i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 0 7 2 e1 1 0 8 0

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Band gap of C3N4 in the GW approximation

Yuan Xu, Shang-Peng Gao*

Department of Materials Science, Fudan University, 220 Handan Road, Shanghai 200433, PR China

article info abstract

Article history: Ab initio calculations based on density functional theory are performed to study the
Received 24 February 2012 stability of newly proposed C3N4 forms. Heptazine-based g-C3N4 was found to be ener-
Received in revised form getically favored relative to other phases. The quasiparticle band energies of different C3N4
26 April 2012 phases are calculated using the GW method. Among the seven phases of C3N4 studied, only
Accepted 28 April 2012 the pseudocubic phase and g-h-triazine phase have direct band gaps, and all of the other
Available online 29 May 2012 phases have indirect band gaps. The band gap of a-C3N4, b-C3N4, cubic-C3N4, pseudocubic-
C3N4, g-h-triazine, g-o-triazine and g-h-heptazine is 5.49 eV, 4.85 eV, 4.30 eV, 4.13 eV,
Keywords: 2.97 eV, 0.93 eV and 2.88 eV, respectively. From the viewpoint of band gap energies, both
Carbon nitride the g-h-heptazine and the g-h-triazine phases can be used as suitable photocatalysts for
GW method hydrogen production using water.
Photocatalyst Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Band gap reserved.

1. Introduction material for super-hard phases. The preparation for g-C3N4

has been reported [8e21].
Carbon nitride, which contains covalent bonds, has recently Graphitic C3N4, with its high stability and moderate band
received new interest as a promising material in various gap, has been a very active research topic because recent
applications, such as a photocatalyst, fuel cell electrode, light- discoveries suggest that graphitic C3N4 can function as
emitting device and chemical sensor. In early research, Liu a metal-free polymeric photocatalyst for splitting water
and Cohen [1] predicted that b-C3N4 possesses compressibility molecules with solar energy [22,23]. In 2008, Wang et al.
comparable to diamond. Then, first-principles studies on the demonstrated that graphitic C3N4 is able to generate hydrogen
hardness of C3N4 polymorphs were investigated [2e4]. The from water in the absence of noble metals, which could
search for different structures of C3N4 has a long history. Teter provide an ideal future renewable energy resource [24,25].
and Hemley [2] investigated five forms of C3N4, including a- Sulfur doped g-C3N4 was reported to show a photoreactivity of
C3N4, b-C3N4, cubic-C3N4, pseudocubic-C3N4 and graphitic H2 evolution 7e8 times greater than pure g-C3N4 [26].
C3N4. Their calculations predicted that a-C3N4 and graphitic Hybridized with other photocatalysts and other dopants have
allotropes are energetically favored relative to b-C3N4. Since enhanced the photoreactivity performance [27e30].
then, much effort has been made for the synthesis of C3N4. All In 1999, Alves et al. [31] proposed a new structure model for
kinds of techniques have been used to elaborate dense pha- the graphitic C3N4 that was based on a new carbon vacancy
ses, including vapor deposition, laser ablation and high- order, resulting in an orthorhombic cell. At the same time,
pressure high-temperature methods [5e7]. Because of the Mattesini et al. [32] found metallic behavior for the ortho-
chemical inertness of C3N4, preparing dense C3N4 phases with rhombic system from a density of states (DOS) analysis. A
large crystalline size for unambiguous characterization is special interest for new materials with low compressibility
difficult. Graphitic C3N4 has potential to be the starting spurred studies on the most stable polymorphs of C3N4.

* Corresponding author. Tel./fax: þ86 21 65643259.

E-mail addresses: [email protected], [email protected] (S.-P. Gao).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2012.04.138
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Recently, another new graphitic structure that could be for g-h-heptazine. The number of bands for the self-energy
prepared with heptazine (tri-s-triazine) derivatives was re- calculation, the energy cutoff for self-energy and the
examined and found to be more stable than triazine-based screening are set to 640, 354 eV (13 Hartree) and 354 eV (13
C3N4 by about 30 kJ mol1 [33]. In addition to theoretical Hartree), respectively, for heptazine-based C3N4 phase. The
evidence [34], further experimental results indicate that, parameters for other phases are chosen accordingly with
under moderate temperature, the decomposition of tri- equivalent or better convergence.
chloromelamine results in CNxHy that contain larger In the calculation of enthalpy under pressure, CASTEP code
heptazine-like building blocks [35]. Pyrolysis, which uses tri- [53] is employed for two reasons: (1) pseudopotential with
cyanomelaminates as a precursor, found final products that smaller cutoff radius should been constructed to avoid over-
conformed to a heptazine-based structure [36]. Heptazine- lapping spheres between pseudopotentials in the high pres-
based precursors have been utilized to form a C3N4 network sure study. A smaller cutoff radius implies larger cutoff energy
[33,37]. Other researches have demonstrated the prevalence of of plane-wave basis set. Ultrasoft pseudopotential [54] can be
the heptazine-based structure [9,10,12,16,38e40]. generated in CASTEP on-the-fly with a specified cutoff radius.
Determining the band structure of g-C3N4 is a crucial task (2) DFT with semi-empirical dispersion correction [55,56]
because the band gaps of photocatalyst candidates need to be implemented in CASTEP can predict the phase trans-
larger than 1.23 eV to overcome the endothermic character of formation of g-C3N4 phases more reliably because the correct
water-splitting and smaller than 3.1 eV to absorb light in the longerange interaction tail is absent from popular LDA or
visible range. Considering thermodynamic losses and over- generalized gradient approximation (GGA) for exchange-
potentials in the photocatalytic process, photocatalyst correlation functional. We want to emphasize that the
candidates should have band gaps between 2 eV and 3.1 eV CASTEP code is only used for pressure induced phase trans-
[41]. These values are strongly dependent on the electronic formation study in this work and this do not affect the
property of the candidate. Earlier ab initio calculations on C3N4 consistency of our band gap results obtained from ABINIT
have attempted to elucidate the mechanical and electronic code.
properties of C3N4. Considering the problem that density
functional theory (DFT) with local density approximation
(LDA) often underestimates the band gaps of semiconductors 3. Results and discussion
and insulators, the GW approximation is a good solution for
correcting the band structure [42e47]. Corkill and Cohen [48] 3.1. Structure and relative stability of C3N4 phases
predicted a large indirect gap of b-C3N4. The band gaps of
pseudocubic compounds including C3N4 were calculated by Lü Graphitic C3N4 has a laminar structure. The sp2-bonded C and
and Zheng [49]. However, a more systematic study of the N atoms form the graphitic planes that are stacked in a stag-
electronic properties of C3N4, especially for g-C3N4, is needed. gered fashion. Different building blocks of the honeycomb
Motivated by the unclear properties of g-C3N4, we investi- network within layers have been proposed. Two of these
gate band gap characters for three models of g-C3N4 and the phases are built on triazine (C3N3) rings: one with a hexagonal
other dense forms of C3N4 based on both DFT-LDA and GW unit cell, referred to as g-h-triazine (Fig. 1 (a)) in this paper, and
method. Furthermore, we investigate the structural and the other with an orthorhombic unit cell, g-o-triazine (Fig. 1
electronic properties of g-C3N4. (b)). In the g-h-triazine phase, the unit cell contains 14
atoms and three-coordinated nitrogen atoms connecting the
triazine rings, while in the g-o-triazine phase, there are direct
2. Computational method CeN bonds between the rings. The difference of the phases
can also be described as a difference in the stacking order
Both DFT calculation, that determines structure parameters, between adjacent 1D-melon strands formed by triazine units.
band energies and wavefunctions as input in GW calculation, The third phase, labeled as g-h-heptazine (Fig. 1 (c)), is con-
and the GW calculation are performed using the ABINIT structed from heptazine units (C6N7), which consist of three
package [50]. LDA is employed for exchange-correlation fused s-triazine rings connected by nitrogen atoms. To
energy with the plane-wave basis set and norm-conserving simplify the calculation, we assume that these models are in
pseudopotentials by Troullier and Martins [51]. The ABAB-stacking order. Corrugation effects are not considered.
Monkhorst-Pack scheme [52] is used for k points sampling The primitive cell models contain 2 layers for all the 3
over the Brillouin zone (BZ). The energy cutoff of 816 eV (30 graphitic C3N4 phases. Number of atoms in each primitive cell
Hartree) is chosen for the plane-wave functions after a careful is 14 for both g-h-triazine and g-o-triazine, 28 for g-h-hepta-
convergence study. zine. Primitive cells of 4 dense C3N4 phases are shown in Fig. 2.
The one-shot G0W0 method using a plasmon-pole model The primitive cell contains 28 atoms for a-C3N4, 14 atoms for
[43e45] is applied in the GW calculation. To choose the k-point b-C3N4, 14 atoms for cubic-C3N4 and 7 atoms for pseudocubic-
grid used in the GW calculation, the following two criterions C3N4.
have been considered: (1) the interested special k-points to The optimized equilibrium lattice parameters are listed in
determine the band gap should be included in the grid, and (2) Table 1. The calculated lattice constant, 7.083 Å, of the g-h-
a balance between convergence and cost. The Monkhorst- heptazine phase is in good agreement with other calculations
Pack k-point grid is 3  3  4 for a-C3N4, 3  3  8 for b-C3N4, [57,58]. Experimental results obtained by X-ray diffraction and
7  7  7 for cubic-C3N4, 8  8  8 for pseudocubic-C3N4, high-resolution electron microscopy (HRTEM) micrograph
6  6  4 for g-h-triazine, 6  6  4 for g-o-triazine and 4  4  4 found that the inter-planar distance is between 3.19 Å and
11074 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 0 7 2 e1 1 0 8 0

Fig. 1 e Crystal structure of 3 g-C3N4 phases viewed as one graphitic-like layer: (a) g-h-triazine, (b) g-o-triazine and
(c) g-h-heptazine.

Fig. 2 e Primitive cells of 4 dense C3N4 phases: (a) a-C3N4, (b) b-C3N4, (c) cubic-C3N4 and (d) pseudocubic-C3N4. Carbon and
nitrogen atoms are depicted in big and small balls respectively.
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Table 1 e Structural parameters and total energies for

different C3N4 phases.
Space group Lattice Z
parameter (Å)

Alpha P31c (159) a¼ 6.465,a 4

c¼ 4.709b
Beta P3 (143) a¼ 6.406,c 2
c¼ 2.406d
Cubic I-43d (220) a¼ 5.411e 2
Pseudocubic P-42m (111) a¼ 3.426 1
g-h-triazine P-6m2 (187) a¼ 4.746, 2
c¼ 6.586
g-o-triazine P2mm (25) a¼ 4.147, 2
b¼ 4.754,
c¼ 6.474
g-h-heptazine Cmc21 (36) a¼ 7.083, 4
b¼ 12.269,
c¼ 6.871

a 6.425 in Ref. [5].

b 4.715 in Ref. [5].
c 6.419 in Ref. [5].
d 2.425 in Ref. [5].
e 5.36 in Ref. [6], 5.8 in Ref. [7].

3.4 Å [9,10,36,38e40]. From our calculations, the distance is

3.436 Å, which matches the experiment value.
Enthalpies (E þ PV) of C3N4 phases under different hydro-
static pressure are shown in Fig. 3. At zero pressure, our
results indicate an energy trend that is consistent with the
previous results [2,34,59,60]. The heptazine-based phase has
the lowest energy. Thus, this phase is thermodynamically
most stable among all the allotropes at ambient pressure.
Results from both LDA and GGA calculations show that dense
forms of C3N4 will be more stable than the graphitic forms
under high pressure. a-C3N4 will be more stable than g-h-
heptazine under a hydrostatic pressure larger than about
9 GPa predicted by DFT-LDA (18 GPa by DFT-GGA).
Since g-o-triazine and g-h-triazine have the same building Fig. 3 e Enthalpies (in eV, per C3N4 unit) of 7 C3N4 phases
blocks, a further calculation of the bond length is shown in under different hydrostatic pressures calculated using LDA
Table 2. d1 and d2 mark two varieties of bonds. d1 represents approximation (a) and GGA approximation (b) respectively.
bond lengths in the aromatic rings, and d2 represents bond Enthalpy of g-h-heptazine is taken as reference (set to
lengths that connect the rings as bridges. The optimized bond 0 eV).
length, d1, is 1.317 Å in the orthorhombic cell and is increased to
1.320 Å in hexagonal cell. To illustrate this difference,
a comparison of the structures shows a different bonding
conjugation due to the participation of the N1 atom (labeled in
Fig. 1) in the p-delocalisation. In the g-o-triazine phase, the two 3.2. Band structures
coordinated N1 atoms build a connection between the double-
bond resonance in the adjacent CeN heterocycles. Then, All of the band gap results calculated by DFT-LDA and GW
electron dislocalization is possible among the whole graphitic method are shown in Table 3. First, we compare the band
layer resulting in a reduced bond length. In the g-h-triazine structures of the four dense forms of C3N4 (a-, b-, cubic and
phase, the conjugation is confined only within the heterocy- pseudocubic) (Fig. 4). The a-C3N4 has the largest band gap
cles. Shorter bonds confer higher bonding energy. This finding among them. Fig. 4 (a) shows that a-C3N4 has an indirect gap
confirms the higher energy of the orthorhombic phase, which with the maximum of the valence band (VBM) at K and that
is mentioned above. The bond lengths of the heptazine-based the minimum of the conduction band (CBM) is (1/2, 0, 1/3) in
structures are also listed in Table 2. We may see that the g-h- the MeL direction, agreeing with previous DFT-LDA calcula-
heptazine phase has even larger bond lengths than the g-h- tions [59]. The LDA band gap is 3.76 eV while the GW band gap
triazine phase because of larger p-conjugated rings. Moreover, is 5.49 eV (Table 3). The GW band gap is larger than the LDA
the heptazine ring contains a nitrogen atom with sp2 hybrid- band gap by 1.73 eV. This corresponds to approximately 46% of
ization in the center, thus making it the most stable phase. the LDA band gap energy.
11076 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 0 7 2 e1 1 0 8 0

which is smallest among the dense phases. The GW band gap

Table 2 e Average CeN bond length of g-C3N4 phases.
of 4.13 eV agrees with that from Lü and Zheng’s study
d1 (Å) d2 (Å) (4.19 eV). The above four phases all have a wide gap because of
Our Literature Our Literature the sp3-hybridization of the carbon atoms and strong covalent
work work bonding.
In Fig. 5, we show the DFT-LDA band structure of g-h-
g-o-triazine 1.317 1.440
g-h-triazine 1.320 1.316a, 1.32b,c 1.444 1.43,c triazine and g-o-triazine. g-h-triazine (Fig. 5 (a)) has a direct
1.442a, 1.45b energy gap at the G point. The LDA band gap is only 1.16 eV
g-h-heptazine 1.335 1.342d 1.458 1.48d compared with the GW band gap 2.97 eV. This result is
expected since LDA commonly underestimates the band gap
a Ref. [59].
b Ref. [61].
of many semiconductors. The band gap is significantly
c Ref. [62]. enlarged by the GW approximation. Estimated by UVevis
d Ref. [57]. spectra, the optical band gap is approximately 3.1 eV [8].
Though similar in crystal structure with g-h-triazine, the
orthorhombic phase shows a different band structure. The
The b-C3N4, as studied by Corkill and Cohen [48], displays stronger electron dislocalization results in metallic behavior,
an indirect gap as shown in Fig. 4 (b). The VBM is at the G point, as shown in the LDA band structure in Fig. 5 (b). This finding
and the CBM is (1/3, 1/3, 0.261) in the KeH direction. We obtain agrees with the previous DOS analysis using the FP-LAPW
an LDA band gap of 3.12 eV compared with 3.11 eV from Ref approach [32,60]. However, the band gap changes to that of
[48]. From the G0W0 correction, the band gap is 4.85 eV, which a semiconductor with the GW correction, which shows
is much smaller than the previous result (6.4 eV). The differ- a narrow indirect band gap of 0.93 eV. The VBM shows a flat
ence in the results is probably because Corkill and Cohen [48] curve along the GeZ direction, and the CBM creates a platform
only calculated the self-energy correction at G, M, L and A and along the XeU direction. Since the minimum band gap
performed an extrapolation to determine the band gap, which requirement cannot be met, g-o-triazine is not a qualified
may introduce uncertain errors. candidate as a photocatalyst for water-splitting.
Fig. 4 (c) shows that cubic-C3N4 also has an indirect gap Finally, we begin to examine the g-h-heptazine phase, with
with the upper valence band edge in the GeN direction (0, 0, its larger unit cell and lower energy than the above two g-C3N4
0.429) and the lower conduction band edge in the GeH direc- phases. The g-h-heptazine phase has an indirect band gap
tion (0.288,0.288, 0.288). Cubic-C3N4 has a smaller band gap shown in Fig. 6. Similar to g-h-triazine, the band gap is
than b-C3N4 with 2.87 eV (LDA) and 4.30 eV (GW). As shown in widening from 0.89 eV (LDA) to 2.88 eV (G0W0) with the VBM at
Fig. 4 (d), unlike the above three phases, pseudocubic-C3N4 has the G point and the CBM at the Y point. The reported experi-
a direct band gap at the G point. The LDA band gap is 2.53 eV, mental band gap energies have a range from 2.67 eV [40],

Table 3 e Calculated LDA and GW band gaps, Eg, of C3N4.

LDA Other LDA G0W0 Other Experiment (eV) DEg (eV)
(eV) work (eV) (eV) GW work (G0W0-LDA)
(eV)

Alpha 3.76 3.80a, 3.85b 5.49 1.73

Beta 3.12 3.11c, 3.2d, 3.21a, 3.25b, 3.56e 4.85 6.4c 1.73
Cubic 2.87 2.90b, 2.91a 4.30 1.42
Pseudocubic 2.53 2.53f, 2.59a 4.13 4.19f 1.60
g-h-triazine 1.16 1.25a, 1.48g (FP-LAPW) 2.97 3.1h 1.81
g-o-triazine e 0.93 e
g-h-heptazine 0.89 2.88 2.67i, 2.7j, 2.73k, 1.99
2.75e2.8l, 2.95m

a Ref. [59].
b Ref. [2].
c Ref. [48].
d Ref. [63].
e Ref. [64].
f Ref. [49].
g Ref. [32].
h Ref. [8].
i Ref. [40].
j Refs. [24] and [30].
k Ref. [26].
l Ref. [65].
m Ref. [10].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 0 7 2 e1 1 0 8 0 11077

Fig. 4 e The band structures for a-C3N4 (a), b-C3N4 (b), cubic-C3N4 (c) and pseudocubic-C3N4 (d) calculated by DFT-LDA.

Fig. 5 e The band structures for g-h-triazine and g-o-triazine calculated by DFT-LDA.
11078 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 0 7 2 e1 1 0 8 0

Fig. 6 e The band structure for g-h-heptazine calculated by

DFT-LDA.

Fig. 7 e Site-projected partial density of states (DOS) of g-h-

2.7 eV [24,30], 2.73 eV [26], 2.75e2.8 eV [65] to 2.95 eV [10], our heptazine: (a) p orbitals and (b) s orbitals.
calculated GW band gap (2.88 eV) is closer to the experimental
results reported by Thomas et al. [10] The GW band gap of g-h-
heptazine is very close to the corresponding value of g-h-
triazine. This finding implies that g-h-triazine and g-h-hep-
tazine have similar electronic properties because they share direct band gap at Y (2.94 eV) is only 0.06 eV larger than the
a similar geometric structure. minimum band gap between G and Y, indicating a quasi-direct
For all the C3N4 phases, GW method gives larger band band gap characters for g-h-heptazine.
gap energy comparing to the DFT-LDA. Qualitative Fig. 7 shows the site projected partial density of states
disagreement has been found for g-o-triazine, which is (DOS) based on DFT-LDA for the g-h-heptazine phase. The
predicted to have metallic behavior by DFT-LDA and to be three species of nitrogen atoms are labeled as NAro, NTet and
a semiconductor by GW method. Nevertheless, the trend for NCen (see Fig. 1 (c)). The upper valence band, which lies
the change of band gaps by DFT-LDA is consistent with between w-0.14 eV and 0 eV, is mainly contributed by the 2p
those by GW method. orbitals of NAro and NCen. The lower conduction band consists
To clearly demonstrate the different band gap results predominantly of the 2p orbitals of carbon and NCen. At
between DFT-LDA and GW, the band energies of g-h- w1.7 eV above the VBM, the density of NAro exceeds that of
heptazine at different k points are listed in Table 4. We select NCen. This increased density can be induced by electron dis-
the upper valence band and lower conduction band for localization in the heptazine ring. The higher conduction band
comparison. GW commonly obtains a lower energy for the gradually shows more sp-hybridized characteristics of NTet. A
valence band and a higher energy for the conduction band. As previous report also confirmed this electron transition
a consequence, the band gap is larger than DFT-LDA. The scheme from VBM to CBM [24].

Table 4 e LDA and GW energy eigenvalues at high symmetry k points in BZ and energy gaps, Eg (eV), for g-h-heptazine.
G S Y Z T R

LDA GW LDA GW LDA GW LDA GW LDA GW LDA GW

E64v 3.71 2.99 3.58 2.91 3.60 2.93 3.69 2.97 3.59 2.92 3.57 2.90
E1c 5.46 6.80 4.63 5.92 4.60 5.87 5.71 7.09 4.79 6.09 4.77 6.07
Eg 1.75 3.81 1.05 3.01 1.00 2.94 2.02 4.12 1.20 3.17 1.20 3.17
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 1 0 7 2 e1 1 0 8 0 11079

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