Available online at www.sciencedirect.

com

ScienceDirect
Procedia Engineering 139 (2016) 117 – 122

MRS Singapore – ICMAT Symposia Proceedings

8th International Conference on Materials for Advanced Technologies

Surface Engineering of Pbs Colloidal Quantum Dots Using

Atomic Passivation for Photovoltaic Applications
Mohammad Mahdi Tavakolia,*
a
Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran, Iran

Abstract

Solution-processed quantum dots (QDs) have attracted significant attention for the low-cost fabrication of optoelectronic devices.
Here, we synthesized PbS QDs via hot injection method and passivated the trap states by using short thiols and dopant elements
for photovoltaic application. In order to study the effect of dopants on photovoltaic application, PbS QDs were doped by using
three different cations: Cadmium, Calcium, and Zinc. We utilized Time resolvel Photoluminescence measurement to study the
carriers lifetime for different samples and found that the carriers life time increases ~80% by using Cd as a dopant compared with
undoped sample. In addition, the results of J-V measurement showed that Cd dopant has a better improvement than Ca and Zn
dopants due to the enhancement of the efficiency of PbS QDs solar cell. Finally, we achieved solar power conversion efficiencies
of 5.81% using Cd therapy.
©©2016
2015TheTheAuthors.
Authors. Published
Published by by Elsevier
Elsevier Ltd.Ltd.
This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or peer-review under responsibility of the scientific committee of Symposium 2015 ICMAT.
Selection and/or peer-review under responsibility of the scientific committee of Symposium 2015 ICMAT
Keywords: Colloidal quantum dots; Solar cell; PbS; Atomic passivation; ligand exchange

1. Introduction
PbS quantum dots (QDs) are attracting increasing attention because of their optoelectronic properties promising for
photovoltaic (PV) applications because of facile and cheap synthesis process, large Bohr radius (~20 nm), and its
tunable bandgap [1-6]. Despite the many advantages of PbS QDs, the presence of trap states and weak charge
transfer between the dots degrades the PV performance of solar cells [7-10]. In order to tackle theses problems,

* Corresponding author. Tel.: +98 (21) 6600 5717; fax: +98 (21) 6600 5717.
E-mail address: mmtavakoli@ust.hk

1877-7058 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or peer-review under responsibility of the scientific committee of Symposium 2015 ICMAT
doi:10.1016/j.proeng.2015.08.1122
118 Mohammad Mahdi Tavakoli / Procedia Engineering 139 (2016) 117 – 122

many studies have recently been performed [11,12]. The main approaches include ligand exchange by short
molecules to decrease the interparticle distance, obtain a more compact structure, and passivation of surface traps by
transition metals [13,14]. Further improvements have been achieved by atomic-ligand passivation [15] and
construction of quantum junction devices [16-18]. Recently, a record solar conversion performance of 8.55% has
been reported for PbS QD solar cells using a short ligand (1,2-ethanedithiol) [19-27]. In the present work, PbS QDs
were synthesized via a hot injection method. Then, the QDs were surface-passivated with oleic acid followed by Cd,
Ca, and Zn therapy in three different processes. In order to study the effect of doping, the optical properties of QDs
and their nanostructured films were investigated. The prepared QDs were used to fabricate bulk heterojunction solar
cells by solid-state ligand exchange through spin-coating. Finally, the PV performance was measured and the
highest efficiency was achieved for the passivation of mid-gap trap states of QDs by Cd.
2. Experimental
In order to prepare the PbS QDs with a band-gap of about 1.34 eV, a solution-based approach, hot injection method,
was utilized. 0.45 g of PbO, 1.5 ml of oleic acid, and 3 ml of 1-octadecene (ODE) were mixed in a three-necked
flask at 110 °C for 16 h to produce a lead oleate solution. Then 15 ml of ODE was added to the flask and a solution
containing 210 ȝl of Bis (trimethylsilyl) sulfide (TMS) dissolved in 10 ml of ODE was swiftly injected into the
flask. After washing, PbS QDs were dispersed in octane (50 mg/ml). In order to do doping, different cations M2+
(Cd, Ca, and Zn) were used. In this regard, 2 mmol MCl2, 0.1 g tetradecylphosphonic acid (TDPA), and 10 ml
oleylamine (OLA) were mixed in a flask and heated at 100°C for 30 min. 12 ml of PbS QDs were mixed with 4 ml
of the M-containing solution. After washing and preparing 50 mg/ml PbS QDs in octane, the PV devices were
prepared through a layer-by layer spin-coating process on TiO2-coated FTO substrates. The methods used for the
preparation of these substrates are explained elsewhere [8].
3. Results and Discussion
A high-resolution TEM image of the synthesized PbS QDs is shown in Fig. 1a. The nanocrystals have an average
size of ~3 nm with narrow size distribution. Fig. 1b shows the magnified TEM image of the PbS QDs which are
highly crystalline. The EDS chemical analysis (Fig. 1c) illustrates the quality of the as-synthesized PbS QDs. The
XRD pattern of the nanoparticles (Fig. 1d) also indicates their high crystallinity and shows that it has a good
agreement with the standard diffraction pattern of PbS (JCPDS 02-0699).

Fig. 1. (a,b) HRTEM images, (c) EDS analysis, and (d) X-ray diffraction patterns of PbS QDs synthesized by using hot injection method.
 Mohammad Mahdi Tavakoli / Procedia Engineering 139 (2016) 117 – 122 119

The effect of doping was studied by using the optical characterizations of PbS QDs. UV-vis-near infrared absorption
and photoluminescence (PL) spectra of PbS QDs before and after doping are shown in Fig. 2. Referring to Fig. 2a, a
well-defined excitonic peak at about 923 nm can be seen for PbS QDs without doping. The sharp peak indicates that
the dots have a narrow size distribution with an optical band gap of about 1.34 eV.

Fig. 2. (a) Absorbtion and (b) photoluminescence spectra of PbS QDs before and after elemental doping.

This peak becomes a little bit broader and shifts to the red after doping using Zn, Ca, and Cd, however, the amount
of red-shift is different for these cations. For Cd-doped nanocrystals, the excitonic peak further shifts to the red,
which is beneficial in terms of the improved near-infrared absorption of the solar spectrum. Similar to the absorption
spectra, the PL spectrum of M-doped PbS QDs exhibits a red shift compared with the PbS QDs, while the PL
spectrum of M-doped nanocrystals has nearly the same spectral width as for PbS QDs but further shifts to the red.
The largest red-shift PL is for Cd-doped QDs (Fig. 2b). The photoluminescence quantum efficiencies (PLQE) of
undoped PbS, Zn, Ca, and Cd doped PbS QDs were 27, 28, 28.7, and 32 percent, respectively, and as a result, Cd
atoms showed the best improvement of PLQE.
To further study the effect of different cation doping on PbS QDs film, X-ray photoelectron spectroscopy (XPS) and
Time-resolved PL (TRPL) were employed. As shown in Fig. 3a, the corresponding peaks to M elements (Zn, Ca,
and Cd) in the PbS QDs were determined. Furthermore, in Cd-doped PbS QDs, there was a trace of chlorine doping
at the surface of the PbS QDs, as shown in Fig. 3a. In addition, TRPL results demonstrated a lifetime enhancement
of PbS QDs using different cation doping, of which the Cd-doped nanocrystals showed the best carrier lifetime
compared with the others (Ca and Zn).
120 Mohammad Mahdi Tavakoli / Procedia Engineering 139 (2016) 117 – 122

Fig. 3. (a) XPS spectra, and (b) time-resolved photoluminescence lifetime of PbS QDs spectra before and after elemental doping using different
cations.

The maximum carrier lifetime was for the Cd doped sample with 1.41 µs which has almost an 80% improvement
compared with the undoped sample. Adsorption of M cations on the surface of the PbS QDs reduces the trap
formation due to the change of charge balance. In order to investigate the effect of cation doping on the photovoltaic
application, bulk heterojunction PbS QDs solar cells were fabricated. In this regard, a layer-by layer spin-coating
process on TiO2-coated FTO substrates was afforded. The methods used for the preparation of these substrates are
explained elsewhere [5]. Spin coating was performed at 2500 rpm and solid-state ligand exchange was applied by
1% v/v (Mercapto propionic acid) MPA in methanol. The thickness of the PbS film was about 300 nm. The top
contacts were deposited by thermal evaporation of MoO3 and Au. Fig. 4 shows the characteristics of the devices.
The device architecture and schematic of the PbS QD after doping are shown in Fig. 4a and 4b, respectively. Fig. 4c
andd show the current density-voltage (J-V) curves under simulated (AM 1.5 G) solar irradiation, and the external
quantum efficiency (EQE) spectrum of the cells, respectively. The figures of merit for these cells are summarized in
Table 1. The highest power conversion efficiency (PCE) was for the Cd doped PbS QDs device with a 5.81%
efficiency. The high current density (Jsc) and open circuit voltage (Voc) of this device is attributed to the longer
lifetime of carriers due to the surface doping of PbS QDs by Cd atoms [20]. Compared with the undoped device
with a 3.77% PCE, we improved the device performance by about 54% using Cd doping. In addition, Ca and Zn
dopants enhanced the PCE of the devices up to 5.3% and 4.85%, respectively. As a result, cation doping presents an
 Mohammad Mahdi Tavakoli / Procedia Engineering 139 (2016) 117 – 122 121

effective approach to improve the PCE of QD solar cells due to the enhancement of Jsc and Voc. As can be seen in fig
4d, the EQEs of these devices have a good agreement with J-V measurements.

Fig. 4. Device characterizations: (a) Cross-sectional SEM and schematic images of device, (b) Schematic of PbS QD doped with different
cations, (c) Photovoltaic measurement under 1.5 AMG, and (d) External quantum efficiency vs. wavelength of bulk heterojunction PbS QDs
device.

Table 1. The figures of merit for doped and undoped PbS QDs solar cells.
Device Voc (V) Jsc (mA/cm2) FF (%) PCE (%)

PbS 0.53 13.2 54 3.77

PbS-Cd 0.59 20.1 49 5.81

PbS-Ca 0.59 17.4 52 5.3

PbS-Zn 0.57 16.7 51 4.85

4. Conclusions
We introduced a hot-injection procedure to synthesize monodispersed, highly crystalline PbS QDs with an average
size of 3 nm. Optical studies and TRPL measurements further revealed that Cd doped PbS QDs have a longer PL
lifetime (1.41 µs) compared with undoped PbS QDs (0.78 µs). These favorable characteristics of PbS QDs allowed
us to use them as active layers of solar cells with an efficiency of 5.8%. Our study demonstrates the importance of
proper heterostructure design of hybrid materials for photovoltaic applications. When passivation with M2+ cations
was performed, the current density increased as well as the open circuit voltage due to passivation of the mid-gap
trap states. As a result, the power conversion efficiency (PCE) was improved by Cd doping by up to 54%.
References
[1] E.H. Sargent, Colloidal quantum dot solar cells, Nat. photon. 6 (2012) 133-135.
[2] M. Graetzel, R.A.J. Janssen, D.B. Mitzi, E.H. Sargent, Materials interface engineering for solution-processed photovoltaics, Nat. 488 (2012)
304-312.
[3] E.H. Sargent, Infrared photovoltaics made by solution processing, Nat. Photon. 3 (2009) 325-331.
122 Mohammad Mahdi Tavakoli / Procedia Engineering 139 (2016) 117 – 122

[4] M.A. Hines, G.D. Scholes, Colloidal PbS nanocrystals with size-tunable near-infrared emission: observation of post-synthesis self-narrowing
of the particle size distribution, Adv. Mater. 15 (2003) 1844-1849.
[5] A.H. Ip, S.M. Thon, S. Hoogland, O. Voznyy, D. Zhitomirsky, R. Debnath, L. Levina, L.R. Rollny, G.H. Carey, A. Fischer, K.W. Kemp, I.J.
Kramer, Z. Ning, A.J. Labelle, K.W. Chou, A. Amassian, E.H. Sargent, Hybrid passivated colloidal quantum dot solids, Nat. nanotech. 7 (2012)
577-582.
[6] O. Voznyy, D. Zhitomirsky, P. Stadler, Z. Ning, S. Hoogland, E.H. Sargent, A charge-orbital balance picture of doping in colloidal quantum
dot solids, ACS Nano 6 (2012) 8448-8455.
[7] A.G. Pattantyus-Abraham, I.J. Kramer, I.J. Barkhouse, A.R. Wang, X. Konstantatos, G. Debnath, R. Debnath, L. Levina, I. Raabe, M.K.
Nazeeruddin, M. Gratzel, E.H. Sargent, Depleted-heterojunction colloidal quantum dot solar cells, ACS Nano 4 (2010) 3374-3380.
[8] M.M. Tavakoli, A. Tayyebi, A. Simchi, H. Aashuri, M. Outokesh, Z. Fan, Physicochemical properties of hybrid graphene–lead sulfide
quantum dots prepared by supercritical ethanol, J. Nanoparticle Research 17 (2015) 1-13.
[9] M.M. Tavakoli, R. Tavakoli, P. Davami, H. Aashuri, A quantitative approach to study solid state phase coarsening in solder alloys using
combined phase-field modeling and experimental observation, J. Comput. Electron. 13 (2014) 425-431.
[10] M.M. Tavakoli, S.M. Abbasi, Effect of molybdenum on grain boundary segregation in Incoloy 901 superalloy, Mater. Design. 46 (2013)
573-578.
[11] M.M. Tavakoli, A. Simchi, H. Aashuri, Supercritical synthesis and in situ deposition of PbS nanocrystals with oleic acid passivation for
quantum dot solar cells, Mater. Chem. Phys. 156 (2015) 163-169.
[12] A. Tayyebi, M. M. Tavakoli, M. Outokesh, A. Shafiekhani, A. Simchi, Supercritical Synthesis and Characterization of “Graphene-PbS
Quantum Dots” Composite with Enhanced Photovoltaic Properties, Industrial & Engineering Chemistry Research 54 (2015) 7382í7392.
[13] S.A. McDonald, G. Konstantatos, S. Zhang, P.W. Cyr, E.J.D. Klem, L. Levina, E.H. Sargent, Solution-processed PbS quantum dot infrared
photodetectors and photovoltaics, Nat. Mater. 4 (2005) 138-142.
[14] D. Aaron, R. Barkhouse, R. Debnath, I.J. Kramer, D. Zhitomirsky, A.G. Pattantyus-Abraham, L. Levina, L. Etgar, M. Grätzel, E.H. Sargent,
Depleted bulk heterojunction colloidal quantum dot photovoltaics, Adv. Mater. 23 (2011) 3134-3138.
[15] D. Zhitomirsky, Q. Voznyy, S. Hoogland, E.H. Sargent, Measuring charge carrier diffusion in coupled colloidal quantum dot solids, ACS
Nano 7(2013) 5282-5290.
[16] S. Xiong, B. Xi, D. Xu, C. Wang, X. Feng, H. Zhou, Y. Qian, L-cysteine-assisted tunable synthesis of PbS of various morphologies, J. Phys.
Chem. C 45 (2007) 16761-16767.
[17] S.M. Thon, A.H. Ip, O. Voznyy, L. Levina, K.W. Kemp, G.H. Carey, S. Masala, E.H. Sargent, Role of Bond Adaptability in the Passivation
of Colloidal Quantum Dot Solids, ACS nano 7 (2013) 7680-7688.
[18] M.J. Speirs, D.M. Balazs, H.H. Fang, L.H. Lai, L. Protesescu, M.V. Kovalenko, M.A. Loi, Origin of the increased open circuit voltage in
PbS–CdS core–shell quantum dot solar cells, J. Mater. Chem. A 3 (2015) 1450-1457.
[19] Z. Ning, O. Voznyy, J. Pan, S. Hoogland, V. Adinolfi, J. Xu, M. Li, A.R. Kirmani, J. Sun, J. Minor, K.W. Kemp, H. Dong, L. Rollny, A.
Labelle, G. Carey, B. Sutherland, I. Hill, A. Amassian, H. Liu, J. Tang, O.M. Bakr, E.H. Sargent, Air-stable n-type colloidal quantum dot
solids, Nat. mater. 13 (2014) 822-828.
[20] O. Voznyy, S.M. Thon, A.H. Ip, E.H. Sargent, Dynamic trap formation and elimination in colloidal quantum dots, J. Phys. Chem. Lett. 4
(2013) 987-992.
[21] M.M. Tavakoli, S.G. Shabestari, M. Ghanbari, Effect of thixoforming on morphological changes in iron-bearing intermetallics and
mechanical properties of Al–Si–Cu alloys, International Journal of Materials Research 105 (2014) 1210-1217.
[22] Y. Gao, H. Jin, Q. Lin, X. Li, M.M. Tavakoli, S. Leung, W.M. Tang, L. Zhou, H.L. Wa Chan, Z. Fan, Highly flexible and transferable
supercapacitors with ordered three-dimensional MnO 2/Au/MnO2 nanospike arrays, Journal of Materials Chemistry A 3, (2015) 10199-10204.
[23] S.G. Shabestari, M.M. Tavakoli, M. Ghanbari, Effect of Semi-Solid Processing on Iron-Bearing Intermetallic Compounds in A380
Aluminum Alloy, Solid State Phenomena, 217 (2015) 397-404.
[24] M.M. Tavakoli, K. H. Tsui, S. F. Leung, Q. Zhang, J. He, Y. Yao, D. Li, Z. Fan, Highly Efficient Flexible Perovskite Solar Cell with Anti-
Reflection and Self-Cleaning Nanostructures, ACS Nano, (2015) DOI: 10.1021/acsnano.5b04284.
[25] M. M. Tavakoli, H. Aashuri, A. Simchi, S. Kalytchuk, Z. Fan, Quasi Core/Shell Lead Sulfide/Graphene Quantum Dots for Bulk
Heterojunction Solar Cells, J. Phys. Chem. C 119 (2015) 18886–18895.
[26] M.M. Tavakoli, H. Aashuri, A. Simchi, Z. Fan, Hybrid zinc oxide/graphene electrodes for depleted heterojunction colloidal quantum-dot
solar cells, Phys. Chem. Chem. Phys., (2015) DOI: 10.1039/C5CP03571F.
[27] M. M. Tavakoli, L. Gu, Y. Gao, C. Reckmeier, J. He, A. L. Rogach, Y. Yao, Z. Fan, Fabrication of efficient planar perovskite solar cells
using a one-step chemical vapor deposition method, Sci. Rep. (2015) DOI: 10.1038/srep14083.