optical properties and thus regulation of both OV concentration and type via external strain is crucial to exploration of more applications. First-principle calculations of SnO2 ( 110) surface disclose that asymmetric deformations induced by external strain not only lead to its intrinsic surface elastic changes, but also result in different OV formation energy. In the absence of external strain, the energetically favorable oxygen vacancies (EFOV) appear in the bridging site of second layer. When -3.5% external strain is applied along y direction, the EFOV moves into plane site. This can be ascribed that the compressed deformation gives rise to redistribution of electronic wave function near OVs, therefore, formation of newly bond structures.Our results suggest that different type OVs in SnO2 surface can be controlled by strain engineering.

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Surface electronic states in three-dimensional SnO2 nanostructures

Cited by 105 publications

References 34 publications

Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

TiO2-SnO2:F interfacial electronic structure investigated by soft x-ray absorption spectroscopy

Regulation of oxygen vacancy types on SnO2 (110) surface by external strain

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