Asian Journal of Green Chemistry 8 (2024) 15-24

Asian Journal of Green Chemistry

Original Research Article View Article Online │ View Journal

Study of PbS Quantum Dots (QDs) and Proposing Pb@PbS-

QD@CdSe for New Generation of LEDs
Ashraf Heidaripoura,* , Fateme Salmanib
aDepartment of Chemistry, Payame Noor University, Karaj, Iran
bResearch Center Karaj Moallem, Karaj, Iran

ARTICLE INFORMATION ABSTRACT

Submitted: 9 June 2023 PbS quantum dots (PbS-QDs) are one of the best candidates in new
Revised: 26 July 2023 generation of LEDs. When the PbS-QDs are exposed to light spectrum, the
Accepted: 31 July 2023 electrons in the valence band (VB) are excited to the conduction band (CB).
Available online: 5 August 2023 The excited electrons then return from the CB to the VB and release extra
energy by emitting light. The return of electrons to the VB makes it possible
Manuscript ID: AJGC-2307-1398
to repeat the light absorption-emission circle. If the size of the PbS-QDs is
Checked for Plagiarism: Yes
smaller than the Bohr magneton radius (PMR), the probability of the
Language Editor:
electron return to the VB decreases. This leads to phenomena named
Dr. Fatimah Ramezani quantum dot blinking (QDB) in light-emitting diodes (LEDs), which is not
Editor who approved publication:
desirable. In this research, a new approach has been proposed in which the
Dr. Ali Ramazani
addition of a metal substrate for PbS-QDs with a semiconductor shell with a
DOI: 10.48309/ajgc.2024.406146.1398 suitable band edge could increase PbS-QDs efficiency in QD-LEDs and
overcome the QDB problem.
© 2024 by SPC (Sami Publishing Company), Asian Journal of Green
KEYWORDS Chemistry, Reproduction is permitted for noncommercial purposes.
PbS-QDs
Blink
Protective shell
LED
Pb
CdSe

Corresponding authors, email: [email protected] (A. Heidaripour).

Tel.: 9127672157.
Study of PbS Quantum Dots (QDs) … 16

Graphical Abstract

Introduction Size-shape dependence in PbS nanoparticles

When crystalline and micron The shape, size, and elemental composition
semiconductors are converted into amorphous of lead sulfide (PbS) depends on the
with nanometer dimensions, not only retain arrangement and density of atoms. In terms of
their semiconducting property, but also the difference in the ratio of Pb to S (Pb/S), the
acquire other properties that lead to wide predicted size is consistent with the
application. Semiconductor nanocrystals are measurements reported in the literature, as
tiny light-emitting particles on the nanometer displayed in Figure 1.
scale [1]. Researchers have studied these While the surfaces of the smaller particles of
particles and developed them for wide-ranging PbS (diameter < 2.7 nm) are completely
applications such as solar energy conversion, covered with Pb (111) oriented facets, the
optoelectronic devices, molecular and cellular larger PbS, between 2.7 and 7.5 nm, have a
imaging, and ultrasensitive detection [2]. cubic shape with a preferential orientation Pb
The comparison of nanometer (100). As the PbS dimensions increase, the
semiconductor and micron semiconductor Pb/S ratio decreases, although the Pb/S ratio is
shows that the electron bands in nanometer always higher than one [5].
particles have less density [3]. When the
number of atoms reaches 44 in a crystalline PbS quantum dots (PbS-QDs) and BMR
particle, the separation begins in electronic
PbS in bulk state (micron) has a bandgap of
levels. Therefore, the CB moves away from the
0.37 eV. When the PbS size decreases the
VB and the band gap increases. These changes
bandgap increases, so that the PbS size with 10
lead to different behaviors in nanometer
and 3 nm corresponds to bandgap of 0.6 and
semiconductors compared to its micron type
1.3 eV. This results to decrease of absorbed
[4].
wavelength [6, 7].
A. Heidaripour & F. Salmani 17

Figure 1. Relationship between PbS diameter and Pb/S ratio [10]

The bandgap of 0.37 eV is equivalent to an between electron and hole [9, 10]. When light
absorption wavelength of 3350 nm in the with sufficient energy meets the
infrared (IR) range. The bandgap of 0.6 and 1.3 semiconductor and the electron is transferred
eV is equivalent with 2066 and 953 nm, from the VB to the CB, a hole remains in the
respectively. This is a blue shift to lower valence band. The distance between the
wavelength and higher energy regions, i.e. electron and hole is BMR and different from
near-IR. As a theoretical point of view, it is one to another semiconductor. The BMR is an
possible to further reduce the size of PbS to intrinsic characteristic of a semiconductor [11,
reach a band gap of 1.5 eV (826 nm) [8]. In this 12].
case, the absorption range of PbS approaches
the high energy range in the visible region, Quantum limitation and problem design
which is the intense region, and this can be
If the QD size is reduced to such an extent
controversial. When the dimensions of a
that the electronic levels change from
semiconductor are reduced in all three
continuous to discrete, and then approach the
dimensions and become nanometers, they are
state of molecular levels and they will show
called quantum dots (QDs), which are actually
special properties that allow their use in
zero-dimensional nanoparticles.
various applications. However, reducing the
In fact, when the size of the semiconductor
QD size from the permissible size and less than
becomes smaller than the Bohr-magneton
BMR is associated with quantum limitations
radius (BMR), the semiconductor nanoparticle
such as instability and non-belonging of the
is a QD. The BMR is the equilibrium distance
excited electron to a QD [13-17].
Study of PbS Quantum Dots (QDs) … 18

Phenomenon of quantum dots blink (QDB) shell (PS) around it. This is often done to
protect the PbS-QDs from instability caused by
The BMR and electron-hole distance for the the QDs dissolution in the solvent. According to
PbS-QDs is 20 nm. In other words, if the size of Figure 3, by creating a PS around the PbS-QDs,
PbS crystals becomes less than 20 nm, they the electrons are trapped inside the PS and
become the QDs. The electrons in PbS-QDs are cannot escape from the PbS-QDs domain. In
transformed into an excited state by absorbing this way, the electrons have to return to the
light corresponding to their bandgap, and then ground state and be ready to absorb the light.
excited electrons return to their original state Thus, the QDB phenomenon is omitted [16]. It
by emitting light. By this way, they are ready to has shown that change of the PbS-QDs size
absorb light again. Because of this property of results the displacement in VB edge more than
continuous absorption and emission of light, the CB edge. Furthermore, the PS can be an
they emit continuous radiation of light with insulating or a semiconductor. If the PS is an
specific wavelength [13, 14]. If there is no insulator, it prevents the escape of electrons
protective shell (PS) around the PbS-QDs, the from the PbS-QDs domain, but if the PS is a
excited electron can leave the confined space in semiconductor, the electron exchange may
PbS-QDs domain and would not return to the occur between the CB edges of core (PbS-QDs)
ground state. This event causes a discontinuity and the PS. This exchange reduces the PbS-QDs
in light emission, which is called the Quantum efficiency. In this case, it is very important to
Dots Blink (QDB), as indicated in Figure 2. The choose a suitable semiconductor with a well-
phenomenon of QDB reduces the light defined band edge to minimize the excited
radiation efficiency in the QDs [15, 16]. electron exchange between the PbS-QDs and
PS in the CB edges [18]. A lot of work has been
Protective shell around PbS-QDs
done in this field. Creating a protective
Much research has been done on PbS-QDs semiconductor shell from silica, CdS, CdSe,
to solve the size reduction problems. For TiO2, and perovskite materials are just a few
example, one solution is to create a protective examples. [19-24].

Figure 2. Views of the quantum dots blinking [14, 15]

A. Heidaripour & F. Salmani 19

Figure 3. Schematic of a PbS-QD with a PS

Quantum dot light-emitting diodes (QD-LEDs) In addition, there is two ways to increase
PbS-QDs efficiency. One is to deposit PbS-QDs
QD-LEDs are made using a QDs film as the on the metal core to increase the capacity of
emitting layer. When a DC voltage is applied, PbS-QDs based on the electrochemical capacity
electrons and holes are injected into the QDs to pattern (ECP) of metal [11], and the other is to
emit light. In the last two decades, colloidal QD- create a PS on the PbS-QDs to overcome the
LEDs as a new generation of LEDs have been QDB problem [16]. This type of design of
upgraded from less than 0.01% to 18%. Its quantum dots with metal substrate is an
unique feature is high luminescence efficiency innovative and new idea. A schematic view of
and tunable color with specific size of colloidal the final product is shown in Figure 4.
QDs.
Accordingly, QD-LEDs have a high potential Experimental
for use in high-quality and energy-efficient
thin-film displays [23-26]. If the problem of the The fabrication and electrochemical study
QDB is solved, the QD-LEDs are the best of PbS-QDs have all been reported in our
replacement of the current LED made from previous papers. Likewise, the study of the
gallium arsenide (GaAs), gallium phosphide effect of metal (Pb) substrate on the PbS-QDs
(GaP), or gallium arsenide phosphide (GaAsP). capacity has been done by electrochemical
The Ga and As are very dangerous for the method. All electrochemical measurements
environment and health [22, 23]. The were carried out in a conventional three
comparison of Pb with Ga and As, shows that electrodes cell powered by a potentiostat/
all of them are toxic and dangerous. However, galvanostat (EG&G, model 273 A) that was run
the use of PbS-QDs due to its lower amount and by a PC through M 270 and M398 software via
higher efficiency promises that the a GPIB interface, and a frequency response
replacement of PbS-QDs instead of Ga and As analyzer (EG&G, model 1025) [11]. In this
are moving in the direction of green chemistry article, only the theoretical evaluation of the
[22]. results and its application has been discussed.
Theoretical aspect
Study of PbS Quantum Dots (QDs) … 20

The idea followed in this article is that if According to previous our research, the
nanometer particles of the desired metal are formation of Pb substrate for PbS-QD increases
already dispersed in the solution where PbS- the capacity of PbS, which is more noticeable in
QDs are formed, and then the PbS-QDs will the potential of -0.3 to 1.5 V, as demonstrated
settle on the surface of the metal particles and in Figure 6. This potential is very important in
Metal@PbS-QD is formed. Finally, a suitable PS red emitting LEDs. Typically, the LED voltage is
is deposited on the Metal@PbS-QD which between 1.8 and 3.3 volts. A red emitting LED
results Metal@PbS-QD@PS. The procedure is works with a potential of 1.7 to 2.0V, but a blue
depicted schematically in Figure 5. emitting LED requires a potential of about 3 to
3.3V. The Pb@PbS capacity increases by 10 to
Results and Discussion 50% compared to PbS only in the potential
range of -0.3 to 1.5 V. Therefore, Pb@PbS is
Selection of a metal core for PbS-QD
suitable for use in red emitting LEDs.

Figure 4. PbS-QDs deposition on the metal and covered with a PS

Figure 5. Preparation of Metal/PbS-QD/PS

A. Heidaripour & F. Salmani 21

Figure 6. Capacitance of PbS and Pb/PbS

Selection of a semiconducting shell for PbS-QD between the CB edge of the PS (𝐶𝐵𝑃𝑆 ) and that
of the PbS-QD (𝐶𝐵𝑃𝑏𝑆−𝑄𝐷 ) is presented with
When the PS is a semiconductor, its role ΔCB, as indicated in Equation 1. Greater ΔCB
gets a little complicated. Therefore, when PbS- results show more significant electronegativity
QD/PS is subjected to a potential difference, difference (χ), i.e. 𝜒 ≈ Δ𝐶𝐵 . Therefore, the excited
both PbS-QD and PS electrons are excited from electrons in PS are more strongly drawn to the
VB to CB. If the CB edge of PS is higher than CB of PbS-QD. For this reason, the CdSe is the
that of PbS-QD, the excited electrons are best PS for PbS-QD (PbS-QD@CdSe) with
transferred from PS to the PbS-QD. This ΔCB=0.24, compared with PbS-QD/CdS with
process enhances the optical activity of PbS-QD ΔCB=0.12 [27].
because increases the population of electrons
in the CB of PbS-QD. But when the CB edge of CB = CBPS − CBPbS −QD (1)
PS is not placed in the right position and is
lower than that of PbS-QD, the transfer of Pb@PbS-QD@CdSe application in LEDs
electrons from PbS-QD to PS will be done. This
will interfere with the PbS-QD work process The basis of the LED is a diode, and the
because the population of electrons is reduced semiconductor diode is a crystal piece with a P-
in the CB of PbS-QD. N junction, which is connected into two
According to Figure 7, the CB edge of cadmium electrical terminals. The N junction is a
selenide (CdSe) and cadmium sulfide (CdS) is semiconductor with an additional negative
higher than that of PbS. But in the case of charge, and the P junction is actually a
titanium dioxide (TiO2), the CB edge is lower semiconductor with an additional positive
than that of PbS. Accordingly, in most articles, charge. The designed structure of Pb@PbS-
CdSe and CdS have been used as a PS for PbS- QD@CdSe can be embedded within the N
QDs. This selection strengthens the light junction material to strengthen its efficiency, as
emitting in PbS-QDs. In addition, the difference demonstrated in Figure 8.
Study of PbS Quantum Dots (QDs) … 22

Figure 7. VB and CB edges of CdSe, CdS and TiO2 with respect to PbS

Figure 8. Embedding of Pb@PbS-QDs@CdSe in N junction

Conclusion So the Pb@PbS-QD is suitable for use in red

emitting LEDs.
The PbS-QDs are narrow bandgap
semiconductors that absorb in the infrared Acknowledgments
region. By changing the ratio of PbS precursors,
the PbS-QDs with desired size and suitable The authors would like to sincerely thank all
bandgap can be prepared. To stabilize PbS-QDs those who provided them with the laboratory
with dimensions smaller than BMR, it is results. They would like to thank the student
necessary to create a PS around them. CdSe is a research of Moallem for providing them with
suitable PS for this purpose due to have a CB laboratory space. The authors are grateful to
edge higher than the CB edge of the PbS-QDs. those who gave spiritual support and would
Research has shown that the capacity of like to thank Fateme's parents who sincerely
Pb@PbS increases by 10 to 50% compared to and enthusiastically helped reach the goals of
PbS only in the potential range of -0.3 to 1.5 V. the research.
A. Heidaripour & F. Salmani 23

Disclosure Statement [6]. Gan J., Yu M., Hoye R.L., Musselman K.P., Li
Y., Liu X., Zheng Y., Zu X., Li S. Mater Today
No potential conflict of interest was reported Nano., 2021, 13:100101 [Crossref], [Google
by the authors. Scholar], [Publisher]
[7]. Carey G.H., Abdelhady A.L., Ning Z., Thon
Funding
S.M., Bakr O.M., Sargent E.H. Chem Rev., 2015,
This research did not receive any specific grant 115:12732 [Crossref], [Google Scholar],
from funding agencies in the public, [Publisher]
commercial, or not-for-profit sectors. [8]. Choi H., Ko J.H., Kim Y.H., Jeong S. Journal of
the American Chemical Society., 2013,
Authors' Contributions 135:5278 [Crossref], [Google Scholar],
[Publisher]
All authors contributed to data analysis, [9]. Dong Y., Sun W., Huang C., Huang S., Yan C.,
drafting, and revising of the paper and agreed Wen J., Zhang X., Huang Y., Shang Y., Wang
to be responsible for all the aspects of this T. Opt Mater Express., 2022, 12:1838
work. [Crossref], [Google Scholar], [Publisher]
[10]. Kria M., Nautiyal V.V., Lakaal K., El
Orcid
Hamdaoui J., Pérez L.M., Varsha Laroze D.,
Ashraf Heidaripour Prasad V., Long G., Feddi E. Front Phys., 2022,
https://orcid.org/0000-0003-0223-5383 10:942758 [Crossref], [Google Scholar],
Fateme Salmani [Publisher]
https://orcid.org/0009-0002-6470-7614 [11]. Heidaripour A. Journal of the Indian
Chemical Society., 2023, 100:100830
References [Crossref], [Google Scholar], [Publisher]
[12]. Miandari S., Jafarian M., Mahjani M.G.,
[1]. Memming R., Semiconductor
Heidaripour A. Bull Chem Soc Jpn., 2015,
electrochemistry, John Wiley & Sons., 2015
88:209 [Crossref], [Google Scholar],
[Google Scholar], [Publisher]
[Publisher]
[2]. Rogach A.L., Gaponik N., Lupton J.M.,
[13]. a) Elfurawi U., Doctoral dissertation,
Bertoni C., Gallardo D.E., Dunn S., Li Pira N.,
University of Nottingham., 2012 [Google
Paderi M., Repetto P., Romanov S.G., O'Dwyer
Scholar], [Publisher]; b) Chandankar S.M.,
C. Angew Chem Int Ed Engl., 2008, 47:6538
Nerkar P.P., Mahajan H.S. Journal of Medicinal
[Crossref], [Google Scholar], [Publisher]
and Nanomaterials Chemistry, 2022, 5:48
[3]. Link S., Burda C., Wang Z.L., El-Sayed M.A. J
[Crossref], [Publisher]; c) Hamid Abd A., Adnan
Chem Phys., 1999, 111:1255 [Crossref], [Google
Ibrahim O. Chemical Methodologies, 2022,
Scholar], [Publisher]
6:823 [Crossref], [Publisher]; d) Noori H.N.,
[4]. Wang Y., Song Z., Wan J., Betzler S., Xie Y.,
Abdulameer A.F. Chemical Methodologies, 2022,
Ophus C., Bustillo K.C., Ercius P., Wang L.W.,
6:842 [Crossref], [Publisher]; e) Islam J., Kumer
Zheng H. Journal of the American Chemical
A., Chakma U., Alam M.M., Biswas S., Ahmad Z.,
Society., 2022, 144:23474 [Crossref], [Google
Islam M.S., Jony M.I.J., Ahmed M.B. Advanced
Scholar], [Publisher]
Journal of Chemistry, Section A, 2022, 5:164
[5] Beygi H., Sajjadi S.A., Babakhani A., Young
[Crossref], [Publisher]; f) Ali F., Fazal S., Iqbal
J.F., van Veggel F.C. Appl Surf Sci., 2018, 457:1
N., Zia A., Ahmad F. Journal of Medicinal and
[Crossref], [Google Scholar], [Publisher]
Study of PbS Quantum Dots (QDs) … 24

Nanomaterials Chemistry, 2023, 5:106 [20]. Tanaka A. Toxicol Appl Pharmacol., 2004,
[Crossref], [Publisher]; g) López-Dino J., 198:405 [Crossref], [Google Scholar],
Hernández-Paz J., Olivas-Armendáriz I., [Publisher]
Rodríguez González C. Journal of Medicinal and [21]. Shirasaki Y., Supran G.J., Bawendi M.G.,
Pharmaceutical Chemistry Research, 2023, Bulović V. Nat Photonics., 2013, 7:13 [Crossref],
5:915 [Crossref], [Publisher]; h) Mahal E., Al- [Google Scholar], [Publisher]
Mutlaq S. Journal of Medicinal and [22]. Aynehband S., Mohammadi M., Poushimin
Pharmaceutical Chemistry Research, 2023, R., Azar M.H., Nunzi J.M., Simchi A. Mater Res
5:264 [Publisher]; Bull., 2022, 147:111648 [Crossref], [Google
[14]. a) Heidaripour A. Iranian J Chem Chem Scholar], [Publisher]
Eng., 2022 [Crossref], [Google Scholar], [23]. Wang D., Qian J., Cai F., He S., Han S., Mu
[Publisher]; b) Farahani E., Haddadi M. Int. J. Y. Nanotechnol., 2012, 23:245701 [Crossref],
Adv. Biol. Biomed. Res., 2022, 10:288 [Crossref], [Google Scholar], [Publisher]
[Publisher]; c) Shete R., Fernandes P., Borhade [24]. Heidaripour A. Journal of the Indian
B., Pawar A., Sonawane M., warude N. Journal of Chemical Society., 2023, 100:100830
Chemical Reviews, 2022, 4:331 [Crossref], [Crossref], [Google Scholar], [Publisher]
[Publisher] [25]. Heidaripour A., Jafarian M., Gobal F.,
[15]. Peterson J.J., Krauss T.D. Nano Lett., Mahjani M.G., Miandari S. J Appl
2006, 6:510 [Crossref], [Google Scholar], Phys., 2014,116:034906 [Crossref], [Google
[Publisher] Scholar], [Publisher]
[16]. Yuan G., Gómez D.E., Kirkwood N., Boldt [26]. Du M., Shi H. In APS March Meeting
K., Mulvaney P. ACS nano., 2018, 12:3397 Abstracts., 2015, 2015:A15 [Google Scholar],
[Crossref], [Google Scholar], [Publisher] [Publisher]
[17]. Che Y., Zhang Y., Cao X., Song X., Zhang H., [27]. Tu N. In Quantum Dots-Fundamental and
Cao M., Dai H., Yang J., Zhang G., Yao J. Appl Phys Applications., 2020, 68 [Google Scholar],
Lett., 2016,109:263101 [Crossref], [Google [Publisher]
Scholar], [Publisher] How to cite this manuscript: Ashraf
[18]. Ma C., Shi C., Lv K., Ying C., Fan S., Yang Y. Heidaripour*, Fateme Salmani. Study of PbS
Nanoscale., 2019, 11:8402 [Crossref], [Google Quantum Dots (QDs) and Proposing Pb@PbS-
Scholar], [Publisher] QD@CdSe for New Generation of LEDs. Asian
[19]. Moroz P., Liyanage G., Kholmicheva N.N., Journal of Green Chemistry, 8(1) 2024, 15-24.
Yakunin S., Rijal U., Uprety P., Bastola E., DOI:10.48309/ajgc.2024.406146.1398
Mellott B., Subedi K., Sun L., Kovalenko
M.V. Chem Mater., 2014, 26:4256 [Crossref],
[Google Scholar], [Publisher]