Atomic-Scale Tuning of Graphene/Cubic SiC Schottky Junction for Stable Low-Bias Photoelectrochemical Solar-to-Fuel Conversion

Engineering tunable graphene–semiconductor interfaces while simultaneously preserving the superior properties of graphene is critical to graphene-based devices for electronic, optoelectronic, biomedical, and photoelectrochemical applications. Here, we demonstrate this challenge can be surmounted by constructing an interesting atomic Schottky junction via epitaxial growth of high-quality and uniform graphene on cubic SiC (3C-SiC). By tailoring the graphene layers, the junction structure described herein exhibits an atomic-scale tunable Schottky junction with an inherent built-in electric field, making it a perfect prototype to systematically comprehend interfacial electronic properties and transport mechanisms. As a proof-of-concept study, the atomic-scale-tuned Schottky junction is demonstrated to promote both the separation and transport of charge carriers in a typical photoelectrochemical system for solar-to-fuel conversion under low bias. Simultaneously, the as-grown monolayer graphene with an extremely high conductivity protects the surface of 3C-SiC from photocorrosion and energetically delivers charge carriers to the loaded cocatalyst, achieving a synergetic enhancement of the catalytic stability and efficiency.

[1]  M. Syväjärvi,et al.  A nanostructured NiO/cubic SiC p–n heterojunction photoanode for enhanced solar water splitting , 2019, Journal of Materials Chemistry A.

[2]  E. Haller,et al.  Resonant photoluminescent charging of epitaxial graphene , 2010 .

[3]  M. Syväjärvi,et al.  Single Domain 3C-SiC Growth on Off-Oriented 4H-SiC Substrates , 2015 .

[4]  M. Willinger,et al.  Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging , 2016, Nature Communications.

[5]  M. Syväjärvi,et al.  Lateral Enlargement Growth Mechanism of 3C-SiC on Off-Oriented 4H-SiC Substrates , 2014 .

[6]  Qingliang Liao,et al.  Enhanced photoelectrochemical efficiency and stability using a conformal TiO2 film on a black silicon photoanode , 2017, Nature Energy.

[7]  M. I. Chaudhry,et al.  Absorption coefficient of β–SiC grown by chemical vapor deposition , 1992 .

[8]  Joonsuk Park,et al.  One-Step Hydrothermal Deposition of Ni:FeOOH onto Photoanodes for Enhanced Water Oxidation , 2016 .

[9]  Adam C. Nielander,et al.  Photoelectrochemical behavior of n-type Si(111) electrodes coated with a single layer of graphene. , 2013, Journal of the American Chemical Society.

[10]  H. Kang,et al.  A versatile photoanode-driven photoelectrochemical system for conversion of CO2 to fuels with high faradaic efficiencies at low bias potentials , 2014 .

[11]  Epitaxy of Graphene on 3C-SiC(111) Thin Films on Microfabricated Si(111) Substrates , 2012 .

[12]  R. Frost,et al.  Synthesis and Characterization of Cobalt Hydroxide, Cobalt Oxyhydroxide, and Cobalt Oxide Nanodiscs , 2010 .

[13]  M. H. Oliveira,et al.  Contribution of the buffer layer to the Raman spectrum of epitaxial graphene on SiC(0001) , 2012, 1212.1647.

[14]  Mingsen Deng,et al.  Surface polarization matters: enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt-Pd-graphene stack structures. , 2014, Angewandte Chemie.

[15]  A. Zakharov,et al.  Elimination of step bunching in the growth of large-area monolayer and multilayer graphene on off-axis 3C SiC (111) , 2018, Carbon.

[16]  Rose Amal,et al.  Hybrid graphene and graphitic carbon nitride nanocomposite: gap opening, electron-hole puddle, interfacial charge transfer, and enhanced visible light response. , 2012, Journal of the American Chemical Society.

[17]  J. S. Lee,et al.  Highly Conformal Deposition of an Ultrathin FeOOH Layer on a Hematite Nanostructure for Efficient Solar Water Splitting. , 2016, Angewandte Chemie.

[18]  F. Speck,et al.  Work function of graphene multilayers on SiC(0001) , 2017 .

[19]  Mikael Syväjärvi,et al.  Considerably long carrier lifetimes in high-quality 3C-SiC(111) , 2012 .

[20]  T. Kajino,et al.  Solar CO2 reduction using H2O by a semiconductor/metal-complex hybrid photocatalyst: enhanced efficiency and demonstration of a wireless system using SrTiO3 photoanodes , 2013 .

[21]  Jimmy C. Yu,et al.  Enhanced Activity and Stability of Carbon-Decorated Cuprous Oxide Mesoporous Nanorods for CO2 Reduction in Artificial Photosynthesis , 2016 .

[22]  R. Kaner,et al.  Honeycomb carbon: a review of graphene. , 2010, Chemical reviews.

[23]  J. Kelly,et al.  Photoelectrochemistry of 4H-SiC in KOH solutions , 2007 .

[24]  D. Basko,et al.  Raman spectroscopy as a versatile tool for studying the properties of graphene. , 2013, Nature nanotechnology.

[25]  Stacking sequence dependence of graphene layers on SiC (0001−)—Experimental and theoretical investigation , 2010, 1006.1040.

[26]  K. Ohkawa,et al.  Analysis of Products from Photoelectrochemical Reduction of 13CO2 by GaN-Si Based Tandem Photoelectrode , 2016 .

[27]  G. Shi,et al.  Graphene based new energy materials , 2011 .

[28]  A. Zakharov,et al.  Flat-Band Electronic Structure and Interlayer Spacing Influence in Rhombohedral Four-Layer Graphene. , 2018, Nano letters.

[29]  J. S. Lee,et al.  Carbonate-coordinated cobalt co-catalyzed BiVO4/WO3 composite photoanode tailored for CO2 reduction to fuels , 2015 .

[30]  J. E. Crombeen,et al.  LEED and Auger electron observations of the SiC(0001) surface , 1975 .

[31]  K. Rajeshwar,et al.  Efficient solar photoelectrosynthesis of methanol from carbon dioxide using hybrid CuO-Cu2O semiconductor nanorod arrays. , 2013, Chemical communications.

[32]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[33]  David M. Cwiertny,et al.  Adsorption of sulfur dioxide on hematite and goethite particle surfaces. , 2007, Physical chemistry chemical physics : PCCP.

[34]  High Electron Mobility in Epitaxial Graphene on 4H-SiC(0001) via post-growth annealing under hydrogen , 2014, Scientific reports.

[35]  Andre K. Geim,et al.  Raman spectrum of graphene and graphene layers. , 2006, Physical review letters.

[36]  N. English,et al.  Photo-induced charge separation across the graphene-TiO2 interface is faster than energy losses: a time-domain ab initio analysis. , 2012, Journal of the American Chemical Society.

[37]  T. Tsang,et al.  Paramagnetism and shake-up satellites in X-ray photoelectron spectra , 1974 .

[38]  C. Coletti,et al.  Structural and electronic properties of epitaxial graphene on SiC(0 0 0 1): a review of growth, characterization, transfer doping and hydrogen intercalation , 2010 .

[39]  A. Ouerghi,et al.  Evidence for Flat Bands near the Fermi Level in Epitaxial Rhombohedral Multilayer Graphene. , 2015, ACS nano.

[40]  Xiaogang Yang,et al.  Hematite-based water splitting with low turn-on voltages. , 2013, Angewandte Chemie.

[41]  H. B. Weber,et al.  Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. , 2009, Nature materials.

[42]  Juan Li,et al.  Effect of CoOOH loading on the photoelectrocatalytic performance of WO3 nanorod array film , 2013 .

[43]  T. Tang,et al.  Direct observation of a widely tunable bandgap in bilayer graphene , 2009, Nature.

[44]  Chun-Wei Chen,et al.  Blue photoluminescence from chemically derived graphene oxide. , 2010, Advanced materials.

[45]  Takashi Hisatomi,et al.  Ultrastable low-bias water splitting photoanodes via photocorrosion inhibition and in situ catalyst regeneration , 2016, Nature Energy.

[46]  E. Reisner,et al.  Bias-free photoelectrochemical water splitting with photosystem II on a dye-sensitized photoanode wired to hydrogenase , 2018, Nature Energy.

[47]  J. Nørskov,et al.  Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte. , 2019, Chemical reviews.

[48]  M. Cassir,et al.  Direct Low-Temperature Deposition of Crystallized CoOOH Films by Potentiostatic Electrolysis , 2005 .

[49]  Jun Yan,et al.  High-performance asymmetric supercapacitors with lithium intercalation reaction using metal oxide-based composites as electrode materials , 2014 .

[50]  S. Davydov On the electron affinity of silicon carbide polytypes , 2007 .

[51]  Tony F. Heinz,et al.  Observation of an electrically tunable band gap in trilayer graphene , 2011, 1105.4658.

[52]  Haixin Chang,et al.  Graphene-based nanocomposites: preparation, functionalization, and energy and environmental applications , 2013 .

[53]  A. Bartolomeo Graphene Schottky diodes: an experimental review of the rectifying graphene/semiconductor heterojunction , 2015, 1505.07686.