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 Page 1 of 21 Physical Chemistry Chemical Physics
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Electronic Structure and Magnetic Properties of Penta-Graphene

Nanoribbons

Physical Chemistry Chemical Physics Accepted Manuscript

P. F. Yuan, Z. H. Zhang*, Z. Q. Fan, and M. Qiu
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ABSTRACT

Cutting 2D penta-graphene sheet along typical crystallographic orientations to construct

various penta-graphene nanoribbon (P-GNR) models, their electronic structures and magnetic

properties are investigated systemically. It is shown that P-GNRs are very versatile with rich and

unique electronic and magnetic nature. In particular, the bipolar magnetic semiconducting

features can be achieved in the ferromagnetic state for all magnetic P-GNRs, which makes

P-GNRs valuable for developing next-generation information storage devices. More interestingly,

the studies on electric-magnetic coupling reveals that an applied transverse electric field can

transform a P-GNR from a magnetic semiconductor to a half-metal with a wide band gap of

0.88eV, which can achieve complete spin filtering even at room temperature. Important

advantages of magnetism over graphene nanoribbons are thus expected.

Keywords: penta-graphene nanoribbons, bipolar magnetic semiconductor, transverse electric

effect, half-metal.

Institute of Nanomaterial & Nanostructure, Changsha University of Science and Technology, Changsha 410114,
China. *E-mail: zhzhang @csust.edu.cn

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Introduction

Graphene, a single-layer sheet with the sp2 hybridization of carbon atoms, displays

Physical Chemistry Chemical Physics Accepted Manuscript

exceptional electronic properties,1-3 which has attracted considerable research interest.4,5 Many

graphene-based high-performance nanoelectronic devices have been proposed, such as rectifiers,

spin-filtering devices, and field-effect transistors.6-8 Intriguing from the successful fabrication of
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graphene and to achieve more promising materials, exfoliating new single-layer 2D crystal

materials from their bulk materials has been one of the most emerging research field.9-10 In

recent years, numerous 2D crystal materials have thus been discovered and studied widely, such

as single-layer h-boron nitride,11 silicene,12 transition-metal dichalcogenides,13 and phosphorene,14

all of which display novel electronic behaviors.

It is believed that carbon will act as a key material to replace silicon in next-generation

integrated circuits. Thus much attention is paid to carbon-based materials. Beyond graphene,

other 2D materials with extended carbon networks, such as graphane15 and graphdiyne,16have also

recently been synthesized in succession. More recently, a new 2D material known as

penta-graphene17has been proposed. This carbon allotrope is predicted to be able to be exfoliated

from T12-carbon and displays a perfect pentagonal configuration, resembling the Cairo

pentagonal tiling. Two types of carbon hybridizations, sp2 and sp3, coexist in this nanostructure,

which is energetically advantageous compared with the sp-hybridization of carbon atoms such as

involved in graphdiyne, thus resulting in significant energetic, dynamic, thermal, and mechanical

stability in penta-graphene.17 In particular, unlike graphene, penta-graphene has a naturally

existing band gap. These features hold high promise for developing nanoelectronic devices.

As we know, the application of materials to nanodevices or nano-integrated circuits

requires their size reduced to the nanoscale in multiple dimensions, for example, in a nanoribbon

or nanoflake configuration. The electronic properties of such nanostructures are predicted to differ

from those in bulk or 2D configurations owing to quantum confinement effects and edge

states.18-22 For instance, 2D graphene sheet is a nonmagnetic gapless semimetal with Dirac-like
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band dispersion around the Fermi level. However, H-passivated armchair graphene nanoribbons

(AGNRs) possess a band gap (semiconductor) but are always nonmagnetic, whereas H-passivated

zigzag graphene nanoribbons (ZGNRs) can display magnetism owing to unusual edge state

Physical Chemistry Chemical Physics Accepted Manuscript

effects when the electron spin is involved.23-26 Similarly to graphene, penta-graphene can also be

cut along a certain crystallographic orientation to obtain quasi-one-dimensional materials,

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penta-graphene nanoribbons (P-GNRs). However, their electronic and magnetic behaviors still

remain unexplored.

In this present work, we report a detailed first-principles calculation on the

magneto-electronic properties of P-GNRs, based on density functional theory (DFT). Our study

shows that P-GNRs are very versatile with rich and unique electronic and magnetic nature, for

example,the prominent bipolar magnetic semiconductor behaviors are observed in the

ferromagnetic state for all magnetic P-GNRs, which makes P-GNRs more valuable.. More

interestingly,the studies on electric-magnetic coupling reveals that an applied transverse electric

field can transform a P-GNR from a magnetic semiconductor to a half-metal with a wide band

gap of 0.88eV, which has advantages over graphene nanoribbons. These results might be of

interest from the prospects of both fundamental science and its potential applications.

Structure Model and Theoretical Method

Fig.1(a) shows the crystal structure of penta-graphene. To achieve P-GNRs, we consider

two typical crystallographic orientations for tailoring, D1 and D2, with spanning 45º. Cutting

along the D1 direction allows to produce two classes of edge structures, namely zigzag and dimer

(large armchair) atom chain terminated edges, indicated in red and green, and referred to,

respectively, as Z- and A-type edges. The resulting three possible types of nanoribbons are shown

in Fig. 1(b)-(d), denoted as ZZ, ZA, and AA, respectively, depending on the edge types being

joined. Cutting along D2 yields a large sawtooth-type atom chain terminated edge. The

corresponding nanoribbon is denoted as SS, as shown in Fig. 1(e). The nanoribbon width w is

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defined as the number of carbon chains across the width direction, equal to the total number of

zigzag chains and dimer chains for ZZ, ZA, and AA, or the total number of sawtooth-type chains

Physical Chemistry Chemical Physics Accepted Manuscript

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(f)
AA
-8.0
Binding energy(eV)

ZA
ZZ
SS
-8.2

-8.4

5 10 15 20
w

FIG.1. Structural model and geometrical stability. (a) Structure of penta-graphene, with D1and D2 denoting the
“tailoring” orientations. The resulting four typical nanoribbons, with different edge configurations, are denoted
as (b) ZZ, (c) ZA, (d) AA, and (e) SS. The rectangular orange frame denotes one unit-cell of nanoribbon. (f)
Binding energy plotted as a function of the nanoribbon width w for the different penta-graphene nanoribbons.

for SS. The ZZ nanoribbon with width w is denoted as ZZ(w), and an analogous notation is

applied to other three types of nanoribbons, referred to as ZA(w), AA(w), and SS(w). Figures

1(b)-(e) present, respectively, ZZ(7), ZA(6), AA(7), and SS(6) as example. When these bare-edge

nanoribbons are directly optimized, a significant distortion will occur in the edge region because

the special 2D atomic framework of penta-graphene is frustrated upon forming a finite

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nanoribbon structure. To avoid such an issue, nanoribbons are passivated by hydrogen（H）atoms

at both edges to make the bond configuration of the edge atoms similar to that of the inner atoms

by maintaining their sp2 and sp3 hybridizations(3-coordinated and 4-coordinated C atoms,

Physical Chemistry Chemical Physics Accepted Manuscript

respectively) unchanged. This also eliminates the edge dangling bonds simultaneously to ensure

edge-structure stability. The orange dashed boxes denote unit cells, namely, the smallest
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repeatable units of each periodical structure along the ribbon-length direction. Calculations take

into account the super-cell, which consists of two unit cells, to allow the study of the different

spin-polarized states of the P-GNRs, as discussed below.

The magneto-electronic properties of these ribbons are calculated from first principles

within DFT, implemented using the Atomistix ToolKit (ATK) software package.27-29 The

spin-dependent generalized gradient approximation (SGGA) was chosen as the exchange-

correlation functional to solve the Kohn-Sham equation. We employed Troullier-Martins

norm-conserving pseudo-potentials to represent the atom core and linear combinations of local

atomic orbitals to expand the electron valence states. To consider the effect of atom polarization,

the wave function was expanded using the double-zeta plus polarization (DZP) basis for all atoms.

We performed 1×1×500 k-point sampling in the x, y, and z directions, respectively, where the z

axis defines the nanoribbon direction. For balancing calculation efficiency and accuracy, the

energy cut-off was set to 150 Ry to control the size of the real-space integral mesh partitioning

and derive a solution to the Poisson equation. All calculations were performed after optimizing

the geometry so that the residual forces on each atom were no greater than 0.01 eV/Å. We select

10-5 as the convergence criterion for the total energy. To eliminate interactions between the model

and its neighboring “images”, a vacuum layer at least 20 Å was selected in the x and y directions.

For simplicity, the Fermi level was set to zero in all the systems.

Results and Discussion

The structural stability and electronic properties in the nonmagnetic state

We first assessed the stability of the P-GNRs by calculating their binding energy EB,
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defined as EB = (ENR – nCEC – nH EH) / (nC + nH), where ENR denotes the total energy for one

super-cell, and EC (EH) and nC (nH) are, respectively, the energy of one isolated C (H) atom and

the number of corresponding atoms in one super-cell. The computed results for nanoribbons of

Physical Chemistry Chemical Physics Accepted Manuscript

various widths are shown in Fig. 1(f). All the binding energies clearly fall between -7.9 and -8.5

eV in the ribbon-width region (12, 28) Å. For comparison, we also calculated the binding energy
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of zigzag graphene nanoribbons (ZGNRs) and armchair graphene nanoribbons (AGNRs) in a

similar ribbon-width region, which appears in the range (-8.7, -9.2) eV. The P-GNR binding

energies are higher than those of graphene nanoribbons but are all very negative values, reflecting

the high stability of the P-GNRs. Moreover, the variation of the binding energy as a function of

width follows a similar trend for different P-GNRs. The binding energy decreases gradually with

increasing width, meaning that the P-GNRs become more stable with increasing width. Similar

results are observed in nanoribbons derived from other 2D sheets.22 Nanoribbon SS has the most

stable structure when compared with the other three types of P-GNRs with similar width. The

order of binding energies EB(SS) < EB(ZZ) < EB(ZA) < EB(AA) suggests greater stability for

nanoribbons containing more S- or Z-type edges. This is easily explained by the predominance of

sp3 hybridization in such edges. Furthermore, Oppenheimer molecular dynamics (BOMD)

simulations are performed to examine thermal stability of the P-GNRs. Their Geometrical

structure still intact at room temperature (300 K) after 8 ps of simulation. Increasing temperature

further, we can see small deformations occurring at 500K for ZZ and ZA, at 600K for AA, and at

700K for SS after 8 ps of simulation, but no edge reconstruction is observed, as shown in Fig.S1

in the Supporting Information, suggesting that the thermal stability of the P-GNRs are higher.

The energy band structure (BS), total density of states (DOS), and projected density of

states (PDOS) for nanoribbons ZZ(15), ZA(14), AA(15), and SS(11) in the nonmagnetic (NM)

state are shown in Figs. 2(a)-(d), respectively. Here, the PDOS is the DOS projected onto the edge

C atoms. The insets in each BS figure demonstrate the partial charge density distribution of the

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lowest conduction band (LCB, highlighted red) and the highest valence band (HVB, highlighted

blue) near the Fermi level. Clearly, ZZ, ZA, and AA have similar band structures, which are

Physical Chemistry Chemical Physics Accepted Manuscript

metallic because the LCB and HVB intersect at the Fermi level. The DOS and PDOS of

nanoribbons ZZ, ZA, and AA show that the total DOS near the Fermi level originates almost
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entirely from the contribution of edge C atoms. In other words, the metallicity of these

nanoribbons is dominated by the edge C atoms. These nanoribbons thus display prominently

localized edge states, details of which are apparent in the partial charge density distribution drawn

in the insets. The partial charge density of the LCB and HVB is primarily distributed at the

sp2-hybridized C atoms at the nanoribbon edge, namely, appearing at the apex C atoms in the

outermost Z-type chain for the Z-type edge or in the Z-type chain adjacent to the outermost dimer

(a) BS DO S& PDO S BS DO S& PDO S

1 .5 (b ) 1 .5

T o ta l
E d ge C T o ta l
E d ge C
Energy(eV)

Energy(eV)

0 .0 0 .0

ZZ ZA
- 1 .5 -1 .5
Γ Ζ 0 50 Γ Ζ 0 50

(c) BS DO S& PDO S (d ) 1 .5 BS DO S& PDO S

1 .5

T o ta l
E d ge C
T o ta l
Energy(eV)
Energy(eV)

E d ge C

0 .0 0 .0

AA SS
-1 .5 - 1 .5
Γ Ζ 0 100 200 Γ Ζ 0 50

FIG.2. Band structure (BS), total density of states (DOS), and projected density of states (PDOS) for various
P-GNRs. The PDOS is the DOS projected onto the edge C atoms. The insets indicated by arrows show the

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partial charge density distribution of the lowest conduction band (LCB, red) and highest valence band (HVB,
blue). The isosurface value is 0.005 e /Å3. Results correspond to (a) ZZ, (b) ZA, (c) AA, and (d) SS

nanoribbons.

Physical Chemistry Chemical Physics Accepted Manuscript

C chain for the A-type edge. This suggests that the localized edge states of nanoribbons ZZ, ZA,
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and AA, derived by cutting along D1, originate from these specific C edge atoms, as did

ZGNRs.23 However, the partial charge density distributions of the LCB and HVB in ZGNRs is

symmetrically distributed at both upper and lower edges, whereas for nanoribbons ZZ, ZA, and

AA (apart from the HVB of nanoribbon AA), the partial charge density distribution of their

respective LCB and HVB is located at a single edge only. Accordingly, the wave function in

nanoribbons ZZ, ZA, and AA features a higher degree of localization than ZGNRs, making it

more amenable to tuning the electronic property of P-GNRs by an electric field26.

Nanoribbon SS, obtained by cutting along D2, is different, showing semiconductor

behavior with an indirect band gap of approximately 1.45 eV. From Fig. 2 (d), in particular, one

can see that the PDOS for edge C atoms make significantly less contribution to the DOS peak for

the LCB, and the calculated partial charge density distribution confirms that the middle C atoms

are just the contributors. However, the DOS peak related to the HVB originates from the edge C

atoms, and the calculated partial charge density distribution reveals that edge states are located on

both sp2- and sp3-hybridized C atoms. These results indicate that nanoribbon SS does not have

edge states similar to nanoribbons ZZ, ZA, and AA.

Overall, nonmagnetic P-GNRs display rich and unique electronic properties, in which

localized edge states play an essential role. Nanoribbons ZZ, ZA, and AA are metallic; more

importantly, they have an unusual band structure, manifested by a larger band gap between the

energy bands crossing the Fermi level and upper (lower) energy bands, as shown in Figs. 2(a)-(c).

These features hold high promise for developing outstanding negative-differential-resistance

(NDR) devices with a large peak-to-valley ratio. Whereas nanoribbon SS shows semiconducting

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properties with a medium-size band gap, it is very important for developing high-performance

nano-transistors.

Physical Chemistry Chemical Physics Accepted Manuscript

Magnetic properties in the different magnetic states

To fully explore the magnetic structure and magnetic distribution in P-GNRs, six possible
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magnetic configurations (spin alignments) are initially set: (αα, αα), (αα, ββ), (αβ, αβ), (αβ, βα),

(αβ, αα), and (αα, αβ), where α and β denote the different spin orientations. The calculations show

that nanoribbon SS always converges to the spin-unpolarized state regardless of any initial setting

magnetic configurations, suggesting that such a nanoribbon does not have an intrinsic magnetism.

This is because spins are oppositely-orientated in adjacent sp2-hybridized C atoms at the ribbon

edges, so that the magnetic moments cancel out completely. In contrast, nanoribbons ZZ, ZA, and

FIG.3. Schematic of the six different magnetic configurations, based on nanoribbon ZZ. Magenta and cyan
denote the α- and β-spin components, respectively. The values for the α- and β-spin isosurfaces are ±0.005
|e|/Å3. The local magnetic moment is distributed mainly on the specific C atoms denoted C1-C4.

AA maintain magnetic states unambiguously after full convergence, implying that these

states are system solutions of the magnetic structures. As an example, Fig.3 depicts the spin

charge density distribution for nanoribbon ZZ in six magnetic configurations. Their moments are

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highly localized at the edges, and almost entirely concentrated at four specific C atoms labeled

C1-C4 with sp2 hybridization. In addition, nanoribbons ZA and AA also exhibit similar localized

Physical Chemistry Chemical Physics Accepted Manuscript

edge states for spin magnetism (see Fig. S2 in the Supporting Information). Table 1 summarizes

the energies in six different magnetic configurations relative to the ground state (in units of meV
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per super-cell) and electronic features (in parentheses) for nanoribbons. In the case of magnetic

configuration (αα, αα), there is ferromagnetic (FM) coupling individually at each edge and

simultaneously FM coupling to the opposite edge, while for (αα, ββ), there is also FM coupling

individually at each edge but anti-ferromagnetic(AFM) coupling to the opposite edge. However,

both magnetic states have the same energy in each nanoribbon, implying that the magnetic

coupling between the two spin-polarized edges is negligible, similarly to the case of the

single-layer h-BN nanoribbon.30 As we know, for ZGNRs, the spin charge density decreases

gradually from the edge to the center, but the magnetic moments in nanoribbons ZZ, ZA, and AA

Table 1. Energies in different magnetic configurations relative to the ground state (in units of meV per
super-cell)，electronic characteristics (in the parentheses), and the magnetic moment in magnetic configuration
(αα, αα) (in units of µB per super-cell) for three types of nanoribbons. The abbreviations M, S, MS, and BMS
represent metal, semiconductor, magnetic semiconductor, and bipolar magnetic semiconductor, respectively.
NM represents the nonmagnetic state.

Structure NM (αα,αα) (αα,ββ) (αβ,αβ) (αβ,βα) (αβ,αα) (αα,αβ) MM

892.33 88.06 88.06 0 0 37.13 37.13

ZZ 3.99
(M) ( BMS ) (MS) (S) (S) ( BMS ) ( BMS )

1117.96 37.08 37.08 3.65 3.65 0 4.74

ZA 3.992
(M) ( BMS ) (MS) (S) (S) ( BMS ) ( BMS )
1309.88 0 0 7.47 7.47 3.68 3.68
AA 3.976
(M) ( BMS ) (MS) (S) (S) ( BMS ) ( BMS )

are highly localized, almost entirely residing on the specific C atoms as stated above.

Accordingly,the spin-coupling interactions between both edges for P-GNRs are much weaker,
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leading to the same energy for P-GNRs with magnetic configurations (αβ, αβ) and (αβ, βα), as

shown in Table 1. For nanoribbons ZZ and AA, the magnetic configurations (αβ,αα) and (αα,αβ)

Physical Chemistry Chemical Physics Accepted Manuscript

BS DOS&PDOS BS DOS&PDOS
(a) 1.5 (b) 1.5
*

Energy(eV)
Energy(eV)

*
a2 b*2
a1 b*1
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Total Total
0.0 Edge C 0.0 Edge C
α-spin α-spin
a1 β-spin
b1 β-spin
a2 b2

(αα,αα) β-spin α-spin (αα,ββ) β-spin α-spin

-1.5 -1.5
Γ Ζ -20 0 20 Γ Ζ -20 0 20

BS DOS&PDOS (d)1.5 BS DOS&PDOS

(c)1.5
*
c2α d*2α
Energy(eV)
*
Energy(eV)

c1α *
d 1
Total Total
0.0 α-spin Edge C
0.0 Edge C
α-spin
β-spin
c1α d1 β-spin
c2α d2α
(αβ,αβ) β-spin α-spin
(αα,αβ) β-spin α-spin
-1.5 -1.5 Γ
Γ Ζ -20 0 20 Ζ -20 0 20

FIG.4. Magneto-electronics properties of P-GNRs in different magnetic states. (a)-(d) BS and DOS&PDOS of
nanoribbon ZZ in magnetic configurations (αα, αα), (αα, ββ), (αβ, αβ), and (αα, αβ), respectively. (e) Partial
charge density distribution of energy bands near the Fermi level, marked in figures (a)-(d); the isosurface value

is 0.005 e /Å3.

are the same magnetic state owing to geometrical symmetry about the ribbon midline. Intriguingly,

multiple electronic characterizations in different magnetic configurations are observed in P-GNRs,

such as metal (M), semiconductor (S), magnetic semiconductor (MS, spin polarized

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semiconductor), and bipolar magnetic semiconductor (BMS, specific spin polarized

semiconductor). Obviously, P-GNRs promise richer magneto-electronic properties than graphene

nanoribbons. In particular, the BMS cannot occur in intrinsic graphene nanoribbons, but

Physical Chemistry Chemical Physics Accepted Manuscript

nanoribbons ZZ, ZA, and AA can exhibit this property in multiple magnetic states, as can be seen

from Table 1. The so-called BMS materials have a well-defined spin-flip gap created from the
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two spin channels, α and β, thus a two-probe system composed of BMS material cannot realize

spin filtering. Nonetheless, by applying a gate voltage, it is possible to shift the α- or β-spin

channel running into a source-drain bias window, and hence obtain a fully spin-polarized current.

Namely, the direction of spin-polarized currents can be altered by simply switching the sign

(positive to negative) of the gate voltage Vgate, thus forming a bipolar field-effect spin-filtering

device.31,32BMS materials may therefore be very useful for developing next-generation

information storage devices. More intriguingly, BMS features can be achieved in the

ferromagnetic state for all magnetic P-GNRs, which make P-GNRs more valuable. Furthermore,

in Table 1, where MM denotes the magnetic moment of one super-cell in magnetic configuration

(αα,αα) (in units of µB per super-cell), one can see that nanoribbons ZZ, ZA, and AA have almost

identical MM values, ~3.99 µB per super-cell, which almost equals the number of specific C

atoms in one super-cell.

To present the magneto-electronics properties in greater detail, and taking nanoribbon ZZ

as an example, Figs. 4(a)-(d) plot the energy band structure (BS), total density of states, and

projected density of states (PDOS) in various magnetic configurations. Noting that there exist the

same magneto-electronic properties in the magnetic configurations (αβ, αβ) and (αβ, βα) for this

nanoribbon, this is because there exists the negligible magnetic coupling between the two edges,

as mentioned above. All the energy bands are separated and appear above and below the Fermi

level due to spin involved as compared to those in the nonmagnetic state, resulting in a band gap

in each magnetic configuration and giving rise to diverse magnetic properties (BMS, MS, and S).

The energy bands are either spin-degenerate or spin-split, depending on whether there is a FM

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coupling magnetic ordering at the same edge. In other words, the spin-split (spin-degenerate)

energy bands are induced by a FM (AFM) coupling edge. Thus, the energy bands in states (αα, αα)

and (αα, ββ) are spin-split, as shown in Figs. 4 (a)-(b), while the energy band in state (αβ, αβ) is

Physical Chemistry Chemical Physics Accepted Manuscript

entirely spin-degenerate, as displayed in Fig. 4(c), and the co-existence of spin-splitting and

spin-degenerate energy bands arises in (αα, αβ), as exhibited in Fig. 4(d). Meanwhile, the PDOS
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shows that edge C atoms play a crucial role in forming energy bands near the Fermi level. To

demonstrate the contribution from each edge C atom more clearly, we calculated the partial

charge density distribution for energy bands LCB (the lowest conduction band) , LCB+1, HVB

(the highest valence band), and HVB-1, as shown in Fig. 4(e). The corresponding indicators are

marked in Fig.4 (a)-(d). It is noted that only the α-spin band is used to calculate the degenerate

energy bands. The partial charge density of each energy band clearly displays a similar

distribution, i.e., strongly localized on the specific sp2-hybridized C atoms of the upper or lower

edge.

We also computed the BS characteristics and the spatial distribution of magnetic moments

for nanoribbons ZA and AA in the six magnetic configurations (see Fig. S1 in the Supporting

Information). The results are similar to those in nanoribbon ZZ, as presented above. The general

electronic properties of P-GNRs in various magnetic configurations can therefore be summarized

several points: (1)considering spin polarization, irrespective of what the magnetic configurations

are, the energy bands intersecting with the Fermi level in nonmagnetic states split and move

upwards or downwards, thus opening a significant band gap and transforming the metallic

nanoribbon, respectively, into a BMS or MS. (2) For all magnetic configurations and all spin

components (α and β), the edge C atoms contribute predominantly to the states near the Fermi

level, in other words , the energy band near the Fermi level originates from the localized states of

the C atoms on one of the two edges. (3) One ferromagnetic coupling edge always causes the

spin-splitting of energy bands, whereas one anti-ferromagnetic coupling edge produces

spin-degenerate energy bands unambiguously.

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Electric-magnetic coupling effects

Finally, we study electric-magnetic coupling effects by an electric field (Eext) applied to the

Physical Chemistry Chemical Physics Accepted Manuscript

P-GNRs. Nanoribbon ZZ in the magnetic configuration (αα, ββ) is chosen as an example for a

detailed investigation. As mentioned above, this magnetic configuration is not the system ground
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Eext=0.0 0.1 0.3(V/Å)

(b) Upper
Dα(E)

Dβ(E)

Dα(E) Middle

Dβ(E)
Lower
Dα(E) ZZ

Dβ(E) (αα,ββ)

-1.5 0 1.5 -1.5 0 1.5 -1.5 0 1.5

Energy(eV)

0.1 0.2 0.3 0.4 0.5(V/Å)

(c) 1.5Eext=0.0

b*2
Energy(eV)

*
b1

0.0
b1
b2 α-spin
β-spin
ZZ
(αα,ββ)
-1.5
Γ ΖΓ ΖΓ ΖΓ ΖΓ ΖΓ Ζ

FIG.5. Effects of a transverse electric field on nanoribbon ZZ in the magnetic configuration (αα, ββ). (a) An
in-plane transverse electrical field Eext oriented from bottom to top is applied to nanoribbon ZZ. (b)
Spin-resolved PDOS for atoms in three regions changes with the Eext. (c) Spin-resolved band structure changes
with Eext. (d) Partial charge density distribution of bands b1 and b1* change with the Eext. The isosurface value is

0.002 e /Å3.

state, but the magnetic energy, defined as the energy difference per magnetic atom between the

nonmagnetic state and the magnetic state, has a very high value of ~111.5 meV per magnetic

atom. This high magnetic energy suggests that the (αα, ββ) state can exist stably at room

temperature (26 meV).33 On the other hand, according to the Mermin-Wagner theorem, it is

difficult for spontaneous magnetic ordering to be achieved in 1D and 2D spin lattices at finite
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temperatures;34however, the spin correlation length in a nanoscale system can be realized.35

Besides, the magnetic anisotropy, as well as the spin correlation length, could be increased by the

substrate effects.36 In Fig.5(a), an in-plane homogeneous transverse electrical field Eext, oriented

Physical Chemistry Chemical Physics Accepted Manuscript

from bottom to top, is applied to nanoribbon ZZ. The ribbon is divided into three parts across the

width, with the upper and lower regions including the outermost Z-type C chain and H atoms at
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the upper and lower edges, respectively; the remaining C atoms are included in the middle regions.

The atom-PDOSs corresponding to the three region atoms at Eext = 0.0, 0.1, and 0.3 V/ Å are

plotted in Fig.5(b). The PDOS peak positions change distinctively with varying Eext，especially in

the upper and lower regions. The PDOS peak of the α-spin state in the upper region moves toward

higher energies while that in the lower region moves in the opposite direction, as Eext increases.

When Eext reaches 0.3 V/Å, these two PDOS peaks intersect at the Fermi level. However, the

situation with the β-spin state is different. As the PDOS peaks above and below the Fermi level

move only slightly with varying Eext, a large energy gap can be maintained. In other words,

metallic behavior for electrons with one spin state coexists with insulating behavior for electrons

with the other spin state. The so-called half-metallicity of nanoribbon ZZ is realized in this

manner. Half-metals with a wide band gap are a well known essential requirement for developing

high-performance spintronic devices. This is because their sufficiently wide band gap effectively

prevents spin-flip transitions of carriers for thermal excitation and preserves the half-metallic

characteristics at room temperature. Previous work has confirmed that ZGNRs can display

half-metallic properties when Eext is applied,26 and the maximum band gap is 0.3eV.26 In our case,

the gap is 0.88 eV for nanoribbon ZZ, much larger than that for ZGNRs, which can thus prevent

the spin-flipping of carriers at room temperature. This suggests that P-GNRs hold high promise

for designing high-performance spintronic devices.

To demonstrate the electric-field-tunable magneto-electronic properties more intuitively and

more thoroughly, Fig.5(c) shows the evolution of the spin-resolved band structures for

nanoribbon ZZ with Eext ranging from 0.0 to 0.5 V/Å in 0.1 V/Å increments. Clearly, with

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increasing Eext, α-spin bands b1(LCB) and b1*(HVB) all move rapidly toward the Fermi level to

narrow the gap, while the β-spin bands b2 and b2* also shift to the Fermi level, but with a

extremely slow speed. As a result, the nanoribbon displays half-metallic properties, where the β-

Physical Chemistry Chemical Physics Accepted Manuscript

and α-spin states serve, respectively, as the gap-opening and gap-closing states. This situation is

sustained over a broad Eext range. In comparison with ZGNRs,26 a larger band gap for nanoribbon
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ZZ is maintained over a broader Eext range.

To gain insight into the origin of the half-metallicity, the partial charge density

distribution of bands b1 and b1* at three typical field strengths for nanoribbon ZZ is illustrated in

Fig. 5(d). The edge state is clearly localized either at a single edge or at both edges, depending on

Eext. The application of Eext, as shown in Fig. 5(a), produces an electrostatic potential difference

between the two edges. The electrostatic potential at the lower and upper edges are thus
*
respectively lowered and raised. When Eext ≤ 0.3 V/Å, the partial charge density of band b2 is

distributed over the lower edge, and thus the lowering of the electrostatic potential by Eext shifts

band b2* downwards. In contrast, the partial charge density for band b2 is localized at the upper

ZZα-spin
(a) ZZβ-spin
(b) ZZα-spin
2.0 2.0 ZZβ-spin
ZAα-spin ZAα-spin
ZAβ-spin ZAβ-spin
Band gap(eV)

1.5
Band gap(eV)

1.5 AAα-spin AAα-spin

AAβ-spin AAβ-spin
1.0 SS 1.0

0.5 0.5

0.0 (αα,ββ) 0.0 (αα,αα)

0.0 0.2 0.4 0.6 0.8 0.0 0.2 0.4 0.6
Electric field(V/Å) Electric field(V/Å)

FIG.6. Variation of the band gap of various P-GNRs with the electric field strength. (a) In magnetic
configuration (αα, ββ) and (b)in magnetic configuration (αα, αα).

edge, and the corresponding enhanced electrostatic potential shifts this band upwards. These

effects are in good agreement with those seen in Fig. 5(c). When Eext is increased further, for

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example, up to 0.5 V/Å, the partial charge densities for bands b1* and b1 both appear at opposite

edges. This can be understood easily, upon applying a greater Eext, both bands b1* and b1 pass

through the Fermi level, so that the one part of the band is a conduction band and the other part a

Physical Chemistry Chemical Physics Accepted Manuscript

valence band. As mentioned above, the charge in the conduction band is always located at the

lower nanoribbon edge, while the charge in the valence band is always at the upper edge.
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Accordingly, the charge in both bands b1* and b1 are distributed separately at the two edges, so

that, overall, the effect of Eext on bands b1* and b1 is weakened, resulting in a weak dependence of

their energy on Eext.

The dependence of the band gap of four types of nanoribbons on Eext is shown in Fig. 6. In

the magnetic configuration (αα, ββ) , nanoribbons ZA and AA are also transformed like ZZ from

a MS to a half-metal when a crucial field Eext = 0.3 V/Å is reached (see Fig.6(a)). However,

nanoribbon SS is nonmagnetic but its band gap is also very sensitive to an electrical field and

decreases with increasing Eext, finally realizing a semiconductor-metal transition around Eext = 0.3

V/Å. This result can also be attributed to the localized edge state. Furthermore, in other magnetic

configurations, the electronic structure of the nanoribbons also features large variations with Eext,

for example, in the magnetic configuration (αα, αα), as shown in Fig. 6(b). From the changes in

the band gap for different spin orientations, we can conclude that all the energy bands in the

magnetic configuration (αα, αα) shift more quickly toward the Fermi level than those in magnetic

configuration (αα, ββ), and almost all band gaps are closed when Eext reaches ~0.4 V/Å regardless

of their being in the α- or β-spin state, so that the transition from MS to a magnetic metal is

realized. In short, the electronic and magneto-electronic properties of P-GNRs are effectively

modulated by applying a transverse electric field.

The effects of longitudinal compressive and tensile strains on P-GNRs were also

investigated (see Fig. S3 in the Supporting Information). The computed results show that the band

structures and band gaps do not vary significantly with strain, because only a very small variation

occurs along the C-C bond length at the ribbon edges, thereby demonstrating the robustness of the

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P-GNR electronic structure with regard to strain. Finally, we also studied the size effect of

P-GNRs and found that the electronic structures for the same nanoribbon type are essentially

conserved over a wide range of ribbon widths covering 12 to 28 Å. The band gap, as a function of

Physical Chemistry Chemical Physics Accepted Manuscript

the ribbon width, does not change significantly, regardless of P-GNRs in the nonmagnetic or

magnetic state (see Fig. S4 in the Supporting Information).

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Conclusion

To summarize, by cutting penta-graphene sheets along two typical crystallographic

orientations, four different types of P-GNRs can be formed. By passivating their edges with

hydrogen, their magneto-electronic properties can be investigated systematically. It is found that

P-GNRs are very versatile, displaying rich and unique electronic and magnetic characteristics. In

the nonmagnetic state, they can be metallic or semiconducting, a valuable feature for developing

outstanding devices with NDR or high-performance nano-transistors, by exploiting their

particular band structures. Whereas the six possible different magnetic configurations can yield a

semiconductor, magnetic semiconductor, or bipolar magnetic semiconductor, the latter may be

particularly useful for developing the next generation of information storage devices. Bipolar

magnetic semiconducting features can be achieved in the ferromagnetic state for all magnetic

P-GNRs, which make P-GNRs more valuable. More interestingly, a transverse electric field can

make P-GNRs undergo a transformation from magnetic semiconductor to a half-metal with a

wide band gap of 0.88 eV. The advantages over graphene nanoribbons are also to be expected.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos.

61371065, 11674039, and 51302022), the Hunan Provincial Natural Science Foundation of China

(Grant Nos. 12JJ3004, 2015JJ3002, 2015JJ2009, 2015JJ2013), the Scientific Research Fund of

Hunan Provincial Education Department (Grant No. 14A013), and the Hunan Provincial

Innovation Foundation for Postgraduate (Grant No. CX2015B375).

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Supporting Information
Schematic of the six different magnetic configurations and corresponding energy band

structures for nanoribbons ZA and AA; Effects of longitudinal strains on band gaps in various

Physical Chemistry Chemical Physics Accepted Manuscript

P-GNRs; Change of the band gap as a function of the ribbon width.
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