Materials Science and Engineering B 221 (2017) 17–34

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Review

Phosphorene – The two-dimensional black phosphorous: Properties,

synthesis and applications
Apratim Khandelwal, Karthick Mani, Manohar Harsha Karigerasi, Indranil Lahiri ⇑
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India

a r t i c l e i n f o a b s t r a c t

Article history: Black phosphorus (BP) is known to human beings for almost a century. It started receiving more attention
Received 1 December 2016 of scientists and researchers worldwide in last three years, with its ability to exist in two-dimensional
Received in revised form 25 February 2017 (2D) form, popularly known as phosphorene. In the post-graphene-discovery period, phosphorene is
Accepted 11 March 2017
probably receiving most attention, owing to its excellent properties and hence, high potential for practi-
cal applications in the field of electronics, energy and infrastructure. In this article, attractive properties of
phosphorene, which makes it unique and comparable with graphene or transition metal dichalcogenides
Keywords:
(TMDs), are highlighted. As the question of its environmental instability remains critical, a comprehen-
Two-dimensional materials
Black phosphorus
sive overview of synthesis methods of phosphorene and black phosphorus are presented, to inspire in-
Phosphorene situ methods of phosphorene synthesis and fabrication towards improving further investigation into this
Anisotropy wonder material. In addition, the article also focuses on opportunities in nano-electronics, optoelectron-
Exfoliation ics, energy conversion/storage, sensors etc arising from phosphorene’s remarkable properties.
Field effect transistors Ó 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2. Structure and properties of phosphorene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1. Structural characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2. Fundamental properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.1. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.2. Electronic structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.3. Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.4. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.3. Bridging the ‘gap’ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3. Synthesis and preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.1. Bulk black phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.2. Phosphorene/few layer black phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2.1. Top-down scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2.2. Bottom-Up scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1. Phosphorene based devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1.1. Field effect transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1.2. Rechargeable batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.1.3. Optoelectronic devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.1.4. Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.2. Black phosphorus sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2.1. Gas sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2.2. Selective humidity sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

⇑ Corresponding author.
E-mail address: indrafmt@iitr.ac.in (I. Lahiri).

http://dx.doi.org/10.1016/j.mseb.2017.03.011
0921-5107/Ó 2017 Elsevier B.V. All rights reserved.
18 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34

5. Summary and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

1. Introduction acrylic-based adhesive) in 2014 [3]. In similitude with the name

Black phosphorus was first synthesized in 1914 by Bridgeman
through a process involving application of high hydrostatic pres-
sure and temperature (up to 200 °C and 1.2 GPa) to white phospho-
rus [1]. Commercially, black phosphorus is not as popularly used as
its other two most common allotropes – white phosphorus and red
phosphorus. Similar to graphite, BP consists of layers of puckered
structure held together by Van der Waals forces [2]. This was prob-
ably the motivation behind the use of mechanical exfoliation
method for extraction of black phosphorus. Very few layer black
phosphorus was successfully exfoliated from bulk black phospho-
rus using a blue tape (PVC film coated with a pressure sensitive
of ‘graphene’, this isolated single layer of black phosphorus is
called phosphorene.
Until 2013, various 2D materials were known to be fabricated
by mechanical exfoliation method, but graphene was the only
one in its elemental form. The other 2D materials were composed
of more than one element. It might be argued that silicene is also a
stable material at room temperature [4]. However, silicene cannot
be obtained through mechanical exfoliation. So, without any sur-
prise, the discovery of black phosphorus took the scientific com-
munity by storm. Its properties are so unique that it managed to
fill the gap provided by graphene and TMDs. To compare, contrast
and summarize the structure, methods of synthesis and promising

Table 1
A compendium of structure type, year of synthesis, methods of synthesis and promising applications for graphene, other 2D materials and some major TMDs.

2D materials Year Composition and structure Major Methods of preparation Major Applications
of
first
report
Graphene 2004 Carbon; hexagonal honeycomb Exfoliation (Chemical, Liquid & Mechanical) [5], Gas and bio-sensors; Graphene Field
structure Chemical Vapor Deposition (CVD) [5], Substrate- Emission Transparent Electrodes; Electronics,
assisted epitaxial growth [5], Unwrapping CNTs Thermal and Mechanical applications;
[6], Surface Segregation [7], Molecular Beam Epi- Energy storage applications [5]
taxy (MBE) [8]
Hexagonal Boron 2004 Boron Nitride; hexagonal Exfoliation (Chemical [9], mechanical [10] and Nanoelectronics-ultrathin insulating films
Nitride Nano- honeycomb structure liquid [11]), electron beam irradiation and CVD [7], [12], catalysis [8]
Sheets (h-BNNS) Surface Segregation [7]
MoO3 2009 Molybdenum, Oxygen double Modified hot plate method; plasma assisted paste Biosensing, organic light emitting diodes;
layer structure [13] sublimation process; organic solvent assisted hydrogen gas sensing; photoluminescence;
grinding and sonication method [14] field emission [13]
Silicene 2010 Silicon; partially flat hexagonal Substrate (Au/Ag/Al) assisted epitaxial growth FET [19], Topological electronics; Thermo-
honeycomb structure [15] [16], surface segregation on zirconium diboride electric Systems; Nano Electro Mechanical
thin films [17], chemical exfoliation [18] Systems (NEMS) [20]
MoS2 2010 Molybdenum-Sulphur TMD; Exfoliation (chemical, mechanical and liquid); CVD FET; memory device; Photodetector;
hexagonal structure with Mo synthesis via thermal vapor sulfurization (TVS) Photovoltaic device [21]
and S2 atoms located at and thermal vapor deposition (TVD); Vapour-solid
alternating corners growth [21]
WS2 2012 Tungsten, Sulphur TMD; Exfoliation (Chemical and Mechanical) [22], Photo detecting; Chemical sensing [23]
hexagonal structure with W Ambient pressure CVD on gold foils [23]
and S2 atoms located at
alternating corners
WSe2 2012 Tungsten, Selenium TMD; Mechanical exfoliation [24], CVD [25] Photovoltaic; Photoelectrochemical (PEC)
hexagonal structure with W devices [26], FET [27]
and Se2 atoms located at
alternating corners
Germanene 2014 Germanium; nearly flat Epitaxial growth on Au surface [28] Topological electronics, Thermoelectric
honeycomb structure Systems, Nano Electro Mechanical Systems
(NEMS) [20]
MoSe2 2014 Molybdenum, Selenium TMD; CVD via thermal vapor Selenization of MoO3 [29] Optoelectronics; Photo detecting and other
hexagonal structure with Mo nanoelectronic applications [29]
and Se2 atoms located at
alternating corners
Blue Phosphorene 2014 Phosphorus; Out-of-plane Not yet synthesized; Theoretical predictions based Solar cells; Photodetection devices [30]
buckled honeycomb structure on ab initio calculations [30]
with two atom unit cell in zig-
zag orientation [30]
Borophene 2015 Boron; corrugated cardboard Electron beam evaporation (using Ag as substrate) Electronic sensors; semiconductor devices;
structure with out-of-plane [31] tribological applications [31]
buckling [31]
Stanene 2015 Tin; hexagonal honeycomb MBE on Bismuth Telluride substrates [33], Chem- Topological electronics; Thermoelectric
structure [32] ical Exfoliation [34] Systems; Nano Electro Mechanical Systems
(NEMS) [20], Photonics [34]
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
Fig. 1. Publication trend related to black phosphorus and phosphorene for last 15 years (source: scopus.com).
Fig. 2. The crystal structure of black phosphorus [37]. The atoms in different planes
are denoted by black and gray colors and the dotted-box marks the unit cell along
with a1 and a2 marked as in-plane lattice vectors. Black phosphorus has a four-atom
unit cell with an armchair structure along a1 and a zigzag structure along a2. (Ó
Nature Publishing Group, adapted with permission from Ref. [37]).
applications of some of the most important 2D materials from the
perspective of material science research, Table 1 serves as the com-
pendium of the major research done in recent years.
From the table, it is evident that most of the synthesis tech-
niques and applications are derived from graphene and hence the
same applies to phosphorene. It is clear that phosphorene can draw
the required inspiration from the rest of the 2D material family and
may even surpass them. Hence, phosphorene, unlike any other
material shows greater potential in all the aspects.
The on/off ratio, mobility, photo-response, Seebeck coefficient,
electrical resistivity and many other properties of phosphorene
have values in between that of graphene and TMDs, resulting
applications in thermal imaging, thermoelectrics, fiber optics etc.
With this, expectations rise high on phosphorene, leading to a
19
series of questions. Why has it attracted so much attention from
the scientific community in its nascent stage of development (even
more than that of graphene or TMDs)? How useful are its
properties, as compared to graphene or TMDs? What could be
the possible application areas of this new 2D material? Scientists
and researchers worldwide are working on phosphorene to answer
these questions which can be observed in Fig. 1. The number of
publications has increased substantially in the past years, which
indicates the growing interest in the scientific community with
regards to phosphorene, as shown in Fig. 1. Following sections
are focused on summarizing all these research efforts – looking
for a comprehensive solution to all the queries.
2. Structure and properties of phosphorene
Bulk black phosphorus has a higher density of 2.69 g/cm3
when compared to white (1.83 g/cm3) or red phosphorus
(2.05 g/cm3–2.34 g/cm3). It is also more stable as compared to
other two allotropes, as it does not catch fire easily and only
spontaneously ignites after 400 °C [35]. It is a good conductor of
heat and electrons but is less diamagnetic when compared to red
or white phosphorus [35].
2.1. Structural characteristics
Just like graphite, black phosphorus consists of many layers
held together by weak Van der Waals forces. Phosphorene has an
orthorhombic crystal structure, where the phosphorus atom is
directly bonded to three other neighboring atoms via covalent
bonds as shown in Fig. 2 [2]. Unlike graphene, which has a planar
layer structure, the structure of phosphorene is puckered in nature,
having a single layer with honeycomb-like lattice [2]. It is strongly
anisotropic in nature and many of its properties depend on the
number of layers stacked. It has up to 50% higher conductance in
the armchair direction than in the zigzag direction [3]. Its anisotro-
pic conduction behavior can be changed depending on the applica-
tion of strain on the material. The preferred direction for
conductance changes by 90°, on the application of either uniaxial
(less than 6%) or biaxial strain (less than 4%), [36].
20 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
2.2. Fundamental properties
2.2.1. Mechanical properties
Black phosphorus has superior tensile strain in the zigzag (27%)
as well as armchair (30%) direction. It also has superior flexibility,
along with a much smaller Young’s modulus (0.166 TPa in zigzag
and 0.044 TPa in armchair direction) in comparison with graphene
(1 TPa). Phosphorene is more ductile in armchair direction and
exhibits a rather unusual negative value of Poisson’s ratio in an
out-of-plane direction parallel to the pucker [38]. The Poisson’s
ratio also shows an anisotropic behavior in phosphorene [39].
MoS2 and graphene also display good flexibility and survive tensile
strains greater than 25% but Young’s modulus of phosphorene is
much less than that of graphene and MoS2 because of two reasons:
(1) comparatively weak P-P bond strength, and (2) the stretching of
bond angles as compared to linear bond (P-P bond) stretch on
application of tensile stress i.e. the tensile strain stretches the
pucker of phosphorene thereby reducing the required strain
energy. Similar to the anisotropy in electrical properties, its
Young’s modulus is also anisotropic in nature. Simulation studies
on monolayer phosphorene subjected uniaxial strain have pre-
dicted that Young’s modulus of phosphorene is strongly dependent
on the angle being considered – with the value in the armchair
(166 GPa) direction being up to 4 times higher than in the zigzag
direction (44 GPa). This anisotropy within the plane can lead to
novel functionalities [40]. Although Young’s modulus of phospho-
rene is smaller than that of graphene and MoS2, it is still larger than
those of many regular materials. This anisotropy in mechanical
properties of phosphorene can be attributed to the puckered struc-
ture of phosphorene which gets folded/unfolded under the cycles
of compression/tension along the armchair direction [41]. Young’s
modulus of phosphorene can be modified by functionalization.
Processes like sodiation result in increased or decreased values of
Young’s modulus according to the number of adsorbed sodium
atoms on phosphorene. However, the anisotropy is still extant
and could not be eliminated [42].
2.2.2. Electronic structure and properties
2.2.2.1. Band gap. Graphene is a zero band gap semiconductor
whereas phosphorene is a direct band gap semiconductor, which
is also tunable according to the applied strain. Its properties
change with the application of stress, with the number of stacked
layers present and also with the application of electric field [3,43].
Earlier findings reported that the band gap value varies from
0.3 eV in bulk black phosphorus to about 2 eV in the single layer
phosphorene [2]. Liu et al. initially measured the experimental
band gap value of phosphorene [44]. The PL studies performed in
the visible region proved that the band gap in phosphorene
(1.45 eV) was significantly larger than in bulk BP (0.3 eV). But both
Fig. 3. (a) Layer dependence of normalized PL peak intensity vs. layer number. (b) Decreasing energy gaps of 2 L, 3 L, 4 L, and 5 L phosphorene obtained from experimental PL
spectra and theoretical simulation. (Fig 3a and b, data re-drawn and reproduced with permission from Ref. [61]. Copyright Ó 2014 American Chemical Society). (c) Band
structures of monolayer (left) and five–layer (right) phosphorene. (Ó Nature Publishing Group. Adapted with permission from ref [60]).
BP and few layer black phosphorus (exfoliated from bulk BP) con-
tinue to behave as direct band gap semiconductors [45]. Recent
findings by Liang et al. reported an even more accurate value of
band gap in phosphorene (2.05 eV) [46]. The band gap of 2D black
phosphorus undergoes direct-indirect-direct transition on the
application of axial strain. Only 2% compression is enough for
direct to indirect transition to take place in the zigzag direction
[47]. With the application of sufficient expansion (11.3%) or com-
pression (10.2%) strains, the band gap can be tuned from indirect
to direct again [39]. Similar results were presented by Liu et al.
where a compressive strain of 5% triggered the transition from
direct to indirect band gap [44]. Phosphorene can also undergo
semiconductor to metal transition when moderately deformed.
On the application of compression along only one direction, it is
possible to have almost direct band gap to indirect band gap semi-
conductor, semimetal and even metal [32]. Theoretical studies per-
formed by Ospina et al. proposed an equally stable monolayer
black phosphorus called Blue Phosphorene (b-phosphorus) [30].
Displacement of few atoms in monolayer phosphorene results in
a honeycomb structure composed of two sublattices but with
out-of-plane buckling of the atoms arranged in a zigzag manner.
This new arrangement is termed as blue phosphorene and is pre-
dicted to behave as an indirect semiconductor with a band gap of
2 eV. Based on similar ab initio density functional calculations
several other phosphorene polymorphs were also predicted. These
allotropes (b-phosphorus [30,48,49], c-phosphorus [50,51], and d-
phosphorus [52,37]) are predicted to be nearly as stable as BP, but
exhibit unique electronic properties. In order to determine the
energetic stability of the allotropes, Liu et al. [53] have shown that
total energy change involved in the formation of two-dimensional
(b, c and d)-phosphorus with respect to a-phosphorus (most stable
allotrope; taken as 0 eV/atom) is in the increasing order of magni-
tude (0.01 eV/atom, 0.08 eV/atom, and 0.09 eV/atom). This implies
a decreasing trend in relative thermodynamic stabilities from a-
phosphorus to d-phosphorus. The possibility of combining these
different polymorphs of phosphorene into a monolayer hetero-
structure paves the way for dual nature conduction (metallic and
semiconducting) within a single layer of material [50]. It is often
required for electronic materials to undergo band gap tuning in
order to modify or optimize several electrical properties. Strain
engineering is an effective way to tune band gap due to several rea-
sons. Unlike chemical functionalization, doping, etc it involves lit-
tle or no damage/impurity in doing so. Moreover, in contrast to
‘external electric field effect’ which seems to work only for layered
materials, strain engineering is effective even for monolayer sub-
stances as strain can be readily induced by lattice mismatch from
the underlying substrates. Hence with atomic-level engineering,
few layer black phosphorus and phosphorene could prove to be
excellent candidates for various optoelectronic applications.
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
Fig. 4. (a, b) Optical absorption spectra of few-layer phosphorene for light polarized along the armchair direction (a) and zigzag direction (b). Black dashed lines represent an
approximate linear fit to estimate the band edges for the (highly anisotropic) first absorption peaks. (Ó Nature Publishing Group. Adapted with permission from ref [45]). (c)
Photoluminescence spectra for 2–5 layer phosphorene. (Reprinted with permission from Ref. [61]. Copyright Ó 2014 American Chemical Society).
Similar to other 2D materials like graphene [54], TMDs [55] and
hexagonal boron nitride [56], the band gap of monolayer BP
remains unaltered by external electric field but undergoes a signif-
icant change in case of few layer black phosphorus. When an elec-
tric field is applied perpendicular to the plane of few layer black
phosphorus, the band gap effectively reduces from 0.78 eV (at zero
field) to 0.56 eV (up to an electric field of 0.5 V/Å) [57]. Recently,
Liu et al. [58] showed that under the influence of an external field,
few layer black phosphorus can be converted into a topological
insulator and eventually into a metal. With this finding, they
opened up a possibility of converting any normal insulating mate-
rial into topological insulators [58]. This effect due to the external
electric field can serve as a basic principle towards the develop-
ment of novel multifunctional ‘field effect topological transistors’
that could simultaneously manipulate both spin and charge
carriers.
Phosphorene exhibits a strong dependence of band gap on the
number of layers too. As the number of layers is increased, the
band gap decreases (Fig. 3a,b) but remains direct (Fig. 3c) whereas,
in the case of MoS2, one can only see a sharp transition from indi-
rect band gap in bulk to direct band gap in monolayer MoS2 [59]. It
can be seen that with increasing number of layers, the band gap of
few layer black phosphorus reduces gradually from 1.5 eV to
finally saturate at a band gap value of BP (0.3 eV). There is a sharp
decrease in band value from monolayer to tri-layer BP [60]. This
sharp fall in band gap value can be attributed to the quantum con-
finement effect [45].
The band gap of phosphorene encompasses a broad range of
electromagnetic spectrum, more than any other 2D material.
Hence, it carries high interest in the applications of thermoelectric,
fiber optics, thermal imaging, photovoltaics etc. Graphene covers
applications requiring band gap in the range of 0.0–0.2 eV and
TMDs can cover applications requiring the range of 1.0–2.0 eV.
Phosphorene (0.3–2.0 eV) actually bridges the gap between gra-
phene and TMDs. Photocatalysis and photovoltaic energy harvest-
ing applications can be covered with graphene and MoS2 as well,
but thermal imaging, thermoelectric and fiber optics applications
are out of reach for other 2D materials. These applications have
been using three-dimensional materials until recently, but now
phosphorene provides an opportunity to use a 2D structure for
such applications [3].
2.2.2.2. Electronic transport. Phosphorene also has a large on/off
ratio of up to 104 at room temperatures and high mobility of
around 1000 cm2/Vs (along armchair direction), which is very use-
ful for channel materials in transistors [2,40]. Semiconducting 2D
MoS2 lacks mobility whereas metallic graphene lacks a sizeable
21
bandgap but has a very high electron mobility. Phosphorene, on
the other hand, closes the gap in the properties provided by gra-
phene (high mobility, but poor on/off ratio) and MoS2 (low mobil-
ity, but high on/off ratio). Degraded phosphorene, however,
exhibits a decrease in mobility values [62]. Besides instability of
phosphorene in air [2], phosphorene also has a large density of
charge traps that actually limit its mobility [63]. However,
researchers have found ways to prevent degradation via encapsu-
lation techniques. Hetero-structures formed by sandwiching phos-
phorene between layers of hexagonal boron nitride proved to be
stable in ambient conditions and displayed increased mobility val-
ues [64,65]. Upon encapsulation, Wei et al. reported a higher on/off
ratio (105) along with increased mobility value of 1350 cm2/Vs at
room temperatures and 2700 cm2/Vs at lower temperatures [64].
Gillgren et al. reported an even higher value of mobility
(4000 cm2/Vs) on encapsulation of phosphorene with hexagonal
boron nitride [65]. Phosphorene has displayed high anisotropy in
mobility, too. Mobility can go up to 50% higher in the armchair
direction than in the zigzag direction [63]. This anisotropy in
mobility is mostly linked to the puckered structure of phosphorene
[63]. At room temperature, phosphorene displays a hole mobility
of 600 cm2/Vs along the armchair direction and 400 cm2/Vs
along the zigzag direction. Although phosphorene shows higher
mobility values at lower temperatures, the ambient temperature
mobility is still higher than 2D MoS2 (200 cm2/Vs [66]) but is sig-
nificantly lower than graphene (20000 cm2/Vs [66]) and bulk
black phosphorus (60000 cm2/Vs [65,67]).
Besides high mobility values, phosphorene has an ambipolar
field effect, i.e. both n-type and p-type transistor operations can
be realized within a single layer [68]. This, in fact, is a unique prop-
erty considering the fact that most of the 2D semiconductors,
known till now, are n-type semiconductors. When few layer black
phosphorus is exposed to air, a shift of threshold voltage to nega-
tive gate values is observed. The drain current also decreases. Long
term exposure leads to p-type doping, due to adsorbed water
molecules [2]. Few layer black phosphorus can be considered as
a promising candidate for tunable photo-detection due to the wide
range of tunable band gap (0.3 eV to 2.0 eV). The fast and broad-
band photo-detection coupled with ambipolar conduction makes
few layer black phosphorus a promising 2D material for photo-
detection across the visible and near-infrared part of the electro-
magnetic spectrum.
2.2.3. Optical properties
The optical spectra and electron interaction are also dependent
on the number of stacked layers [43,69]. Since strain has a signifi-
cant effect on the band gap of phosphorene, it also affects the opti-
22 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
Fig. 5. Relationship of different semiconductors with (a) mobility and current on/off ratio, (b) responsivity and response time, (c) Seebeck coefficient and resistivity. The
numbers beside their specific pointers correspond to the references provided in the Ref [3]. (Reprinted with permission from Ref. [3]. Copyright Ó 2015 American Chemical
Society).
cal properties of phosphorene [70]. Phosphorene has an anisotropic
optical response where it absorbs polarized light in the armchair
direction but is transparent to polarized light along the zigzag
direction [45,69]. Since it can absorb infrared light and a fraction
of visible light, it can be used as an optical linear polarizer [69].
Graphene has a weak photo-response, but the response time is
less; whereas MoS2 has a strong photo-response but the response
time is more. Phosphorene shows a good balance between
photo-response and the time to respond thereby bridging the gap
between graphene and MoS2 [3].
Both Qiao et al. [45] and Tran et al. [69] found the optical
absorption spectra of phosphorene to be highly anisotropic in nat-
ure (Fig. 4a,b). A substantial difference in the absorption of light
polarized in the armchair and zigzag directions was reported. It
was proposed that this phenomenon can be used to identify the
orientation of few layer phosphorene experimentally [69]. Earlier
studies on optical anisotropy of few layer phosphorene were
mostly limited in the near-infrared (NIR) region [69,71]. Later, for
the first time, Mao et al. [72] reported significant optical anisotropy
of BP (5 nm thick) in the visible region using polarized optical
microscopy and spectroscopy technique. Lan et al. [73] reported
an even more advanced experimental investigation on optical ani-
sotropy of BP (45 nm to 70 nm thick) by unifying the conventional
spectral measurement technique and a uniquely developed inter-
ferometric spectroscopy/imaging technique. This unique modifica-
tion could serve the dual purpose of surface characterization (by
observing the contrast in background and substrate) as well as in
identifying the crystallographic orientation of the layered BP
crystal.
PL measurements done on phosphorene further confirm the
theoretical predictions made by Qiao et al. [45] and Tran et al.
Table 2
A compendium of electronic and mechanical properties of phosphorene, graphene and MoS2.
Material Phosphorene
Type Semiconductor
Conduction type Ambipolar
Band gap (eV) 0.3–2.0
Carrier mobility (cm2/Vs) 1000
On/off Ratio 103–105
Thermal conductance 10–36
(W m 1 K 1)
Thermoelectric figure of merit, ZT 1–2.5
Strain to failure (%) 24–32
Young’s modulus (GPa) 35–166
References* [63], [63], [63], [63]& [44], [37], [80], [40]& [84], [40]
*
The references mentioned, belong to the sections of their respective column in the order so referenced.
[69] on its layer-dependent direct band gap nature. Phosphorene
demonstrates a strong and highly layer dependent photolumines-
cence (PL) [61]. Zhang et al. [61] observed a strong PL in few layer
black phosphorus arising from the direct electronic transitions
with high radiative recombination rate. It can be observed from
Fig. 4c that the PL intensity in bilayer phosphorene is almost an
order of magnitude higher than the PL intensity in five layer phos-
phorene. The PL intensity increases with a decreasing layer thick-
ness despite the lesser volume of thinner layer phosphorene. The
measured PL peaks can be attributed to the nature of excitons rep-
resenting the lower values of the fundamental band gap of phos-
phorene. This indicates that further studies on charge transfer
phenomenon related to phosphorene’s interface with other mate-
rials could open up new possibilities in the field of PL engineering.
A recent attempt by Gan et al. [74] presents one such demonstra-
tion of tunable PL in electrochemically synthesized BP oxide. The
PL was induced due to the localized oxygen-related electronic
states between 620 and 670 nm. A similar but more sophisticated
approach involving vertical integration of BP in 1D photonic crystal
and microcavities by Kriegel et al. [75] proposes an application in
light enhancement/management and sensing. The expected forma-
tion of a photonic band gap in the photonic crystals and a cavity
mode in the microcavity provides similar prospects on manipulat-
ing light.
2.2.4. Thermal properties
Thermal transport in phosphorene is majorly covered by pho-
nons due to the relatively lower electrical conductivity of electrons
[76]. Similar to electrical properties, thermal properties of phos-
phorene are also highly anisotropic. These anisotropic thermal
properties depend upon size, strain and temperature. Zhu et al.
Graphene MoS2
Semimetal Semiconductor
Ambipolar n-type
0 1.2–1.8
200,000 200
5.5–44 106 –108
2000–5000 34.5–52
0 0.4
19.4–38 19.5–36
1000 270 ± 100
[85], [86], [66], [87], [90], [90], [90], [90],
[88], [88], [89]& [84], [89] [84], [91], [92], [93]
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
[77] investigated the size effect on thermal conductivity (G) of
phosphorene. They observed that thermal conductivity was size-
dependent along the zigzag direction (increased with the length
of the sample) whereas along the armchair direction the thermal
conductivity was size-independent. However, on the application
of tensile strain, the thermal conductivity can be reduced by a sig-
nificant factor in both the directions [78]. For example, when a uni-
axial tensile strain (6%) is introduced along the armchair
direction, the thermal conductivity of phosphorene decreases by
a factor of 4.7 along the armchair direction; and by a factor of
2.2 along the zigzag direction [37]. Since the thermal conductiv-
ity of phosphorene is governed by phonons it depends upon tem-
perature as well. The thermal conductivity is inversely
proportional to the temperature according to the power law [79].
Yang et al. [80] investigated the orthogonal relationship between
the prominent electrical and thermal conducting directions in
phosphorene which was responsible for enhancement in electrical
and thermal conductance ratio in phosphorene. Phosphorene thus
possesses a higher thermoelectric figure of merit (ZT) in armchair
direction. Unique device configurations have been proposed to
improve thermal transport management by taking advantage of
this orthogonally anisotropic behavior where the zigzag direction
has highest thermal conductivity and the armchair direction exhi-
bits the highest electrical conductivity [81]. The thermal conduc-
tivity (G) of phosphorene is comparable to MoS2 (G
1.28 nWK 1nm 2) [82] but is lower than that of graphene (G
4.1 nWK 1nm 2) [83]. The relatively lower thermal conductivity
can again be attributed to the puckered structure of phosphorene
[81]. Although the thermal conductivity of phosphorene is lower
than graphene but it has a high ZT value. Besides higher thermo-
electric figure of merit (ZT), a good thermoelectric material is also
characterized by a large Seebeck coefficient, low thermal conduc-
tivity and small electrical resistivity. Graphene has a small Seebeck
coefficient value and also low electrical resistivity, whereas MoS2
has a very good Seebeck coefficient value and high electrical resis-
tivity. Bulk black phosphorus, on the other hand, has an intermedi-
ate value of Seebeck coefficient. By using electrostatic field effect,
the electrical resistivity of black phosphorus can be reduced sub-
stantially, hence making it useful for thermoelectric applications
[3]. However, the thermoelectric behavior of phosphorene is yet
to be confirmed experimentally.
Fig. 6. BP grown on top of the bulk material consisting of either Au3SnP7 and Sn4P3
(873 K) or Au3SnP7 and AuSn (923 K), can be separated mechanically [104]. (a)
Condensed iodide (separated from bottom BP) on the top section of silica ampule.
(b) and (c) Corresponding magnified images of the well separated bulk BP.
(Reprinted with permission from Ref. [104]. Copyright Ó 2007 American Chemical
Society).
23
Fig. 7. A representative batch of black phosphorus grown on top of Au3SnP7/AuSn
bulk. The mineralization agent SnI4 (orange dots) is well separated from the bulk
materials and BP [104]. (Reprinted with permission from Ref. [104]. Copyright Ó
2007 American Chemical Society).
2.3. Bridging the ‘gap’
Phosphorene in every way bridges the gap between the proper-
ties of graphene and MoS2 (Fig. 5). To explicate the potential of
phosphorene based devices/materials over graphene and MoS2,
the electrical and mechanical properties of phosphorene, graphene
and MoS2 have been summarized in Table 2.
Even with these exceptional set of properties, one of the major
problems of using phosphorene in various device applications is
that it undergoes degradation under ambient conditions. When it
is exposed to ambient conditions for a long time, it undergoes
layer-by-layer etching and is eventually reduced to just a single
layer. The layers of the black phosphorus are held together by weak
Van der Waals forces, which are actually weak Keesom forces
(force between two permanent dipoles) that act in the out-of-
plane direction and it is because of these forces that phosphorene
becomes hydrophilic [2]. The dipole moment of phosphorene
reacts with the dipole moment of water. This interaction causes
severe degradation in the structure, as it shrinks by 25%. In short,
black phosphorus undergoes photo-induced oxidation reaction
when it comes in contact with water in the presence of light. How-
ever, hydrophilicity of phosphorene may also be harvested for pos-
sible catalysis applications involving self-assembly methods and as
a water-splitting photocatalyst by hybridizing it with other poten-
tial organocatalysts/organic dyes via electrochemical modes to
produce synergistic effects [2]. For every fundamental property of
phosphorene, there exists a novel application. Even though there
are several possible applications of this wonder material, simple,
low-cost and stable synthesis of this material seems to be a chal-
lenge for now. In the later sections, several current and prospective
experimental methods for the synthesis of phosphorene have been
discussed.
3. Synthesis and preparation
3.1. Bulk black phosphorus
The motivation behind the discovery of black phosphorus (BP)
was probably the need to find a more stable form of phosphorus.
Besides BP, phosphorous has two main allotropes, white and red
phosphorous, both of which are not as stable and promising as
BP. White phosphorus is known to be poisonous, highly reactive
(ignition temperature 30 °C) and is very soft due to weak Van der
Waals forces. Although red phosphorous is less reactive than white
24 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
phosphorous, it still has a very low ignition temperature of 240 °C
which increases the risk factor during high temperature based syn-
thesis techniques, like CVD [94].
Black phosphorus, on the other hand, has shown that it is chem-
ically stable to work with and sublimes, in vacuum, at a higher
temperature of 400 °C [95]. BP, as originally reported by Bridge-
man, proves its stability in both air and vacuum up to 400 °C [1].
Although BP is chemically inert when present in bulk crystal form,
its exfoliated form gets easily oxidized when exposed to air and
water [96]. Recently researchers were successful in synthesizing
electronic grade phosphorene from BP crystal via liquid phase
exfoliation method; the sheets were stable until water was inten-
tionally introduced [97]. With the use of advanced computational
studies on new prospective solvents and their mechanism of exfo-
liation, now it is just a matter of time before chemically stable
exfoliated BP (2D BP or phosphorene) could be synthesized with
much more reliability and ease.
Synthesis of BP is an ongoing episode since 1914 when the first
chemically stable BP crystals were synthesized by Bridgeman. In
1914, Bridgeman modified the white phosphorus by playing with
the pressure and temperature applied to the white phosphorus
[1]. A high pressure, up to 0.6 GPa was applied at room tempera-
ture. White phosphorus was placed in a high-pressure cylinder
under kerosene. The cylinder was then elevated to 200 °C and pres-
sure up to 1.2 GPa was applied. It took 5–30 min for the transition
from white phosphorus to black phosphorus to occur under this
circumstance. A small volume of black phosphorus was found after
cooling the cylinder and relieving the pressure [1]. Keyes tried to
reproduce the same result in 1950s but used a higher pressure of
1.3 GPa. The obtained BP was polycrystalline as compared to
Bridgeman’s which was amorphous [1,98]. It was observed in
Fig. 8. (a) Cleaving the bulk graphite using a scotch tape [111]. (ÓNature Publishing
Group. Reused with permission from Ref. [111]) (b) An image demonstrating visual
analogy in exfoliating the layers of puckered-layered BP to get few layer BP i.e.
phosphorene [112]. (Reprinted with permission from ref. [112]. Copyright Ó 2015
American Chemical Society).
1930s that the Bridgeman’s BP transforms from amorphous to
crystalline structure depending on the applied pressure and tem-
perature [99].
After this successful attempt by Bridgeman, BP was later on
synthesized by using mercury or bismuth flux method. Krebs and
Weitz obtained similar results via mercury catalysis [100]. An
advanced attempt on synthesizing 2D black phosphorus was made
by Kobayashi and group in 1981 when they had successfully pre-
pared BP single crystals and later on tried to intercalate the BP
crystals by using AsF5 vapor. Although not being able to demon-
strate the successful intercalation of the AsF5 within the layers of
BP, they were able to increase the conductivity of the crystals by
several folds [101]. They prepared BP single crystals (typically of
size 5  0.1  0.07 mm3) from a solution of white phosphorus in
liquid bismuth. These BP crystals showed metallic luster along
with a flexible and cleaving character. But this use of bismuth to
synthesize BP crystals was not the original attempt as Brown and
Rundqvist had already prepared the BP crystals using bismuth
solution so as to analyze the crystal structure of BP in 1950s [102].
Another high pressure-temperature method to synthesize BP
was reported in 1981 using red phosphorous as the base material.
Red phosphorus was melted under high temperature and pressure
using a wedge type cubic high-pressure apparatus. Large crystals of
BP were grown with pressure under 3.8 GPa and temperature
higher than 270 °C [103].
Till now, the high pressure requirement for the bulk synthesis
of BP was a major drawback but recently, BP was reported to be
obtained at lower pressures from red phosphorous; Lange et al.
[104] reported a unique low-pressure route to produce high-
quality black phosphorus by using a mineralizer as reaction pro-
moter under non-toxic conditions (Fig. 6 and Fig. 7). Black phos-
phorus was prepared using Au, Sn, SnI4 and red phosphorous.
Black phosphorus was prepared by the reaction of gold
(70.5 mg, 0.358 mmole, 99.9%, foil), tin (42.5 mg, 0.358 mmole,
99.999%, ingots), red phosphorus (155.2 mg, 5.011 mmole, 99.999
+%, pieces), and SnI4 (10.0 mg, 0.016 mmole, recrystallized) in
evacuated (p = 10–3 mbar) silica ampules. The starting materials
were heated to 823 K, 873 K or 923 K and were gradually cooled
to room temperature. The reaction, however, being stable but takes
several hours to complete (5–10 days) [104].
This process was later on simplified by Kopf using Sn/SnI4 as the
only mineralization additive [105]. The same results were repro-
duced in 2008 by Nilges and group so as to prepare and use BP
as lithium battery electrodes [106]. X-ray phase analyses, energy-
dispersive X-ray spectroscopy (EDX), inductively coupled plasma
mass spectrometry (ICP-MS) and optical microscopy were applied
to characterize the resulting black phosphorus. The probable moti-
vation to use Sn and SnI4 as mineralization products was due to the
fact that alkali metals are very reactive towards BP and hence a
proper layered structure was difficult to obtain but Sn/SnI4 proved
to be a quite stable intercalation compound [107].
Although bulk black phosphorus is not an appealing material as
compared to phosphorene, but it is equally important to under-
stand the synthesis routes of bulk black phosphorus so as to inspire
in-situ modes of phosphorene synthesis. Large-scale fabrication
assemblies for phosphorene device fabrication would only come
into existence if the environmental instability issue of phospho-
rene is taken care of. In-situ modes of production will ensure that
the synthesized phosphorene or few layer black phosphorus from
bulk black phosphorus does not undergo degradation (by avoiding
environmental exposure) before, after and most importantly dur-
ing fabrication, thereby delivering the performance as promised
by this remarkable material.
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34 25

Fig. 9. (a) Optical image of multilayer pristine phosphorene; (b) The same as in after Ar + thinning, where nL stands for number of layers (n = integer). (Scale bars in (a) and
(b) are 5 mm). (ÓSpringer. adapted with permission from Ref. [114]).

Fig. 10. Basic characterization from the bulk BP to the exfoliated BP by LPE technique in CHP (a) Structure of BP representing layered analogy (b) Scanning electron
microscopy (SEM) image of a layered BP crystal (scale bar, 100 mm); (c) Photograph of a dispersion of exfoliated few layer black phosphorus in CHP; (d-f) Representative low
resolution transmission electron microscopy (TEM) images of exfoliated FL-BP in CHP (scale bars in d–f: 500 nm, 100 nm and 500 nm) (g) Bright-field scanning transmission
TEM (STEM) image and (h) Butterworth-filtered high-angle annular dark field (HAADF) STEM image of few layer black phosphorus (exfoliated in isopropanol) showing the
intact lattice (scale bars in g and h, 2 and 1 nm) [120]. ((a–h), ÓNature Publishing Group. Reprinted with permission from Ref. [120]).

3.2. Phosphorene/few layer black phosphorus
In appearance, properties and structure BP is very much like
graphite i.e. black, flaky, layered and has a high electrical conduc-
tivity, with a puckered sheets of linked atoms [37]. Not only the
appearance but also the routes to synthesize few layer black phos-
phorus from bulk BP are very much similar to obtaining few layer
graphene from graphite. Just like graphene, few layer black phos-
phorus electronic devices can also be fabricated by top-down and
bottom-up approaches. The top-down approach is well-suited for
placement of large arrays of devices on a chip using standard pat-
terning tools. However, in the case of graphene, the top-down
approach severely compromises the edges of the graphene since
present fabrication tools offer a much coarser resolution, relative
to the 0.1 nm of a C–C bond. The bottom-up approach afforded
exquisite control of the graphene edges; however, placing the
structures in the locations of interest is often impossible and hence
the same behavior is expected for few layer black phosphorus too
[108].
3.2.1. Top-down scenario
3.2.1.1. Mechanical exfoliation. Mechanical exfoliation of graphite
to obtain few layer graphene was successfully performed first in
2004. This was possible because the layers in the graphite are
weakly bonded to each other by Van der Waals bonds. Since layers
of BP are also bonded by weak Van der Waals forces, mechanical
exfoliation method could be reproduced on BP to get phosphorene.
However, BP is much harder to exfoliate due to a relatively stron-
ger interlayer interaction as compared to other 2D materials [69].
Mechanical cleavage produces single-crystal flakes of high purity
that are suitable for fundamental characterization and for fabrica-
tion of individual devices [63]. However, this method is not scal-
able and hence, is limited to use in the laboratory. This method
also lacks in systematic control of flake thickness and size [44].
The method has been modified to increase the yield of the phos-
phorene obtained but still is not scalable to industrial level [109].
Conventional mechanical exfoliation is performed by repetitive
cleaving of the bulk crystal using an adhesive tape (Fig. 8a). The
resultant monolayer is then manually transferred to the required
substrate by placing and pressing the tape onto the substrate.
However, during the peel off it leaves redundant traces of the
adhesive on the substrate surface. Hence to avoid that, an interme-
diate viscoelastic substrate based on poly dimethyl siloxane
(PDMS) can be used to transfer the monolayers from the blue tape
(more elastic and less adhesive than the scotch tape) onto the
required substrate [109]. Blue tape has already been used for effi-
cient cleaving of other bulk layered materials like graphite, MoS2
and hexagonal boron nitride [110].
3.2.1.2. Plasma assisted mechanical exfoliation. Isolation of single
layer BP has already been demonstrated by plasma assisted
mechanical cleavage process which was also used for graphene
and MoS2 [112–114]. Lu and group were successful in fabricating
monolayer phosphorene by mechanical cleavage (on SiO2/Si
26 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
Fig. 11. Edge selective degradation model for BP exposed to pure neutral water. Top
and bottom panel represent reagent (BP edge + three water molecules) and reaction
products (BP defective edge + phosphine + phosphorous acid), with the reaction
energy also given. BP2Vac refers to defective black phosphorus containing two P
vacancies in the BP supercell. Green, red and white spheres represent P, O and H
atoms, respectively [120]. (Fig 11, Ó Nature Publishing Group. Reprinted with
permission from Ref. [120]).
substrates) and by a subsequent Ar+ plasma thinning process
(Fig. 9a and b).
The thickness of phosphorene was unambiguously determined
by optical contrast spectra combined with atomic force microscopy
(AFM). Raman spectroscopy (532 nm) was used to characterize the
pristine and plasma-treated samples. A focused Ar+ plasma (com-
mercial 13.56 MHz RF source with a power of 30 W and a pressure
of 30 Pa) was used to thin few layer phosphorene down to mono-
layer thickness by thermal ablation with a micrometer-scale reso-
lution [114]. This method provides extra control over the thickness
of the phosphorene paving the way for precise device fabrication.
A similar recent work by Gai et al. used oxygen plasma etching
accompanied with immediate alumina passivation [115]. High
quality stable monolayer and few layer black phosphorus was
obtained for convenient device fabrication. A thick BP flake was
first mechanically exfoliated onto a SiO2/Si substrate and then
the sample was treated with oxygen plasma etching. A constant
etching rate was used to control the exfoliation for precise fabrica-
tion. A dynamic equilibrium between the formation and removal of
a protective oxide layer (PxOy) serves to prevent degradation and
provides increased control over the number of layers. Atomic Layer
Deposition (ALD) is then used to passivate phosphorene by alu-
mina to prevent further degradation. The protective PxOy layer also
prevents redundant reaction of phosphorene with precursor gasses
used in the ALD process. This process of oxygen plasma thinning
opens new opportunities for the synthesis of high quality, stable
phosphorene samples for further research and device applications.
3.2.1.3. Liquid phase exfoliation (LPE). Another method to get bulk
phosphorene is the liquid phase exfoliation which involves the
use of large BP crystals and generally a polar aprotic solvent to
provide ions for intercalation [116]. LPE, in fact, gives results of
comparable quality, the exfoliated layers were reported to be
exhibiting characteristics matching the mechanically exfoliated
ones [117]. The idea is to use the ions of the solution to interca-
late/exchange ions between the layers of the bulk BP and hence
exfoliate the sheets apart to form few layer black phosphorus in
large quantities. Besides direct intercalation/exchange of ions,
few other exfoliation mechanisms based on oxidation and surface
passivation also exist [118]. A large chunk of black phosphorus
crystal (few milligrams) is immersed into a solvent (such as alco-
hols, chloro-organic solvents, ketones, cyclic or aliphatic pyrroli-
dones, N-alkyl-substituted amides, and organosulfur
compounds) to allow the ionic species to intercalate. Although
LPE of BP is generally carried out in amide solvents like N-
cyclohexyl-2-pyrrolidone (CHP) (Fig. 10) or N-methyl-2-
pyrrolidone (NMP) [119] but in some instances, isopropanol
(IPA) also gave stable BP sheets [120]. The mixture is sonicated
to break down the interlayer Van der Waals bonding and acceler-
ate the process. Upon completion of the exfoliation process, the
dispersion is centrifuged for some time at a rate of 1000–
1500 rpm. Sonication time is a critical parameter deciding the
quality of phosphorene sheets as prolonged sonication can intro-
duce many structural defects and can also reduce the flake size of
the phosphorene [120].
Yasaei et al. [121] found that aprotic and polar solvents such
as dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO)
are also appropriate solvents for the synthesis of atomically thin
phosphorene nano-flakes and can produce uniform and stable
dispersions after sonication. After the centrifugation, the super-
natants are carefully collected by a pipet and the residue is col-
lected for further examination and characterization [121].
Graphene, TMDs, hexagonal boron nitride and bismuth telluride
produced by this method have already shown good performance
in electronics [11]. Thus, it is expected that solution-based phos-
phorene production will also provide good prospects for making
flexible electronics. LPE is able to produce large quantity (order
of grams) and high quality monolayer and few layer black phos-
phorus but the reactivity of phosphorene towards water and oxy-
gen is yet to be explained, which results in failure of the above
method [116]. As soon as the phosphorene so produced comes
in contact with air and moisture it oxidizes, to produce degraded
phosphorous (Fig. 11) which has no practical applications. The
degradation can be avoided by using moisture free solvents like
iso-propanol, mentioned earlier; water can be avoided and the
separation becomes easier by vaporizing out all the propanol after
the process completion [121]. LPE, although provides us with a
possibility of scalability, but the key challenge is still to find an
effective, non-toxic and low-cost solvent. The solvent selection
remains critical as was the case with graphene [122]. Currently,
only anhydrous and oxygen-free solvents can be used for LPE of
BP but an ideal solvent would be the one with high dielectric con-
stant and high surface tension, capable of minimizing degradation
and aggregation of phosphorene within the solution [116]. In the
past, many chemical surfactants have been used to enhance the
performance of liquid phase exfoliated graphene [120]. Recent
research on the use of certain biomolecules as exfoliating and dis-
persion agents for synthesis of several 2D materials has opened
up the possibility of obtaining superior quality phosphorene
[123]. Various biomolecules like proteins, peptides, nucleotides,
nucleic acids (RNA, DNA), polysaccharides, etc. have been already
used to produce high-quality graphene, 2D MoS2 and WS2 [124–
126]. Biomolecule-assisted exfoliation of phosphorene expands
the possible application scenario of phosphorene by encompass-
ing areas of biomedicine and catalysis (by enabling easy surface
functionalization) as well.
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
Fig. 12. Photograph of a representative silica glass ampoule after the synthesis of
black phosphorus. SnI4 (orange) and red phosphorus from the gas phase are
condensed at the right hand side of the ampoule. Black phosphorus has been
formed in large bunches. Excessive Sn has reacted to sn-Phosphides, which are
present in small round spheres [105].
3.2.1.4. Prospective methods. Some chemical methods like lithiation
[127] and electrochemical exfoliation [128] which can provide
more control (as compared to normal LPE) and high yield are not
yet reported for phosphorene production. Electrochemical exfolia-
tion requires the application of an alternating voltage between the
anode i.e. the species to be exfoliated, and the cathode (counter
electrode usually Pt) dipped in an electrolyte of suitable require-
ment. The requirement may be based on the exfoliation rate (con-
centration of electrolyte), the size of ions (intercalating species)
and various other factors. Lithiation might not be as promising as
electrochemical exfoliation due to phosphorus’ strong interaction
with lithium thereby decreasing lithium’s mobility within the solu-
tion. Similar to any electrochemical method, lithiation involves an
electrochemical cell with a lithium foil anode and a layered-
material-containing cathode. The exfoliation on the resulting Li-
intercalated material is assisted by sonication in water as in the
case of liquid phase method mentioned earlier (see Section 3.2.1.3).
Monolayer MoS2, WS2, hexagonal boron nitride and graphene have
already been obtained using lithiation [129]. Electrochemical exfo-
liation, on the other hand, can provide more stable and faster way
of synthesizing few layer black phosphorus as the electrolytes for
carrying out the synthesis can be directly derived from the liquid
phase exfoliation method and the voltage applications can be
derived from the works performed on graphene. With the success-
ful implementation of this method, one can also open the gates for
in-situ doping of few layer black phosphorus giving us more con-
trol over the band gap of the material similar to the case of gra-
phene [130]. Various other modified processes like microwave-
assisted oxidation/exfoliation [131] and laser induced production
techniques [132] which are used as simple, rapid and efficient
means of synthesizing graphene and various TMDs can also pro-
vide similar pathways of synthesizing phosphorene. Since chemi-
cal processes are highly susceptible towards destabilizing and
affecting electronic properties of phosphorene [133,134], alternate
physical means of BP exfoliation are required. Ball milling is one
such technique which can provide increased control and impurity
free phosphorene (similar to graphene) [135]. Ball milling has
already been known to produce stable and efficient nano-
structured BP-graphite composites for battery applications [136].
Ball milling coupled with ultrasonication can easily exfoliate the
weekly bonded layers of BP into phosphorene. Moreover, process
parameters related to ball milling (speed and time) and sonication
(power and time) can be optimized to achieve greater control over
the exfoliation process.
27
3.2.2. Bottom-Up scenario
Advanced chemical synthesis of phosphorene may draw inspi-
ration from the techniques used for graphene and TMDs, such as
hydrothermal synthesis or CVD growth [109]. As of now, there is
no promising bottom-up method for phosphorene synthesis due
to various reasons.
Most phosphorus precursors are highly toxic and are not suit-
able for CVD fabrication [137]. The precursors used for CVD grown
graphene are generally hydrocarbons like CH4, C2H4 and C2H2
[138,68]. The growth of MX2 type 2D TMDs like MoS2 and WS2
require their corresponding oxide and non-metal sources like
MoO3 and a sulfur source (sulfur powder or H2S gas) are used as
precursors to grow 2D MoS2 [21]. These precursors are easy to han-
dle and a lot of substrates support stable growth in case of gra-
phene and TMDs. In case of other materials like germanene,
borophene, silcene and stanene, (mentioned in Table 1) deposition
via thermal evaporation of their elemental forms seems to be con-
venient due to the availability of suitable substrates/surfaces like
Ag(1 1 1), Au(1 1 1), Pt(1 1 1) and Al(1 1 1). Although CVD [138]
being quite successful for growing monolayer TMDs, graphene,
etc., does not seem to be a reliable approach to grow phosphorene
mainly due to the absence of a suitable substrate to deposit phos-
phorene on. For the same reason, substrate-assisted epitaxial
growth also seems to be a challenge. Hydrothermal Synthesis
[139] on the other hand might be suitable for materials which
are stable under high temperature and moisturizing conditions
but BP’s increasing instability in presence of moisture (under high
pressure) will limit its usage. The degradation mechanism of few
layer black phosphorus, as proposed by Y. Huang et al. [140] states
that oxygen plays a major role in degradation hence phosphorene
could be stable in oxygen-free water. Hence boiling water used for
hydrothermal synthesis might provide a suitable environment for
the growth of stable BP. Similar to hydrothermal synthesis, several
other wet-chemical methods like solvothermal synthesis [141],
template assisted growth [142] and self-assembly methods [143]
pose a critical challenge of preventing phosphorene degradation.
However, these methods have been successfully used to produce
TMDs, graphene and other 2D materials and thus can provide us
with a significant future prospect towards synthesizing phospho-
rene as well.
In-situ growth methods are the ones which show maximum
potential and reliability in case of BP and few layer black phospho-
rus because of the easy and process convenient preventive mea-
sures that can be taken in order to avoid degradation of
phosphorene. Recently, Köpf and group [105] modified the Sn/
SnI4 mineralization method to synthesize both phosphorene and
BP via successful intercalation of SnI4 vapors into the BP layers
(after the reaction is completed). The phases could be mechanically
separated from one another after the completion of reaction
(Fig. 12). However, the control on the number of layers and yield
of phosphorene is still subjected to further investigation of the
technique.
In another recent attempt by J B Smith et al. [144] an in-situ
high-pressure CVD approach was demonstrated which combines
the above mentioned mineralization processes and conventional
CVD technique to grow 2D BP on Si substrates. First, they grew
amorphous red phosphorus on Si substrates by heating red phos-
phorus powder or bulk BP with Si substrate in the CVD furnace
under vacuum at 600 °C for 30 min. The amorphous red phospho-
rus films deposited on Si were then heated in the presence of Sn/
SnI4 (10 mg) mineralizing agents in argon at high pressure
(27.2 atm) to produce phosphorene and few layer black phospho-
rus thin films as large as 9000 lm2 and with a thickness ranging
from 3.4 nm to 600 nm. Further optimization of the process param-
eters (temperature, pressure, reactant concentration, growth time,
gas flow etc.) can lead to uniform large area few layer black phos-
28 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
Fig. 13. (a) Output (b) Transfer characteristics of Black Phosphorus FET. (Adapted with permission from Ref. [44]. Ó 2014 American Chemical Society).
Fig. 14. I-V characteristics of p-n diode (using BP and MoS2) under different laser
powers [159]. Adapted with permission from Ref. [159]. Ó 2014 American Chemical
Society.
phorus (or few layer phosphorene) which can be used for numer-
ous applications. However, the quest for suitable substrates to sup-
port the growth of high-quality phosphorene still continues due to
the presence of various structural varieties of phosphorus.
4. Applications
4.1. Phosphorene based devices
The semiconducting properties of the black phosphorus have
not been realized until recently, which opens up several possibili-
ties of using 2D black phosphorus (phosphorene) in various device
applications. Recent research progress in phosphorene stabiliza-
tion, as well as fabrication, provides us with ample opportunities
for designing novel devices and applications. Some of these tradi-
tional and prospective applications have been discussed in the sec-
tions below.
4.1.1. Field effect transistors
Because of its inherent and appreciable bandgap, phosphorene
can be used a channel material in field-effect transistors (FET)
[63,71]. Han Liu et al. [35] fabricated a FET device in which they
used black phosphorus as a channel material; thickness of the
channel varies from 2 to 30 nm and the length of the channel
was around 1 mm. In their device, doped silicon was used as the
back gate and SiO2 as the back gate dielectric on top of Si. Exfoli-
ated black phosphorus was transferred onto the substrate; source
and drain contacts were established using lithography.
The drain current as a function of voltage (output and transfer
characteristics) for the given device configuration is shown in
Fig. 13(a) and (b). The maximum drain current that is obtained in
this case (drain bias – 2 V, channel length – 1 mm) is 194 mA/
mm. For a transistor of similar channel length and drain bias made
using TMDs, the drain current is lesser by almost an order of mag-
nitude [35]. Also, the drain current modulation, observed in a
graphene-based FET device, is almost four orders of magnitude les-
ser due to its lack of bandgap and it is comparable to the values
obtained in TMD based devices like MoS2 [66]. This implies that
black phosphorus is a viable material for digital electronics where
high drain current is a necessity. One of the interesting points
observed in black phosphorus as channel material is that in spite
of its dominant p-type conductivity, n-type conductivity is also
shown by black phosphorus [63]. This results from the narrow
band gap in black phosphorus where the Fermi level can be tuned
either near valence band or near conduction band leading to p-type
conductivity and n-type conductivity, respectively.
Devices fabricated with black phosphorus have many advan-
tages. Firstly, it is a prominent p-type conductor whereas the TMDs
are majorly n-type. Therefore, it opens up the possibility of making
2D p-n junctions, 2D heterojunctions which were not so easy pre-
viously. Secondly, it has a non-zero band gap and higher carrier
mobility. This bridges the gap between graphene, which has a neg-
ligible bandgap, and TMDs, which show lesser carrier mobility.
Thirdly, black phosphorus shows anisotropic transport behavior
[36] i.e. the conductivity in the x-y plane (intra-layer) is different
from the conductivity in the z plane (inter-layer). This property
can be utilized for designing unique electro-optical and electro-
thermal devices. The major disadvantage of black phosphorus is
the environmental instability. The mechanism of degradation is
not well understood till now but some researchers claim the exis-
tence of traces of leftover red phosphorus leads to surface oxida-
tion; pure bulk black phosphorus is a chemically stable material
[35].
Reduced channel length and current fluctuations are among
those very few but recent advancements in the research of BP as
the channel material for FETs. Miao et al. [145] fabricated ultra-
short channel length (20 nm) BP FET by successfully combining
and extending the electron beam lithography (EBL) and angle
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
deposition techniques to a multi-step fabrication process. They
also demonstrated the direct dependence of channel length on
the evaporation angle. With alumina as the contact material, these
ultra-short channel FETs exhibit on-current of 174 mA/mm (for
drain-source voltage (VDS)=100 mv) which is quite higher than
the previously reported value of 1 mA/mm [63,145], for the same
VDS valued BP based FET of 5 mm channel length (Au/Ti as the con-
tact material). Moreover, these FETs are capable of maintaining a
decent on-off ratio of 102 and are quite stable in ambient condi-
tions unlike other FETs which are known to cause performance
degradation on exposure to ambient conditions.
Na et al. [146] investigated the effect of alumina passivation on
the characteristics of the BP based FET. They reported a reduction
in current fluctuation and confirmed the same by using a carrier
number fluctuation (CNF) model for the thermally annealed
devices [146]. BP based FETs of channel length 1.1 mm and thick-
ness 2.6 mm were fabricated via EBL and thermal evaporation. To
determine the Al2O3-passivation effect on few layer BP FETs, addi-
tional static device parameters such as field-effect mobility (lFE),
hysteresis, subthreshold slope (SS), and interface trap density
(Dit) were studied qualitatively and quantitatively. A comparative
study of these parameters for the alumina passivated and unpassi-
vated devices confirmed the reduction in current fluctuation by
observing a decrease in the interface trap density values. These
FETs were also reported to be stable in ambient conditions for even
a longer period of time.
Although, phosphorene based FETs exhibit promising character-
istics, it may take some time to achieve the standards of tradition-
ally available silicon-based FETs possessing superior on/off ratio
(107) and high mobility values (1400 cm2/Vs) at room temper-
ature [63,147].
4.1.2. Rechargeable batteries
Rechargeable batteries, in particular, Li-ion batteries, have sev-
eral advantages over disposable batteries. Li-ion batteries are
widely used due to their high energy density, high storage capacity,
minimal memory effect and low loss of charge. However, Li-ion
batteries are unable to provide high power density which is quite
essential for modern day requirements. In the past, besides gra-
phene [148,149], several attempts have been made to explore
new anode materials in Li-ion batteries [150–153]. Recently, BP
and BP-graphite composites have received growing interest as a
potential high-performance anode material in both Li-ion and
Na-ion batteries [136,154]. Phosphorene can be considered as a
very promising anode material for Li-ion batteries due to fast and
directional Li diffusion on it [155,156]. Also, phosphorene nano rib-
bons were recently reported to be as anode materials with super
high rate and large capacity for Li-ion batteries [157]. First-
principle calculations have shown that the puckered structure of
phosphorene makes the migration of Li atoms anisotropic (more
favorable in zigzag direction) and the low diffusion barrier along
zigzag direction leads to ultra-high diffusivity [155,156]. This
ultra-high diffusivity of atoms on phosphorene gives access to
rapid charging/discharging of Li-ion batteries. Furthermore, the
uniform distribution of Li atoms over phosphorene is not affected
by its unique structure [155]. In contrast, the Li atoms on graphene
are known to cluster together, thereby hindering diffusion [158].
This makes phosphorene a better anode material than graphene
for Li-ion batteries. Besides ultra-high diffusivity (low diffusion
barrier), phosphorene based Li-ion batteries were predicted to give
a very high charging voltage (2.9 V) with enhanced electrical con-
ductivity [155]. Recent efforts on phosphorene based batteries
have shown good performances and with increasing interest in
phosphorene research, superior performance batteries can be cer-
tainly expected to arise in the near future.
29
4.1.3. Optoelectronic devices
Direct, narrow band gap and high carrier mobility along with
the anisotropic transport behavior, makes black phosphorus a
promising candidate for functional optoelectronic device applica-
tions. TMDs like MoS2 have direct band gap only in its monolayer
form, whereas black phosphorus shows thickness dependent band
gap ranging from 0.3 eV in its few layer form to 2 eV in its single
layer form [3]. The relatively small band gap and high carrier
mobility makes black phosphorus a viable candidate for optoelec-
tronic and solar cell application, with fast response and broadband
photo-detection.
Black phosphorus can be used in two ways to make p-n junction
diodes. One is the homojunction black phosphorus diode and the
other one is the combination of p-type black and n-type MoS2
Van der Waals heterojunction diode, which has been demonstrated
very recently [159]. A schematic of the heterojunction, along with
the I-V characteristics of the diode, is shown in Fig. 14. BP was
exfoliated on the CVD grown MoS2 to form the p-n junction; doped
Si was used as the back gate and SiO2 as the gate dielectric. When
used as a photodiode, the device shows strong photoresponse to
the incident laser and the photocurrent is reported to increase as
the incident laser power increases [159]. The photoresponsivity
observed for this device is nearly 5 times more than that of CNT-
MoS2 p-n junction diode with much smaller drain voltage [160].
Moreover, this Van der Walls heterojunction formed using BP-
MoS2 can be used as a solar cell by stacking 2D p-n junctions ver-
tically. The efficiency of the solar cell can be increased by reducing
the thickness of black phosphorus layer. According to theoretical
predictions, it is possible to achieve external quantum efficiency
(EQE) up to 18% [57]. The thickness dependent direct band gap of
black phosphorus is advantageous in this respect as the efficiency
can be improved by tuning its thickness to better utilize different
photon energies of the spectrum.
4.1.4. Other applications
In addition to transistors and batteries, phosphorene has the
potential to be used in next generation solar cell devices, thermo-
electric devices, photocatalysis and composite materials.
Solar cells generate electricity based on the principle of photo-
voltaic effect [161]. Phosphorene can be considered as a promising
photovoltaic material. Phosphorene’s efficient and broadband light
absorption coupled with its direct band gap character and high
mobility makes it an ideal material for multi-junction solar cells.
Density functional theory (DFT) calculations by Hu et al. [162]
and first principle calculations by Dai et al. [57] showed that phos-
phorene can be effectively used in heterojunction solar cells too.
Also, recent work on phosphorene based organic solar cells by
Lin et al. [163] showed improved stability and power conversion
efficiency.
As discussed before, phosphorene can serve as a good thermo-
electric material. Phosphorene possesses strong anisotropy in elec-
trical and thermal properties, which can be used to improve its
thermal efficiency [80,164,165]. Phosphorene also has a low ther-
mal conductivity [37] and a high ZT value [80], which are
quintessential for a good thermoelectric material.
Photocatalytic water splitting is an artificial photosynthesis
process which is used for hydrogen production by dissociating
water into its constituent parts, hydrogen (H2) and oxygen (O2),
using either artificial or natural light. Many 2D materials, for exam-
ple, graphene derivatives [166] and MoS2 [167] have been consid-
ered as good photocatalysts for water splitting. Phosphorene could
also be considered as a potential candidate for photocatalysis due
to its flexible (tunable) and appropriate band gap (0.3 to 2.0 eV)
[168]. Recently, Lee et al. [169] demonstrated exceptional photo-
catalytic performance in experimentally synthesized hybrid (BP-
TiO2) photocatalysts. With the recent knowledge on band gap
30 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34

Fig. 15. (a) Schematic image of BP FET used for chemical sensing (b) A bias stress test of BP FET in air to study the stability in air (change in relative conductance is less than
4%) [174]. Adapted with permission from Ref. [174]. Ó 2015 American Chemical Society.

modification and stability of phosphorene, undoubtedly, one can

expect phosphorene to become a prospective next generation
photocatalyst.
Phosphorene’s impressive and exceptional mechanical proper-
ties can be readily harvested for designing ultra-high strength
composite materials. In the most recent attempt by Hanlon et al.
[120], phosphorene was reinforced into polyvinyl chloride (PVC).
The composite showed an improved value of Young’s modulus
along with a sixfold improvement in tensile toughness. Such an
enhancement in mechanical properties of reinforced PVC shows
that phosphorene, as a strengthening material, possesses even a
higher potential than graphene [170].

4.2. Black phosphorus sensors

4.2.1. Gas sensors

Fig. 16. NO2 gas sensing performance of multilayer BP FET. The above figure shows
the plot relative conductance change (DG/G0) vs time (sec) for varying concentra-
tions of NO2 [174]. Adapted with permission from Ref. [174]. Ó 2015 American
Chemical Society.
A large surface to volume ratio of nanomaterials makes them a
suitable candidate for chemical gas sensing applications. In recent
times, chemical and gas sensing have been studied for various
nanomaterials such as graphene, carbon nanotubes (CNTs) [171]
and nanowires [172]. Theoretical calculations of adsorption of var-
ious gas molecules such as CO, CO2, NH3, NO and NO2 on mono-
layer phosphorene predict a better performance of phosphorene
as a gas sensor material, as compared to its other 2D counterparts

Fig. 17. (a) Response of the BP sensor to different analytes. The inset (right) magnifies the same curves for clarity. The inset (left) shows the schematic of a typical BP film
sensor fabricated. (b) Comparison of sensitivities of a typical BP film, graphene and MoS2 sensors [175]. Adapted with permission from Ref. [175]. Ó 2015 American Chemical
Society.
 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34 31

i.e., graphene and TMDs [173]. The structure, electronic and trans- NH3 as well. In near future, experimental data generated for these
port properties of 2D black phosphorus with the adsorption of the gas sensors will surely be able to demonstrate the sensing poten-
gas molecules were studied extensively from first-principle calcu- tial of BP as compared to other nanomaterial-based sensors.
lations. It reveals that phosphorene is more sensitive to nitrogen
containing compounds such as NO, NO2, since their binding to
4.2.2. Selective humidity sensing
phosphorene is the strongest among the gasses studied. Black
In addition to gas sensing, black phosphorus also shows poten-
phosphorus gas sensors for sensing NO2 has also been demon-
tial for humidity sensing. Recently, the humidity sensing character-
strated experimentally and it agrees well with the theoretical cal-
istics of BP films were studied and an ultrasensitive and selective
culations [174]. In an experiment to demonstrate sensing by Black
response toward humid air is observed with trace level detection
phosphorus flakes, a BP FET was designed, as shown below (Fig. 15)
capability [175]. BP films used in this study were prepared using
[174]. Fig. 15 shows a schematic diagram of the black phosphorus
liquid phase exfoliation through sonication of ground black phos-
gas sensing device. Bulk black phosphorus was synthesized using
phorus powder in dimethyl formamide (DMF) or dimethyl sulfox-
chemical methods and it was exfoliated, using a scotch tape, on
ide (DMSO). After the synthesis of BP films, they were cut into
SiO2/P++ Si substrate, where source/drain were lithographically
required shape and electrical contacts were established using gold
defined using Ti/Au contacts. BP FET, on exposure to varying levels
paste or gallium-indium eutectic. The sensing performance of the
of NO2 concentrations, showed changes in the relative conductance
fabricated films was studied in a dynamic condition using the pulse
values. On adsorption of NO2 on BP, the conductance increased due
injection method [175,176]. 2nL (nanolitre) of selected chemicals
to hole doping charge transfer by NO2 molecules. The relative con-
including water vapor, alcohols, ketones, benzenes were injected
ductance change was discernible for concentrations as low as
and the current modulation of the sensor was studied at a constant
5 ppb surpassing the sensitivity of other 2D sensor materials, such
(direct current) DC bias of 0.5 V in identical conditions. Current
as MoS2. Desorption and reversible adsorption of NO2 on BP are
modulation with respect to time plot is shown in Fig. 17a. Nearly,
possible by flushing the device with argon enabling the recovery
a 5-fold increase in the drain current was observed upon injection
of original conductance values. This means the device can be used
of water vapor, whereas the response to other analytes was much
for repeated sensing.
smaller. Also, direct flow of hydrogen, oxygen and carbon dioxide
In this study, performed by Abbas et al. [174], relatively thick BP
gasses induces a negligible response in the sensor. This selective
flakes were used in the device. Although theory predicts thinner
response of BP towards water vapor makes it viable for practical
flakes would give a better performance, it also undergoes faster
humidity detection as it overcomes cross-sensitivity and false-
degradation in performance under ambient conditions, which
positive issues. The film also shows full recovery of the response
affects the operation of the device. Several studies have focused
within 1–5 s of injection, depending upon the volume of water
on to encapsulate and passivate BP using different chemicals, to
vapor injected.
maintain the performance of thinner flakes [96]. However, for
Yasaei et al. also compared the water vapor sensing character-
gas sensing applications, BP has to be in direct contact with the
istics of BP films to those of graphene and molybdenum disulfide
environment, which increases the chances of degradation. Using
(MoS2). Fig. 17b shows the sensitivity S (where S = ((I I0)/I0)%)
thicker flakes alleviates this problem ensuring stability of the
of different sensors with respect to reciprocal recovery time (1/T)
device and reduced degradation, with negligible loss in the perfor-
upon injection of water vapor. Under identical conditions, BP sen-
mance. A bias stress test, performed in air, showed less than 4%
sors exhibited higher sensitivity (by 2 orders of magnitude) and
variation in the relative conductivity change, which predicts negli-
faster recovery (2-fold faster) compared to other tested
gible contribution from other species present in the air, such as
nanomaterial-based sensors. Also, in static sensing experiments,
water vapor and oxygen.
the drain current of the sensor increases by 4 orders of magni-
In an effort to understand the repeatability of the sensor, BP FET
tude as the relative humidity varies from 10% to 85%. This level
was exposed to varying levels of NO2 concentrations, successively,
of sensitivity compares with the highest levels ever reported for
with flushing by Argon for 5 min, after exposure to a particular
humidity sensing [177–179]. It is also observed that the response
concentration of NO2. After exposing to all concentrations, the
of BP films remains unchanged even after prolonged periods of
device was flushed with Argon to return to its original conductance
ambient exposure [175]. In conclusion, black phosphorus sensors
values. The results of the gas sensing experiment are shown in
show higher sensitivity with faster recovery while remaining
Fig. 16. The relative conductance change DG/G0 is plotted vs time.
stable for several months under ambient conditions making it a
In this set of experiments, DG = G G0 where G is the instanta-
promising candidate for humidity sensing.
neous conductance of the device when NO2 is passed and G0 is
the conductance before the initiation of the experiment.
The inset of Fig. 16 shows the time when NO2 of concentration 5. Summary and perspectives
5 ppb was introduced (ON state). From the results presented, it is
apparent that BP can be used to detect the concentration of NO2 This article reviews recent progress in BP and phosphorene
as low as 5 ppb. Performance of the device can further be improved research encompassing areas of synthesis, properties and applica-
if number of layers of black phosphorus used could be reduced. The tions. Several attractive properties of phosphorene which make it
response time for black phosphorus sensor varied from 4 min to unique and comparable with graphene and TMDs, are highlighted
6 min for different concentrations. This is a direct indication of and discussed in detail. The article also subsumes a critical discus-
the rate of absorption and desorption of gas molecules on the sur- sion on recent progress in synthesis and possible applications, aris-
face of black phosphorus and is comparable to other sensors based ing from these exciting properties.
on 2D materials like 2D MoS2. Besides graphite, black phosphorous is the only other known
Till date, BP FETs were used experimentally for only NO2 gas elemental allotrope that can be mechanically exfoliated to get
sensors. Sensitivity of BP toward NO2 concentrations is comparable atomic layer thickness. The scotch tape method can easily be
to sensors made using other 2D materials. Raman studies, before reproduced on BP to get high-quality pristine phosphorene. The
and after the sensing experiments, showed stability of BP for the three bonds in phosphorus take up all three valence electrons mak-
given time frame [174]. These results lay the groundwork for ing it behave like a semiconductor. Graphene is a zero band gap
studying the chemical, gas and biosensing by BP. Theoretical calcu- semiconductor whereas phosphorene is a direct band gap semicon-
lations predict that there is a potential for sensing CO, CO2, NO, ductor, which is also tunable according to the applied strain. Its
32 A. Khandelwal et al. / Materials Science and Engineering B 221 (2017) 17–34
properties change with the application of stress and also with the
number of stacked layers present. The band gap value varies from
0.3 eV in bulk black phosphorus to about 2 eV in the single layer
phosphorene. Transistors work more efficiently when the electrons
are confined to move in a two-dimensional space and this is
exactly what phosphorene offers. It also has a large on/off ratio
of up to 104 (at room temperature) and high mobility of around
1000 cm2/Vs; when these properties are coupled together it makes
phosphorene very attractive for its use as a channel material in
transistors and can open new doors to quantum computing as well.
Unlike any other 2D material the superior properties of phos-
phorene are fundamentally rooted in its unique structural arrange-
ment. Graphene has a planar layer structure whereas the structure
of phosphorene is puckered in nature, having a single layer with
honeycomb-like lattice, giving us an armchair direction and a zig-
zag direction. In simple words, phosphorene possesses an in-plane
anisotropy. The structural anisotropy of phosphorene greatly
affects its functionality, imparting anisotropic character to its fun-
damental properties. For example, phosphorene shows anisotropic
optical response and the yield strength (YS) values and electron
mobility varies along the two directions. One of the key challenges
in phosphorene research is its environmental stability. The single
layers (even few layer phosphorene) are reactive towards water
and oxygen resulting in redundant reactions specifically initiating
on the edges of layers which ultimately degrade the material and
its properties.
In the recent past, a lot of attention has been given to the syn-
thesis of black phosphorus and phosphorene. Recently researchers
were successful in synthesizing electronic grade phosphorene from
BP crystal via liquid phase exfoliation method as well; the sheets
were stable until water was intentionally introduced. With the
use of advanced computational studies on new prospective sol-
vents and their mechanism of exfoliation, now it is just a matter
of time before chemically stable exfoliated BP (2D BP or phospho-
rene) could be synthesized with much more reliability and ease.
LPE remains the most reliable synthesis method but with the
emergence of several interesting strategies like O2 plasma thin-
ning, ball milling and other chemical methods, increased control
over the quality, stability and yield of phosphorene can possibly
be achieved in near future.
2D black phosphorus or phosphorene is unique from materials
point of view and has many properties which distinguishes phos-
phorene from graphene, TMDs or other 2D materials. The band
gap of graphene could not be tuned to a great extent. Advent of
other 2D materials like MoS2 solved the issue of band gap, but their
low carrier mobility has restricted their applications. Black phos-
phorus is expected to bridge this gap between graphene and TMDs
by demonstrating significant, thickness dependent band gap and
good carrier mobility. These two properties combined with its ani-
sotropic transport behavior have expanded the horizons for appli-
cation of black phosphorus in various electronic applications. Field
effect transistors, fabricated using black phosphorus, are superior
to the TMD based transistors in terms of performance. Since phos-
phorene has a net dipole moment in the out-of-plane direction, it is
hydrophilic in nature and can also be used for sensing and catalysis
applications. However, developing an effective model for surface
functionalization of phosphorene nanosheets is highly desirable
before advancing future scope for catalysis applications.
Photoresponse and the response time shown by phosphorene
are optimum and make it a promising candidate for optoelectronic
and solar cell applications. Phosphorene based solar cells also
deserve a great deal of attention as counter electrodes based on
phosphorene incorporated TMDs, graphene, etc. can be expected
to show improved efficiency of dye-sensitized solar cells (DSSCs)
owing to the excellent performance of TMDs and graphene based
electrocatalysts. Phosphorene can also be used as a promising
material for anode applications in Li-ion and Na-ion batteries. It
is important to deal with the fabrication challenges related to
phosphorene’s instability so as to expect a future for phosphorene
based supercapacitors, which is another important energy storage
system. Furthermore, the peculiar orthogonal anisotropic behavior
possessed by electrical and thermal properties of phosphorene can
be utilized to design highly efficient thermoelectric materials. Also,
because of its high mechanical strength, phosphorene can be used
as a potential reinforcement in composite materials.
Two major challenges limit the practical application of phos-
phorene, large scale synthesis of mono/few layer black phosphorus
and degradation of phosphorene. Hence a robust method is
required so as to synthesize large-scale phosphorene with precise
control over number of layers. To meet and surpass the standards
of silicon-based electronics, it is highly essential to tackle the issue
of degradation as well. Also, recent predictions on phosphorene
derived nano-structures, phosphorene polymorphs, prospective
applications, growth mechanisms and properties, pose several
questions to the experimentalists. It will be interesting to know
if these predictions can be validated in near future and if phospho-
rene based nano-structures can be grown. In addition, the interac-
tion studies between phosphorene, growth substrates and other
2D materials (graphene and TMDs) can open up new opportunities
to develop advanced and more stable electronic devices. Keeping in
mind the recent reports on PL studies of few layer black phospho-
rus, BP oxide and monolayer phosphorene, it can be stated that,
phosphorene has the potential to serve as a new model material
to enhance our understanding of physics of polaritons (excitons,
plasmons) which can further help us to build novel PL engineering
models.
The need to research arises so as to escalate the basic research
work to a marketable product. Phosphorene’s vast potential can
only be realized by drawing even more scientists, innovators, man-
ufacturers, engineers and industrialists towards its joint develop-
ment and synthesis. 2D black phosphorus is an emerging
material which is anticipated to find applications in diverse fields.
Notwithstanding the recent advancements in the research of black
phosphorus, the amounts of experimental results available are still
inadequate. In near future, phosphorene is expected to be studied
extensively to gain more knowledge about its unique properties
and possible applications.
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