A First-Principles Study of

Graphitic and Monolayer C3N4

Andres Bethavan Situmorang a, Viet-Duc Le a, Yong Hyun Kim a,b
a 
Department of Physics, KAIST, Daejeon, South Korea
b 
Graduate School of Nanoscience an Technology, KAIST, Daejeon, South
Korea
Contents
• Introduction
• Research motivation
• Fabrication method, characterization, and performance test

• Method
• Computational method
• DFT+D and SCAN review

• Result
• Result and summary
Contents
• Introduction
• Research motivation
• Fabrication method, characterization, and performance test

• Method
• Computational method
• DFT+D and SCAN background

• Result
• Result and summary
Research motivation

Albero et al,
Coordination Chemistry Review (2014) Samsung Display

• Electronic structure of QD:

o Intermediate state between molecule and bulk semiconductor
o The collapse of bulk bands into discrete energy states due to quantum confinement  adjustable band gap

• State of the art:

o Heavy-metal based QD, metal-halide perovskite (environmentally unfriendly)  Graphene QD
o Graphene QD’s drawbacks: undesirable EL wavelength change, low color purity, etc.
Fabrication and Characterization

Sungjin Park et al.

• Precursor : Urea (UCN), methoxy-benzene diazonium salt (MD)

• XRD : peak at 27°  dominant (002) plane
• FT-IR : MD addition  the attachment of CH3O-phenyl group at UCN
• Spectroscopy : Egap = 2.59 eV
Performance Test

Sungjin Park et al.

• First efficient LEDS with C3N4 materials
• EL() : peak at 506 nm (green light) ~ 2.5 eV
• EQE(): 0.91% (compared to graphene QD’s 1.28% and carbon nanodots’ 0.6%)
Contents
• Introduction
• Research motivation
• Fabrication method, characterization, and performance test

• Method
• Computational method
• DFT+D and SCAN review

• Result
• Result and summary
Method
• Bulk • Monolayer
o PBE, PBE+D2, PBE+D3, PBEsol, PBEsol+D3, o PBE, PBE+D2, PBE+D3, PBEsol, PBEsol+D3,
SCAN+rVV10 exchange correlation functional SCAN+rVV10 exchange correlation functional
o PAW ionic core potential o PAW ionic core potential
o Plane wave energy cutoff = 550 eV o Plane wave energy cutoff = 550 eV
o 6 x 6 x 6 k-point set o 6 x 6 x 1 k-point set
o SCF energy criterion < 10-6 eV o SCF energy criterion < 10-6 eV
o Force relaxation < 10-3 eV/Å o Force relaxation < 10-3 eV/Å
A

H
L Γ

M K

Atomic structure of bulk (left) and monolayer (right) C 3N4 and special k-path in BZ (middle).
Method
• Phonon calculation
o PBE-based finite differences method
o PAW ionic core potential
o Plane wave energy cutoff = 800 eV
o 3 x 3 x 1 k-point set
o SCF energy criterion < 10-8 eV
o Force relaxation < 10-3 eV/Å
Theoretical Background
• DFT+D correction

𝐸=𝐸 𝐷𝐹𝑇 + 𝐸𝑑𝑖𝑠𝑝

DFT+D2 Grimme et al, J. Chem. Phys.

(2010)
DFT+D3
where is the dispersion coefficient for atom and and is a damping term.

• SCAN+rVV10
o Non-empirical semi-local functional
o Satisfy all known possible exact constraints
o Appropriately normed on systems for which semi-local functionals can be extremely accurate; i.e. rare gas and non-bonded interactions
Result
• Introduction
• Research motivation
• Fabrication method, characterization, and performance test

• Method
• Computational method
• DFT+D and SCAN review

• Result
• Result and summary
Bulk C3N4 c-value
• PBE and PBEsol functional both show
small curvature suggesting weak
interlayer interaction.
• The experimental value is 6.42 Å
• SCAN, PBE+D2, and PBEsol+D3 give a
reasonable result.

  PBE PBE+D2 PBE+D3 PBEsol PBEsol+D3 SCAN

a (A) 7.135 7.137 7.137 7.135 7.135 7.134

c (A) 7.62 6.45 6.68 7 6.45 6.41

Aligned Potential Surface

𝐸 𝑏𝑖𝑛 𝑑=𝐸𝑚𝑜𝑛𝑜 – 𝐸 𝑏𝑢𝑙𝑘

(Left) The monolayer C3N4 energy is set as the zero
reference. (Top) Binding energy of bulk C3N4 for 2x2
supercell (8 f.u.) in eV.
Band Structure of Bulk C3N4

Bulk PBE+D2 Bulk HSE PBE+D2 (top) & HSE(bottom)

• Indirect (Γ-K) band gap with Egap = 0.7 eV for PBE+D2 and Egap = 2.05 eV for HSE.
• The VBM is mostly composed of N’s 2px orbital.
• C’s 2pz and N’s 2pz mix to make up the CBM.
 Monolayer vs Bulk C3N4 (HSE)

Monolayer HSE Bulk HSE

Bulk HSE (top) & monolayer

• Indirect (Γ-K) band gap for both cases. Monolayer’s Egap = 2.40 eV > bulk’s Egap = 2.05 eV. HSE (bottom)
• No dramatic VBM and CBM profile change. The VBM is mostly composed of N’s 2px orbital.
• C’s 2pz and N’s 2pz mix to make up the CBM.
Corrugated
Comparing the geometry
of planar and corrugated
one (lattice constant,
angle, etc..)

Eplanar

Ebulk

Ecorrugated

• The existence of negative frequency  planar structure is unstable  corrugated structure.

• Corrugated structure is more stable than the planar structure by about 3.5 eV in 2 x 2 supercell (8 f.u.).
• Corrugated structure is also more energetically favorable compared to the bulk structure. However, due to energy
barrier, bulk structure can be synthesized.
Corrugation Effect of Monolayer
• adf

Planar HSE Corrugated HSE

Planar HSE (top) &
corrugated HSE (bottom)

• Direct band gap at Γ for corrugated structure. Corrugated Egap = 2.30 eV < planar Egap = 2.40 eV.
• Corrugation  out-of-plane protrusion  Mixing of N’s 2px and N’s 2pz at VBM.
 Mixing of C’s 2pz and C’s 2px at CBM.
Summary
• Experimentally, C3N4 is shown to be a good candidate for green LED.
• Our theoretical study shows the experimental c-parameter (6.42 Å) can be reproduced within a
reasonable error by using DFT+D correction or SCAN+rVV10.
• Bulk  planar monolayer
o DOS : No dramatic difference in VBM and CBM profile
o Band: Both structure have indirect (Γ-K) band gap but Egap increases from 2.05 to 2.4 eV.

• Corrugation is suggested to exist. Planar  corrugated monolayer

o DOS : Out of plane protrusion causes mixing of N (C) 2px and N (C) 2pz at the VBM (CBM).
o Band : Indirect (Γ-K) to direct (at Γ) band gap transition.
Band gap slightly decreases from 2.4 to 2.3 eV but still exists in a green light range.