Photovoltaic conversion of visible spectrum by GaP capped InP quantum dots grown

on Si (100) by metalorganic chemical vapor deposition

Nripendra N. Halder, Pranab Biswas, P. Banerji, Souvik Kundu, B. Nagabhushan, Krishnendu Sarkar, Sisir
Chowdhury, and Arunava Chaudhuri
Citation: Applied Physics Letters 106, 012103 (2015); doi: 10.1063/1.4905345
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APPLIED PHYSICS LETTERS 106, 012103 (2015)

Photovoltaic conversion of visible spectrum by GaP capped InP quantum

dots grown on Si (100) by metalorganic chemical vapor deposition
Nripendra N. Halder,1 Pranab Biswas,2 P. Banerji,2,a) Souvik Kundu,3 B. Nagabhushan,2
Krishnendu Sarkar,2 Sisir Chowdhury,2 and Arunava Chaudhuri2
1

Advanced Technology Development Centre, Indian Institute of Technology, Kharagpur 721 302, India
Materials Science Centre, Indian Institute of Technology, Kharagpur 721 302, India
3
Center for Energy Harvesting Materials and Systems (CEHMS), Virginia Tech, Blacksburg,
Virginia 24061, USA
2

(Received 29 September 2014; accepted 19 December 2014; published online 5 January 2015)
Growth of GaP capped strained InP quantum dots was carried out by metal organic chemical vapor
deposition technique on Si (100) substrates to explore an alternative material system for photovoltaic
conversion. Studies on reflectance spectroscopy show higher absorption of visible photons compared
to scattering. Smooth and defect free interface provides low dark current with high rectification ratio.
A solar cell made of five periods of quantum dots is found to provide a conversion efficiency of
4.18% with an open circuit voltage and short circuit current density of 0.52 V and 13.64 mA/cm2,
C 2015 AIP Publishing LLC.
respectively, under AM 1.5 solar radiation. V
[[Link]
Quantum confined systems such as quantum dots (QDs)
and quantum wells have been proposed as potential device
structures for next generation solar cells. Extended absorption can be achieved using semiconductor QDs which in
effect increase short circuit current and overall efficiency.1,2
Semiconductor superlattice structures containing InAs QDs
in GaAs matrix are being investigated over decades to convert solar energy. Recently, Guimard et al.2 and Sablon
et al.3 reported fabrication of solar cells made of InAs
QDs/GaAs superlattice with conversion efficiency (CE) of
13% and 14%, respectively. As the energy band gap of both
the materials, which were used to grow QDs and barrier
layer, lies in the infrared region,4 the photons having wavelength in the visible range cannot be collected with this
structure. An alternative material system can be proposed
with InP QDs in GaP matrix so that visible spectra can be
absorbed since InP has a bulk band gap of 1.35 eV. In the
literature, it is found that some works were carried out to
explore the physical properties of InP QDs/GaP system;510
however, in all such reports, InP QDs are found to be grown
on III-V (GaP or GaAs) substrates which are both expensive
and brittle. On the other hand, for the next generation low
cost heterogeneously integrated on-chip electronic circuits,
growth on Si substrates is mostly envisaged due to its mature
process technology and abundance. Its lower mass density
together with higher hardness and thermal conductivity compared to III-V materials are added advantages. Thus, one can
think of an on-chip InP QDs/Si based heterostructures for
efficient photovoltaic conversion which will be able to drive
other microelectronic circuits integrated on the same chip.11
However, batch to batch growth of multilayer InP QDs/Si
with a chemical vapor deposition (CVD) system is elusive as
deposition of Si by cracking silane (SiH4) requires
1200  C,12 the temperature which the QDs cannot withstand
a)

Author to whom correspondence should be addressed. Electronic mail:

pallab@[Link]. Tel.: 91 3222 283984. Fax: 91 3222
255303.

0003-6951/2015/106(1)/012103/5/$30.00

and will be smeared out. Thus, GaP, another III-V material,

can be used as a capping material on InP QDs (in lieu of Si)
as it has almost similar lattice constant that of Si. Besides its
ability to provide a higher energy barrier due to large indirect
band gap of 2.3 eV, GaP will be transparent to visible spectrum.10 For a QD embedded system, the medium can be
treated as optically inhomogeneous and scattering loss
affects the absorption process.13 Thus for photovoltaic applications of a material system consisting of InP QDs grown on
Si substrates and capped by GaP, the overall absorption need
to be enhanced by minimizing the scattering from the alloy
which is formed at the interface due to interdiffusion of
elements during growth.
While growing QDs of a material X in a matrix Y, a
graded alloy of XY is formed at the interface due to interdiffusion of elements from X to Y which enhances scattering of
light along with higher recombination. Reports of elemental
interdiffusion and change of barrier layer composition in
InAlAs/AlGaAs, InGaAs/AlGaAs, and InGaAs/GaAs
systems have been discussed by Lobo et al.14 While growing
InP QDs in InAlGaP matrix, Zhang et al.15 also observed
such kind of alloy intermixing which is reported to increase
with increase in growth temperature.
In this study, we have thus investigated the absorption
properties of GaP capped InP QDs on Si (100) substrates
grown by metalorganic chemical vapor deposition technique.
Higher absorption of visible spectra by the QDs compared to
scattering has been observed. Strategic growth conditions
have been adopted to eliminate the alloy intermixing at the
interface between the QDs and capping layer. Generation of
photo induced carrier by the absorption of light has been
studied by the current voltage measurements on illuminating
the samples with light of different wavelengths. Photovoltaic
response of the samples having five layers of QDs has been
studied under standard solar environment of AM 1.5.
An atmospheric pressure horizontal reactor was used to
grow InP QDs on p-Si substrates, the details of which have
been described elsewhere.16 The QDs were capped by GaP

106, 012103-1

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V

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Halder et al.

cladding layer followed by a thermal quenching along with a

growth stop to prevent the formation of InGaP at the interface. The temperature profile of the substrates during the
growth of InP QDs and GaP cladding layer along with the
growth stop has been shown in Fig. 1(a). Trimethylindium
(TMIn), trimethylgallium (TMGa), and phosphine (PH3)
were used as precursors for this growth. Another set of samples with five layers of InP QDs capped by GaP have been
grown following the above procedure. However, the capping
GaP layer on the top surface has been doped n-type by
hydrogen sulphide in all the samples.
The formation of discrete InP QDs on Si substrate and
capped by GaP layer, as observed by transmission electron
micrograph (TEM), is shown in Fig. 1(b). An average diameter of the QDs and the thickness of the GaP capping layers
were found to be around 10 nm and 25 nm, respectively. As
the dimension of the InP QDs is within the exciton Bohr
radius,11 quantum confinement is expected to occur in the
dots. The single crystalline nature of the QDs and the capping
layer has been found from the spotted selected area (electron)
diffraction (SAED) pattern shown in the inset of Fig. 1(b).
The growth of InP QDs on Si and capped by GaP without formation of InGaP at the interface has been confirmed
by the sputter depth X-Ray photo electron spectroscopy
(XPS). The presence of Ga and P at the upper surface and In,
Ga, and P at the InP QDs/GaP interface have been observed
from the wide scan spectra and are shown in Figs. 2(a) and
2(b). Though as discussed earlier, there was a possibility of
InGaP formation at the InP QDs/GaP interface, the narrow
scan for In and Ga 3d spectra is found to be free from any
peak related to InGaP bonding. The corresponding narrow
scan XPS for In and Ga 3d have been shown in Figs. 2(c)
and 2(d), respectively. The P 2p core level spectrum shown
in Fig. 2(e) was found to consist of two sub peaks originating
from In-P and Ga-P bonding which suggests the presence of
both InP and GaP at the interface. The intensity and area
under the curve corresponding to Ga-P spectrum qualitatively show the presence of higher amount of GaP at the
interface. Binding energy of Ga-P is found to be higher than
that of In-P due to shift of the covalent electron pair. During
formation of covalent bonds with pentavalent phosphorous
to satisfy the stable electronic configuration in GaP and InP,
the electron pairs shift closer to gallium (for GaP) compared
to indium (for InP) due to lower electronegativity of gallium
though both of them are trivalent. The presence of elemental

Appl. Phys. Lett. 106, 012103 (2015)

FIG. 2. Wide range XPS of (a) GaP capping layer and (b) InP QDs/GaP
interface. Narrow scan XPS for (c) Ga 3d, (d) In 3d, and (e) P 2p show spectra with binding energies corresponding to GaP and InP without any other
alloy formation.

phosphorus in the samples and formation of InGaP at the

interface are not observed. Moreover, no signature of any
other compound or defect was also found. Due to high PH3
to TMIn ratio, growth stop, and PH3 over pressure during
increase in temperature (as shown in Fig. 1(a)), no free In
adatoms were available to diffuse in the GaP layer to form
InGaP. All the spectra were compared with the standard
binding energy lookup table of XPS International, Inc.17
Thus, the optical properties which are discussed further are
solely due to InP QDs.
The absorption spectra of the sample have been obtained
from the diffuse reflectivity using the relation A log10 R.18
Convoluting the absorption spectra (shown in Fig. 3(a)), three
different absorption peaks arising from band to band transition
of InP and GaP along with confined states of InP QDs have
been identified. The corresponding transitions can be visualized from the minima of second derivative of the absorption
spectra and have been shown in Fig. 3(b). The relative intensities of the convoluted peaks suggest that absorption by the
InP QDs dominates over InP or GaP layers. From the diffuse
reflectance (R), the KubelkaMunk (K-M) function can be
2

K
defined by the relation F R2 1R
2R S , where K and S
are the KM coefficients. According to diffusion approximation by Van Gemert et al.,19 K and S are associated with the
absorption co-efficient (la ) and scattering co-efficient (ls ) by
the following relations:

K 2la
and
3
1
3
1
S 1  gls  la us  la ;
4
4
4
4

FIG. 1. (a) Graphical representation of initiation, interruption, and termination of the growth process. (b) Cross sectional TEM image of the GaP
capped InP QDs. SAED pattern of the sample (inset) affirms crystalline
nature of the sample.

where us is a multiplicative function of ls and scattering

anisotropy coefficient (g). Thus, inverse of K-M function
can produce a qualitative measure of scattering to absorption
ratio by the capped QDs. For a sample with capped QDs,
the absorption can be visualized as transformation of the
incident photons into electron-hole pairs and scattering as
redirection of the photons after interaction. It has been found
from Fig. 3(c), though the scattering dominates over the

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Halder et al.

Appl. Phys. Lett. 106, 012103 (2015)

FIG. 4. (a) Dark and illuminated current-voltage characteristics of the sample. (b) Change of reverse current with illumination wavelength at different
bias voltage. (c) Variation of rectification ratio with illumination
wavelength.

FIG. 3. (a) Absorption spectra of the InP QDs capped with GaP. The corresponding peaks suggest the absorption due to band to band transition in InP
and GaP along with quantum confined states of the QDs. (b) Minima of second derivative of the absorption spectra with respect to energy exclude other
transition in the system. (c) Scattering to absorption ratio of the structure
obtained from diffuse reflectance of the sample.

absorbance for the band to band transition, for QD it is

otherwise. The decrease in scattering by the QDs suggests
formation of smooth interface between InP QDs and the
embedding matrix, whereas higher absorption is an indication of efficient carrier conversion. The reflection response
of QD nanostructures can be explained using effective medium theory20 as the dimensions of the QDs are small compared to the wavelength of the illuminated light and can be

treated as electrically small objects.21 The effective permittivity is thus different from its bulk value due to quantum
confinement and small volume fraction compared to the host
or embedding materials. With increase in the band gap due
to quantization, effective refractive index of the QDs
decreases which lead to decrease in effective permittivity
and minimizing attenuation index (imaginary part of the
complex refractive index), as a result of which the absorption
of the electromagnetic wave is enhanced in the QDs. Low
energy photons will pass through the QDs without transferring their energy to the electrons in the valance band,
whereas the high energy photons will interact with the capping GaP layers.
The effect of visible light absorption in the generation of
photo induced carriers by the QDs has been studied by the

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Halder et al.

FIG. 5. Current density (J) versus voltage (V) characteristics (black line)
and output power (blue line) of the fabricated solar cell with five periods of
InP QDs.

current-voltage measurements on illuminating the samples

with different wavelengths. The highly rectifying behavior
of the dark current-voltage characteristics with rectification
ratio of 221 at 62 V and low reverse current of 5.98  108
A indicate growth of highly crystalline InP QDs and GaP
capping layers with low defect densities. It has been found
that the reverse current increases with decrease in wavelength of the incident radiation, whereas the forward current
remains almost same over the whole wavelength range and
has been shown in Fig. 4(a). The forward current-voltage
characteristic
 is found to follow the diode equation
qV
with an ideality factor g of 4.7. Such high
I I0 exp gkT
value of g is due to the formation of additional junction at
InP/GaP interface.22 The reverse current is found to increase
with decrease in the illuminating wavelength. Minima of the
reverse currents are found to be shifted towards positive voltage with decrease in wavelength of the incident radiation
which corresponds to generation of higher photo induced
charges in the device. The change in rectification ratio with
illuminating wavelength has been shown in Fig. 4(b).
Increase in energy of the incident light enhances the photo
generated carriers in the InP QDs and the reverse current is
thus found to increase. However, the rate of increase in the
photo generated current does not have a linear relationship
with the wavelength. The change of photo induced current
with the illuminating wavelength at different bias voltage
has been shown in the inset of Fig. 4(c). The rate of generation of photo induced carriers (corresponds to slope of the
curve) is found to increase exponentially with the energy of
the incident radiation. At lower energy, the excitons were
generated by the absorption of the photons by the QDs,
whereas high energy photons will create carriers in the
capping region. The generation of carrier in the capping GaP
enhances the photo generated current efficiently.
The photovoltaic property of the device made of
p-Si/InP QDs/GaP structure having five layers of InP QDs in
GaP matrix has been studied on illuminating it with standard
1.5 AM solar spectrum (100 mW/cm2) at room temperature.
The upper most GaP capping layer was doped with S to
make it n-type with a carrier concentration of 2.3  1017
using H2S. The corresponding current-voltage characteristic
has been shown in Fig. 5. The photo induced electron-hole

Appl. Phys. Lett. 106, 012103 (2015)

pairs are generated when solar radiation is absorbed in the

QDs and collected efficiently at the electrodes due to built-in
electric field at the p-Si/n-GaP heterojunction. From the
photovoltaic current-voltage measurements, an open circuit
voltage of 0.52 V and a short circuit current density of
13.64 mA/cm2 are obtained. The plot of the output power as
a function of voltage suggests that the cell can deliver the
maximum power at Vm 0:38 V with a corresponding
current density of Jm 10:98 mA=cm2 . Thus, the fill factor
(FF) and CE of the cell have been found to be 59% and
oc Isc
 100%.
4.18% following FF VVocM IIMsc and CE FFV
APin
The measured open circuit voltage and short circuit current
of the cell are found to be lower than the theoretically calculated values of 1.85 V and 23.78 mA/cm2, respectively,
due to decrease in minority carrier lifetime in the device as
a result of several recombination mechanisms such as
Shockley-Read-Hall, Auger and trapping of the carriers in
the strained QDs.2326 For an ideal case, the maximum efficiency of this structure is 44% and 63%, respectively, for
unconcentrated and fully concentrated solar radiations.26
Low efficiency of the cell can be attributed to the following:
the finger electrode has covered almost one fourth of the cell
area and the rear contact was made on the p-Si, which has
reduced the effective absorption of the structure and a potential drop across the wafer. The efficiency can be enhanced by
using lithographic tool to make the front contacts over GaP
with 10% surface coverage,27 proper contact engineering,
and increasing the periods of QDs.
In conclusion, growth of GaP capped InP QDs, free
from InGaP interfacial layer, on Si (100) substrates has been
demonstrated using PH3 over pressure followed by a strategic growth stop. Solar cells based on such QD embedded
semiconductor heterostructure with high absorption to scattering ratio can be potential energy harvesting systems for
the future with its capability of absorbing photons in the visible region and efficiently convert them to photo induced current. Conversion efficiency of 4.18% with an open circuit
voltage of 0.52 V has been measured for a device with five
periods of GaP capped InP QDs on illuminating them with
standard AM 1.5 solar radiation.
N. N. Halder thankfully acknowledges the financial
support received from DST, India (Sanction No. 100/IFD/
196/2010-11, dated 03/06/10). We are thankful to Mr. S. R
Gollu (IIT Bombay) and Mr. Palash Das (IIT Kharagpur) for
their support.
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