Spin-gapless semiconducting graphitic carbon nitrides: A theoretical design from first principles

Abstract The Dirac cones in the electronic band structures of graphene cause exotic properties, such as Dirac fermions, but these cones are spin-degenerated. In this study, from first principles, we demonstrate that a honeycomb lattice of modified tri-s-triazine (C7N6) units has spin-polarized Dirac cones in the band structures and exhibits features of spin-gapless semiconductors (SGSs). The hybrid honeycomb lattice of the C7N6 and s-triazine (C3N3) units, however, is a SGS with parabolic energy–momentum dispersion relations near the Fermi level. Ferromagnetic ordering is stable with a Curie temperature (Tc) of 830 and 205 K for the two lattices, as revealed by Monte Carlo simulations within an Ising model. The two honeycomb lattices have topologically nontrivial electronic states with a Chern number of C = −1, implying that the quantum anomalous Hall effect (QAHE) states could be achieved in metal-free materials.

[1]  Yong Wang,et al.  Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry. , 2012, Angewandte Chemie.

[2]  Yong Wang,et al.  Synthesis and characterization of polyether structure carbon nitride , 2004 .

[3]  Yoshiyuki Kawazoe,et al.  First-Principles Determination of the Soft Mode in Cubic ZrO 2 , 1997 .

[4]  Q. Xue,et al.  Experimental Observation of the Quantum Anomalous Hall Effect in a Magnetic Topological Insulator , 2013, Science.

[5]  F. Wei,et al.  Gram-scale synthesis of nanomesh graphene with high surface area and its application in supercapacitor electrodes. , 2011, Chemical communications.

[6]  Y. Xu,et al.  Band gap of C3N4 in the GW approximation , 2012 .

[7]  S. Sanvito,et al.  Origin of the half-metallic properties of graphitic carbon nitride in bulk and confined forms , 2013 .

[8]  Chao Zhang,et al.  Zero-gap materials for future spintronics, electronics and optics , 2010 .

[9]  Xiao-Gang Wen,et al.  High-temperature fractional quantum Hall states. , 2010, Physical review letters.

[10]  M. Antonietti,et al.  A metal-free polymeric photocatalyst for hydrogen production from water under visible light. , 2009, Nature materials.

[11]  Zhongqin Yang,et al.  Electronic structures and spin gapless semiconductors in BN nanoribbons with vacancies , 2010 .

[12]  R. Ruoff,et al.  Carbon-Based Supercapacitors Produced by Activation of Graphene , 2011, Science.

[13]  Hiroaki Ishizuka,et al.  Dirac half-metal in a triangular ferrimagnet. , 2012, Physical review letters.

[14]  Feng Liu,et al.  Flat Chern band in a two-dimensional organometallic framework. , 2012, Physical review letters.

[15]  A. B. Jorge,et al.  H2 and O2 Evolution from Water Half-Splitting Reactions by Graphitic Carbon Nitride Materials , 2013 .

[16]  C. Cao,et al.  Self-assembled one-dimensional carbon nitride architectures , 2006 .

[17]  Haldane,et al.  Model for a quantum Hall effect without Landau levels: Condensed-matter realization of the "parity anomaly" , 1988, Physical review letters.

[18]  Jun Yan,et al.  Easy synthesis of porous graphene nanosheets and their use in supercapacitors , 2012 .

[19]  R. N. Brown,et al.  Interband Magnetoreflection and Band Structure of HgTe , 1967 .

[20]  A. Du,et al.  Spin-polarization and ferromagnetism of graphitic carbon nitride materials , 2013 .

[21]  Noèlia Pueyo Bellafont,et al.  Identifying atomic sites in N-doped pristine and defective graphene from ab initio core level binding energies , 2014 .

[22]  E. Kroke,et al.  Novel group 14 nitrides , 2004 .

[23]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[24]  S. Dai,et al.  Fluidic Carbon Precursors for Formation of Functional Carbon under Ambient Pressure Based on Ionic Liquids , 2010, Advanced materials.

[25]  Xiaolin Wang,et al.  Proposal for a new class of materials: spin gapless semiconductors. , 2008, Physical review letters.

[26]  Feng Liu,et al.  Spatially separated spin carriers in spin-semiconducting graphene nanoribbons. , 2013, Physical review letters.

[27]  G. Fecher,et al.  Realization of spin gapless semiconductors: the Heusler compound Mn2CoAl. , 2012, Physical review letters.

[28]  T. Jacob,et al.  Strong excitonic effects in the optical properties of graphitic carbon nitrideg-C3N4from first principles , 2013 .

[29]  Richard Dronskowski,et al.  Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations , 1993 .

[30]  W. Wang,et al.  A new spin gapless semiconductors family: Quaternary Heusler compounds , 2013, 1301.7488.

[31]  Stefan Blügel,et al.  Electrically tunable quantum anomalous Hall effect in graphene decorated by 5d transition-metal adatoms. , 2012, Physical review letters.

[32]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[33]  K. Zhao,et al.  Carbon self-doping induced high electronic conductivity and photoreactivity of g-C3N4. , 2012, Chemical communications.

[34]  Xiaoming Zhang,et al.  Half-metallicity of a kagome spin lattice: the case of a manganese bis-dithiolene monolayer. , 2013, Nanoscale.

[35]  E. J. Mele,et al.  Z2 topological order and the quantum spin Hall effect. , 2005, Physical review letters.

[36]  M. Antonietti,et al.  Synthesis of g‐C3N4 Nanoparticles in Mesoporous Silica Host Matrices , 2005 .

[37]  Aijun Du,et al.  First-principles prediction of metal-free magnetism and intrinsic half-metallicity in graphitic carbon nitride. , 2012, Physical review letters.

[38]  Zhansheng Lu,et al.  First-principles studies of BN sheets with absorbed transition metal single atoms or dimers: stabilities, electronic structures, and magnetic properties , 2012, Journal of physics. Condensed matter : an Institute of Physics journal.

[39]  G. Fiete,et al.  Topological insulators and fractional quantum Hall effect on the ruby lattice , 2011, 1105.4381.

[40]  Á. Rubio,et al.  Evidence of a low compressibility carbon nitride with defect-zincblende structure , 1997 .

[41]  Xiaoming Zhang,et al.  Topological insulator states in a honeycomb lattice of s-triazines. , 2014, Nanoscale.

[42]  Richard Dronskowski,et al.  Analytic projection from plane‐wave and PAW wavefunctions and application to chemical‐bonding analysis in solids , 2013, J. Comput. Chem..

[43]  Volker L. Deringer,et al.  Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. , 2011, The journal of physical chemistry. A.

[44]  M. Antonietti,et al.  Polymeric Graphitic Carbon Nitride for Heterogeneous Photocatalysis , 2012 .

[45]  K. Özdoğan,et al.  Search for spin gapless semiconductors: The case of inverse Heusler compounds , 2012, 1210.5355.

[46]  R. Schlögl,et al.  Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts , 2008 .

[47]  Wei Zhao,et al.  Production of Nitrogen-Doped Graphene by Low-Energy Nitrogen Implantation , 2012 .

[48]  Feng Liu,et al.  Quantum anomalous Hall effect in 2D organic topological insulators. , 2013, Physical review letters.