Structure-sensitive oxidation of the indium phosphide (001) surface

Chen, G.; Visbeck, S.; Law, D. C.; Hicks, Robert F.

doi:10.1063/1.1471577

Cited by 52 publications

(72 citation statements)

References 43 publications

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“…On other surfaces where M -M dimers are not present, M -O-P bonds should dominate. These conclusions are consistent with suggestions from several experiments on InP and GaP oxidation 23,24,26,[66][67][68][69] . However, we should note that for the (100) surface, M -O-M is an exclusively surface-adsorbed topology, whereas M -O-P features oxygen incorporated in the subsurface.…”

Section: Discussionsupporting

confidence: 82%

“…Of the possible oxygen local bond configurations, two should dominate oxygen chemisorption and subsequent native oxide nucleation based on their relative stability: M -O-P and M -O-M . Notably, these same two topologies have been suggested based on x-ray photoemission spectra of InP(001) 23 , as well as calculations on InP nanowires 65 . Both topologies can also branch to form an additional M -O bond with some cost in energy.…”

Section: Discussionmentioning

confidence: 99%

“…Of these, experiments on InP(001) have shown that the P-rich surface features stable P-P dimers that exhibit weak oxygen uptake at ambient temperature, whereas the M -rich mixed-dimer δ(2×4) surface reacts readily with oxygen 23 . Since we are interested in surface oxygen binding, we therefore consider only the M -rich surface in the present study.…”

Section: Methodsmentioning

confidence: 99%

“…Although dissociative chemisorption of molecular oxygen is known to take place at III-V surfaces at ambient temperature 23 , experiments suggest that different local thermal and electrochemical growth conditions lead to significant variation in the composition and morphology of the resulting native oxide films 9,10,[24][25][26][27][28][29][30] . The discrepancies point to a complex free energy surface featuring competing variants whose expression is determined by a combination of kinetics and thermodynamics.…”

Section: Introductionmentioning

confidence: 99%

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Local structural models of complex oxygen- and hydroxyl-rich GaP/InP(001) surfaces

Wood

Ogitsu

Schwegler

2012

The Journal of Chemical Physics

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We perform density-functional theory calculations on model surfaces to investigate the interplay between the morphology, electronic structure, and chemistry of oxygen-and hydroxyl-rich surfaces of InP(001) and GaP(001). Four dominant local oxygen topologies are identified based on the coordination environment: M -O-M and M -O-P bridges for the oxygen-decorated surface; and M -[OH]-M bridges and atop M -OH structures for the hydroxyl-decorated surface (M =In,Ga). Unique signatures in the electronic structure are linked to each of the bond topologies, defining a map to structural models that can be used to aid the interpretation of experimental probes of native oxide morphology. The M -O-M bridge can create a trap for hole carriers upon imposition of strain or chemical modification of the bonding environment of the M atoms, which may contribute to the observed photocorrosion of GaP/InP-based electrodes in photoelectrochemical cells. Our results suggest that a simplified model incorporating the dominant local bond topologies within an oxygen adlayer should reproduce the essential chemistry of complex oxygen-rich InP(001) or GaP(001) surfaces, representing a significant advantage from a modeling standpoint.

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Section: Discussionsupporting

confidence: 82%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Local structural models of complex oxygen- and hydroxyl-rich GaP/InP(001) surfaces

Wood

Ogitsu

Schwegler

2012

The Journal of Chemical Physics

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“…The dangling bonds of surface In atoms react with water, introducing O atoms into the In-P bonds to form In-O-P bonds. 29 This process is energetically more favorable than the formation of In-O-In or P-O-P bonds. 30 It was reported that the anodization of InP leads to the formation of compositionally inhomogeneous oxides.…”

Section: Structural Chemical and Electronic Properties-mentioning

confidence: 99%

Photoelectrochemical Conditioning of MOVPE p-InP Films for Light-Induced Hydrogen Evolution: Chemical, Electronic and Optical Properties

Muñoz¹,

Heine²,

Lublow³

et al. 2013

ECS J. Solid State Sci. Technol.

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Homoepitaxial p-InP(100) thin films prepared by MOVPE (metallorganic vapor phase epitaxy) were transformed into an InP/oxidephosphate/Rh heterostructure by photoelectrochemical conditioning. Surface sensitive synchrotron radiation photoelectron spectroscopy indicates the formation of a mixed oxide constituted by In(PO 3 ) 3 , InPO 4 and In 2 O 3 as nominal components during photo-electrochemical activation. The operation of these films as hydrogen evolving photocathode proved a light-to-chemical energy conversion efficiency of 14.5%. Surface activation arises from a shift of the semiconductor electron affinity by 0.44 eV by formation of In-Cl interfacial dipoles with a density of about 10 12 cm −2 . Predominant local In 2 O 3 -like structures in the oxide introduce resonance states near the semiconductor conduction band edge imparting electron conductivity to the phosphate matrix. Surface reflectance investigations indicate an enhanced light-coupling in the layered architecture. Solar hydrogen generation from water represents a viable route for establishing a carbon-neutral energy infrastructure based on renewable energy resources.1-4 To achieve this long-term objective, numerous approaches are currently being pursued comprising adapting systems derived from photosynthesis, 5-7 identification of appropriate catalysts, 8 development of transition metal oxide photoelectrodes 9,10,11 as well as devising efficient semiconductor tandem structures.12-14 Because biomimetic systems inspired by natural photosynthesis are characterized by rather low theoretical efficiencies, 6 the use of photoresponsive semiconductor materials for the splitting of water appears currently most promising. It can be shown that dual-bandgap systems reach theoretically efficiencies well above 40% at AM1.5. 15 The development horizon suggests therefore the use of technologically advanced semiconductor materials which would allow comparably fast technical realization. Further, the orthogonalization of charge carrier and photon pathways as well as an increased built-in potential by interfacial doping was recently exploited to achieve efficiencies near 10% using Si as substrate. 16 p-type InP is one of the most efficient photocathode materials for hydrogen evolution available. Heller and Vadimsky 17 have shown three decades ago that hydrogen evolution can occur with an efficiency of 12% if rhodium is deposited as catalytically active and optically transparent thin-film on top of an In 2 O 3 /InP structure. In this work, a new approach based on thin film photoelectrodes is presented. The photocathode is realized by homoepitaxial growth of thin films onto InP wafers which allows the use of liftoff procedures already known for photovoltaic systems. 18,19 The removal of the thin film photocathodes from the growth substrate is thereby possible after fabrication of the devices. This approach reduces production costs, which is a decisive factor for many III-V devices. In this report, we evaluate the applicability of homoepitaxial devices with emphasis in...

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In Situ Characterization of Interfaces Relevant for Efficient Photoinduced Reactions

Supplie

May

Brückner

et al. 2017

Adv Materials Inter

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which he pioneered and established. In general, interfaces do not only determine electronic properties of the final device; their atomic order also highly affects growth kinetics and defect formation. Moreover, the design of solid-liquid and hybrid interfaces determines their chemical reactivity and stability. In situ monitoring of interface preparation, formation, and interfacial reactions thus promises efficient process control. Paired with a detailed understanding of interface formation mechanisms, however, the true power of in situ control is to allow for specific modification and tuning of interface formation for the device of choice. There are several excellent reviews on in situ approaches covering wide ranges of materials from basic science to applications as well as varieties of preparation and analysis techniques. [2][3][4][5][6][7][8][9][10][11] As indicated in Figure 1, this review will be focused on in situ control over interfaces of materials that are relevant for photoinduced reactions in high-efficiency solar energy conversion and sensing applications with in situ control of semiconductor/polymer/ biological interfaces. We will restrict the techniques to realistic and complex, non-ultrahigh-vacuum (UHV) ambient, where in situ control is most demandingbut also highly desired. The more complex the interfacial reactions are, the more important is the in situ characterization. Ex situ approaches can contribute to an indirect understanding of interface formation, but to understand and, finally, control the dynamic processes taking place, real-time measurements are appropriate. The challenge, we are facing, is twofold: On the one hand, increased interaction with the surrounding ambient causes higher complexity. Yet at the same time, it decreases the number of applicable techniques. On the other hand, those techniques are often elaborate and not necessarily easy to interpret. In a nutshell, we will discuss four main topics:(i) Surface preparation during growth of structures for highefficiency solar energy conversion: World-record conversion efficiencies in both photovoltaics [12,13] and solar water splitting [14] are achieved with multijunction solar cells based on epitaxial III/V compound semiconductor structures. We will discuss in situ controlled preparation Solar energy conversion and photoinduced bioactive sensors are representing topical scientific fields, where interfaces play a decisive role for efficient applications. The key to specifically tune these interfaces is a precise knowledge of interfacial structures and their formation on the microscopic, preferably atomic scale. Gaining thorough insight into interfacial reactions, however, is particularly challenging in relevant complex chemical environment. This review introduces a spectrum of material systems with corresponding interfaces significant for efficient applications in energy conversion and sensor technologies. It highlights appropriate analysis techniques capable of monitoring critical physicochemical reactions in situ during non-vacuu...

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Structure-sensitive oxidation of the indium phosphide (001) surface

Cited by 52 publications

References 43 publications

Local structural models of complex oxygen- and hydroxyl-rich GaP/InP(001) surfaces

Local structural models of complex oxygen- and hydroxyl-rich GaP/InP(001) surfaces

Photoelectrochemical Conditioning of MOVPE p-InP Films for Light-Induced Hydrogen Evolution: Chemical, Electronic and Optical Properties

In Situ Characterization of Interfaces Relevant for Efficient Photoinduced Reactions

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