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Growth of 2D black phosphorus film from chemical vapor deposition

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 Nanotechnology

Nanotechnology 27 (2016) 215602 (8pp) doi:10.1088/0957-4484/27/21/215602

Growth of 2D black phosphorus film from

chemical vapor deposition
Joshua B Smith, Daniel Hagaman and Hai-Feng Ji1
Department of Chemistry, Drexel University, Philadelphia, PA 19104, USA

E-mail: hj56@drexel.edu

Received 23 December 2015

Accepted for publication 23 March 2016
Published 18 April 2016

Abstract
Phosphorene, a novel 2D material isolated from bulk black phosphorus (BP), is an intrinsic
p-type material with a variable bandgap for a variety of applications. However, these
applications are limited by the inability to isolate large films of phosphorene. Here we present an
in situ chemical vapor deposition type approach that demonstrates progress towards growth of
large area 2D BP with average areas >3 μm2 and thicknesses representing samples around four
layers and thicker samples with average areas >100 μm2. Transmission electron microscopy and
Raman spectroscopy have confirmed successful growth of 2D BP from red phosphorus.
Keywords: thin film, 2D, black phosphorus

(Some figures may appear in colour only in the online journal)

Abbreviations issues with single layer graphene is that it is intrinsically a

zero band gap conductor [3, 11], i.e. it cannot be switched off.
BP Black phosphorus For use in electronic devices that require a semiconductor,
CVD Chemical vapor deposition doping of graphene is necessary. Today, materials researchers
SBP Substrate black phosphorus continue to search for new 2D materials with applications in
various fields such as energy, biology, environmental etc.
SEM Scanning electron microscope
Some examples are MoS2, WS2, WSe2, MoSe2, but aside
TEM Transmission electron microscope from carbon, there are few examples of 2D materials isolated
SAED Selected area electron diffraction from elemental allotropes.
BF Microscope Bright field microscope Phosphorus has four allotropes, white, red, violet and
black. White phosphorus is made up of four atoms, P4, which
AFM Atomic force microscopy
is extremely unstable [12]. Red phosphorus is made of an
XRD X-ray diffraction amorphous network of phosphorus atoms linked with cova-
lent bonds, and violet phosphorus is a crystalline network
with cage structures [12]. Black phosphorus (BP) is a stable,
semiconducting allotrope of phosphorus that was first dis-
Introduction covered by Bridgman in 1914 [13]. The crystal structure is
composed of corrugated, continuous six-member rings
The isolation of graphene from bulk graphite by the Man- forming sheets of covalently bonded phosphorus atoms
chester group in 2004 has led to extensive research in the field [14, 15]. Different layers are held together by weakly
of 2D materials and their applications [1]. Applications have attracting van der Waals forces. This puckered structure led to
been investigated in areas including field-effect transistors [2– early studies on intercalation of compounds for modification
6], photodetectors [4, 7, 8], solar cells [9, 10], etc. One of the of the electrical properties [14], however, doping of the
material is not necessary, as a layer dependent band gap has
1
Author to whom any correspondence should be addressed. been observed [16–18]. Early electrical characterization

0957-4484/16/215602+08$33.00 1 © 2016 IOP Publishing Ltd Printed in the UK

Nanotechnology 27 (2016) 215602 J B Smith et al

Figure 2. Standard temperature/pressure ramp for growth of SBP

from the red phosphorus thin films. Temperature recorded was that
of the tube furnace.

Figure 1. Schematic of amorphous red phosphorus thin film growth

from vapor deposition of red phosphorus powder/BP piece.

studies showed a temperature dependence of the resistivity of

this material and also found intrinsic p-type doping char-
acteristics [14, 19, 20]. More recently, Li et al found that
crystalline BP can be used as a resource to produce a 2D
semiconducting material, which they coined it phosphor-
ene [21].
Current methods employed to achieve thin pieces of BP
are identical to those proven to work with graphene.
Mechanical exfoliation with tape [21] and liquid exfoliation
[22] methods have shown the most progress so far, however,
one of the limiting factors for the applications of 2D BP is
that current methods cannot achieve large area few/single
layer phosphorene. It was also recently discovered that
application of high pressures from an anvil press to red
phosphorus allowed for the growth of polycrystalline BP [23].
In this work, we report a new method to mass produce thin
films of BP with average areas >100 μm2 and thicknesses on
the length scale of tens of nanometers. Early studies carried
out by Bridgman suggested the only possible synthetic route
to BP was under controlled temperatures and high pressures
[13, 24]. However, moderately low pressure and temperature
conditions with red phosphorus powder in the presence of a
mineralizing agent have produced bulk BP [25–27]. For the
first time, we demonstrate the synthesis of 2D BP from red
phosphorus directly on a silicon substrate in a chemical vapor
deposition type approach. We also report the growth of and
characterization of thin films from another phosphorus allo-
trope—red phosphorus, which was first fabricated in vacuum
and then converted to BP under high pressure, similar to what
was most recently published by Li et al [23].
Methods
Red phosphorus (Mallinckrodt) was purified in boiling DI
water for 15 min and then rinsed with DI water until neutral
and dried in a vacuum oven prior to use [28]. Tin powder
(Fisher Scientific) was purified by shaking in 10% aqueous
NaOH solution for 10 min followed by filtering and rinsing
Figure 3. Schematic for growth of SBP on substrate from amorphous
red phosphorus thin film in pressure vessel reactor.
with DI water until neutral and dried in a vacuum oven prior
to use [28]. All samples were stored in a desiccator until use.
Tin (IV) iodide was prepared by mixing 0.5 g of tin powder
with 2.0 g of iodine (Aldrich) and refluxing in 25 ml of 1:1
acetic anhydride/acetic acid until the violet color dis-
appeared. Upon cooling, the formation of orange crystals
were observed and they were isolated from the reaction
mixture by suction filtration and purified by recrystallization
from chloroform [29]. Bulk BP was prepared in a sealed
ampoule by methods identical to that of Nilges et al [27].
Silicon/silicon dioxide wafers (300 nm oxide thickness,
Montco Silicon) were cut to a desired size of roughly
0.75 cm×0.25 cm and were cleaned by sequentially soni-
cating in dichloromethane, methanol, water, and acetone. The
sonication was followed by immediately drying with N2 gas
and a 20 min treatment in a UV/Ozone Cleaner (BioForce
Nanosciences ProCleaner Plus).
Red phosphorus thin films were prepared by heating
0.5 mg of red phosphorus powder or one piece of bulk BP
(approximately 0.5 mg) in a tube furnace to 600 °C in the
presence of a silicon substrate for 30 min under vacuum. After
30 min, the tube furnace was turned off and the chamber was
allowed to cool. The presence of the red phosphorus thin film
was indicated by a thin green film on the substrate. Samples

2
Nanotechnology 27 (2016) 215602
Figure 4. Optical and SEM images of amorphous red phosphorus films grown from vapor deposition. (a) Bright filed image of 40 nm thick
red phosphorus film. (b) The film noticeably folds over itself upon rinsing with acetone and drying with N2. (c) Extremely thin blue colored
red phosphorus film. (d) SEM image of separated red phosphorus thin film.
were transferred to a desiccator until further use. The sche-
matic of the experimental setup is shown in figure 1.
The following method describes the conditions used to
grow the 2D substrate BP, which will be denoted as SBP
referring to the 2D BP on substrates. Substrates containing the
amorphous red phosphorus thin films were transferred to a
12 ml Kimble conical-bottom glass centrifuge tube (Fisher
Scientific) also containing the purified Sn (20 mg) and SnI4
(10 mg) mineralizing agents. The centrifuge tubes were then
placed into the pressure vessel reactor (Pressure Product
Industries) and the vessel was sealed, evacuated, and back-
filled with argon (3×) and adjusted to a final pressure of
400 psi (27.2 atm). The vessel was then secured into the tube
furnace and heated up to an external temperature of 950 °C
(temperature setting of tube furnace). Once the furnace
reached 950 °C, the temperature was then decreased at a rate
of 50 °C every 30 min. The furnace was held at both 700 °C
and 600 °C for 1 h until it was turned completely off. The
temperature and pressure were monitored during each run and
a typical ramp is shown in figure 2. The schematic of the
experimental setup is shown in figure 3.
Bright-field microscope images were obtained with an
Olympus Microscope (Model BX51) equipped with a Pix-
eLINK camera (PL-A662). Scanning electron microscopy
(SEM) images were obtained on a Hitachi Tabletop SEM (TM-
1000). Atomic force microscopy (AFM) images were run in
tapping mode with a scanning probe microscope system (Veeco
3
J B Smith et al
Metrology, Inc., Multimode Nanoscope IIId) with Veeco FESP
cantilevers. Raman spectra were obtained using a Renishaw
Ramascope (RM-1000) with a confocal Raman microscope
(Olympus BH-2) equipped with a HeCd laser (Kimmon) with
an excitation wavelength of 441.6 nm. Transmission electron
microscope (TEM) images and selected area electron diffraction
(SAED) patterns were obtained at 120 kV on a TEM/STEM
(JEOL JEM2100) equipped with a LaB6 electron gun. TEM
samples were prepared by spin coating the substrate with a 2%
solution of poly(methyl methacrylate) in methyl ethyl ketone.
The polymer film (containing the sample) was then floated off
the substrate into a beaker of water and then fished out with the
TEM grid. The polymer film was then dissolved by rinsing with
acetone so only the sample remained on the grid.
Results and discussion
Fabrication of red and BP thin films
Our first attempts to grow BP thin films from direct vapor
deposition of red phosphorus or bulk BP in vacuum or in
argon were not successful. Both red phosphorus and BP was
found to deposit as an amorphous red phosphorus thin film
under vacuum, while no film was observed under a steady
flow of argon. The appearance of red phosphorus from the
thermal decomposition of BP was also recently discovered in
Nanotechnology 27 (2016) 215602 J B Smith et al

Figure 5. (a) TEM image of an amorphous red phosphorus thin film with the respective inset of the SAED pattern. Scale bar is 50 nm. (b)
AFM image of a 40 nm green colored film showing inset of the height profile.

Figure 6. (a) A bright field image and (b) a SEM image of 600 nm thick SBP sample.

Figure 7. SEM images of additional thin SBP samples on the substrates.

another work [30]. It has been noted previously that red
phosphorus vapor will condense as red phosphorus when
under vacuum [31]. However, under lower temperature in
both sealed ampoule and pressure vessel experiments, red
phosphorus condensed on the surface as white phosphorus.
This was apparent from the formation of a white/yellow
powder that combusted on exposure to air. It is noted that we
did not investigate whether a red or BP film can be prepared
from white phosphorus to avoid the safety steps involved in
handling reactive white phosphorus. Therefore, red

4
Nanotechnology 27 (2016) 215602 J B Smith et al

Figure 8. AFM image of SBP thin film on silicon substrate. (a) Layering of material with magnified inset showing spacing between individual
layers. (b) Height profile of the inset image and a gap of roughly 8.5 Å between two layers. (c) Thin film of SBP with 0.35 μm2 area. Inset:
height profile for SBP thin film showing thickness of approximately four layers (3.4 nm). (d) AFM of larger area thin film of SBP with
respective inset of height profile that is also representative of four layers and 4 μm2.

Figure 9. (a) TEM image of a small piece of SBP sample detached from a silicon substrate and the respective (b) SAED pattern showing
crystallinity of the SBP.

5
Nanotechnology 27 (2016) 215602
Figure 10. Raman spectra of (a) 2D amorphous red phosphorus film,
(b) exfoliated black phosphorus from bulk and (c) SBP sample.
Figure 11. Raman spectra of (a) SBP sample without polarization
and (b) with y-polarization bringing out the 365 cm−1 band.
phosphorus thin films can be grown under controlled condi-
tions from both red phosphorus powder and pieces of BP.
Characterization of red phosphorus thin films
Red phosphorous thin film growth was found to be highly
reproducible with these methods. Simple analysis with bright-
field microscopy allows us to estimate the thickness of the red
phosphorus thin films. A green colored red phosphorus thin
film corresponds to a thickness of around 40 nm and the blue
color corresponds to thinner films with a thickness of <10 nm,
which were confirmed by AFM measurements (figures 4(a)–
(c)). Figure 4(d) shows an SEM image of a separated film.
Figure 5(a) shows the TEM image of the 2D red phosphorus
thin film. The inset SAED pattern shows the clear characteristic
rings of an amorphous material, verifying this is a 2D red
phosphorus film because of its lack of crystallinity [32].
Characterization of SBP
These amorphous red phosphorus thin films were then used to
grow 2D BP directly onto the silicon substrates. When sub-
strates containing the amorphous red phosphorus thin films
6
J B Smith et al
were heated in the presence of Sn/SnI4 (10 mg) mineralizing
agents in argon according to our method at high pressure
(27.2 atm), SBP of various thicknesses were found to grow
directly on the silicon substrate with continuous regions as
large as 9000 μm2 (figure 6). This specific SBP sample is
roughly 600 nm thick, however, thinner samples were
observed throughout the substrate with thicknesses down to
3.4 nm. Figure 7 shows thin SBP samples, although of much
smaller areas.
Figure 8(a) shows a clear layering of an SBP sample. The
height profile (figure 8(b)) shows a difference of approxi-
mately 0.85 nm between two layers which is representative of
a single layer of BP [33]. Figures 8(c) and (d) shows 3.4 nm
thick SBP with an area of 0.35 μm2 that is representative of
four layers, and thus few-layer phosphorene. Similar samples
can be found throughout the substrate by scanning with AFM
and are visible with brightfield microscopy as a faint green
color. TEM analysis was also performed on the SBP samples
(figure 9). The measured d-spacings of 2.64 Å, 1.74 Å, and
1.30 Å match those of the (004), (006), and (117), respec-
tively, from x-ray diffraction data of bulk BP [15].
The characterization of the SBP film was further inves-
tigated by using Raman spectroscopy (figure 10). BP contains
five active Raman bands but only three bands are commonly
observed. The three bands are typically at 365, 442, and
470 cm−1, corresponding to the Ag1, B2g , and the Ag 2 bands,
respectively [34]. In our measurements, the peaks at 442 and
470 cm−1 are strong, but the Ag1 mode at 365 cm−1 is very
weak in the SBP sample. A weak signal was observed for the
365 cm−1 peak in the bulk BP sample as well. This can be
explained by the angular dependence of the Raman response
since BP is an anisotropic material [35, 36]. Using polarized
Raman experiments, the 365 cm−1 band becomes visible and
verifies the SBP as BP (figure 11). The presence of an extra
small broad peak around 397 cm−1 in the SBP sample can be
explained by the slight decomposition of the material to
phosphoric acid as an oxidation product [37]. The air sensi-
tivity of the material was also observed with AFM studies as
the sample noticeably decomposed and phosphoric acid
formed on the surface from exposure to air for 48 h.
Decomposition was prevented by storing samples in a
vacuum desiccator.
Electrical characterization of the samples was carried out
by transferring the SBP to a substrate containing pre-depos-
ited gold electrodes as lithography techniques were not
available. The typical I–V curve for BP was also visible with
the transferred SBP sample representing that of a semi-
conductor material [38]. Field-effect transistor measurements
were carried out using a bottom silicon gate with a silicon
dioxide insulating layer. The effects on the I–V curve verified
the p-type character of the SBP as a negative gate provided
greater electron flow (figure 12(a)). The transfer curve shows
a high on/off for the transistor of ∼104 (figure 12(b)).
However, as this sample was rather thick, we believe that
similar result can be attained with the thinner samples as
shown above.
Nanotechnology 27 (2016) 215602
Figure 12. Field effect characteristics of SBP samples. (a) I–V characteristics at varying gate voltages showing p-type characteristics. The
inset shows a brightfield image of transferred SBP sample over gold electrodes. (b) Source–drain current (Ids) with varying gate voltages in
both linear scale (orange/left side) and logarithmic scale (blue/right side). Channel length was 10 μm and the Vds was held at 1 V.
It should be noted that sealed ampoule experiments
provide only bulk BP since a large amount of red phosphorus
is initially required to reach the necessary pressure. By uti-
lizing the pressure vessel, a thin film of red phosphorus can be
used since the addition of argon provides the proper pressure
conditions. Also, it significantly simplifies the preparation for
growth of the material. A major issue with the ampoule
experiments was the difficulties in sealing the glass while
maintaining vacuum conditions. Decreasing the amount of
initial red phosphorus also decreases the danger in forming
hazardous white phosphorus, which can be the case if the
proper temperature/pressure conditions are not reached in the
sealed ampoule experiments and/or the ampoule ruptures.
Conclusions
It has been recently reported that a thin film of red phosphorus
has been obtained from a similar method to the one we
describe here [23], however, we show that this is possible
from both red phosphorus and BP and show the investigated
scalability in this work. We report the independent develop-
ment of an amorphous thin red phosphorus film of large size
by using vapor deposition of bulk red or BP. We have also
demonstrated a new method to growing SBP directly on a
silicon substrate beginning with a thin film of red phosphorus.
This process eliminates the problems associated with the
sealed ampoule growth, such as difficulties in sealing the
ampoule and potential combustion and also eliminates use of
expensive anvil cells. Films as thin as four layers have been
obtained and we believe through optimization they can be
achieved on much larger scale. Decreasing the air sensitivity
of BP is currently under investigation, however, much
research has been done with encapsulation and has been
shown to be successful with increasing the lifetime of the
material [39, 40]. Optimization of the pressure/temperature
ramp is currently ongoing aiming at the growth of super large
area BP films with few-layer BP sheets for a variety of
practical applications.
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J B Smith et al
Acknowledgments
We would like to thank Professor Reinhard Schweitzer-
Stenner and his graduate student David DiGuiseppe for
assisting us with Raman analysis of our samples. Funding was
provided from the SARIDrexel grant: 0003.
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