CHAPTER 2

Fundamentals of Quantum Dots

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2.1 Structure and Classification of Quantum Dots
Quantum dots (QDs) are nanoscale crystalline semiconductor structures with
dimensions typically ranging from 1 to 20 nanometres—small enough that quantum
mechanical effects dominate their physical and optical behaviour [1]. The term
"quantum dot" was first coined by Mark Reed in 1988, though the theoretical
framework and experimental synthesis preceded this by several years [2].
Structurally, quantum dots consist of a crystalline core of inorganic
semiconductor material, such as cadmium selenide (CdSe) or zinc sulfide (ZnS),
surrounded in most engineered variants by a protective shell and an outer ligand
layer. The core governs the primary optical response, the shell passivates surface
defects and improves quantum yield, and the ligands provide colloidal stability and
permit surface functionalisation. This core–shell–ligand architecture is central to the
high photostability and tuneable emission observed in high-performance QDs [1].
Quantum dots can be classified along two broad axes: by their physical
dimensionality and by their chemical composition. From a dimensionality standpoint
they are zero-dimensional (0D) objects—charge carriers are confined in all three
spatial dimensions—which distinguishes them from quantum wires (1D) and
quantum wells (2D). Compositionally, the principal classes are semiconductor QDs
(Group II–VI and Group III–V compounds), carbon QDs, graphene QDs, and
perovskite QDs, each discussed in detail in Section 2.5 [3].

2.2 Quantum Confinement Effect

The defining physics of quantum dots is the quantum confinement effect,
which arises when the physical dimensions of a semiconductor crystal are reduced
to a length scale comparable to or smaller than the exciton Bohr radius of the
material. In bulk semiconductors, energy levels form continuous bands; as the
crystal size is reduced to the nanoscale, these bands resolve into discrete, quantised
energy levels—analogous to the particle-in-a-box problem of elementary quantum
mechanics [1].
Quantitatively, the size-dependent band gap energy E_gap(r) of a spherical
quantum dot can be approximated by the Brus equation:
E_gap(r) = E_bulk + (ℏ²π²) / (2r²) × (1/m_e* + 1/m_h*) − 1.8e² /
(4πε₀εr)

where r is the dot radius, m_e* and m_h* are the effective masses of the
electron and hole respectively, and ε is the dielectric constant of the material. The
principal prediction of this model—that band gap energy increases as particle size

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decreases—has been confirmed experimentally across a wide range of QD systems
[2]. This relationship is the fundamental origin of the size-tuneable optical properties
that make quantum dots so technologically attractive.
The confinement regime is commonly categorised as strong (r << a_B),
intermediate (r ≈ a_B), or weak (r >> a_B), where a_B is the exciton Bohr radius.
Cadmium selenide, one of the most widely studied QD materials, has a Bohr radius
of approximately 5.6 nm, making dots of 2–10 nm diameter accessible for strong-to-
intermediate confinement studies [3].

2.3 Optical and Electronic Properties

The discrete energy-level structure produced by quantum confinement
translates into a set of optical and electronic properties that are qualitatively distinct
from those of bulk semiconductors [1]. The most striking of these is size-dependent
photoluminescence: a single semiconductor material (e.g., CdSe) can be made to
emit light across the entire visible spectrum simply by varying the nanoparticle
diameter, without altering chemical composition.
Key optical characteristics of quantum dots include: (i) broad, continuous
absorption spectra that allow excitation at any wavelength shorter than the first
exciton peak; (ii) narrow, symmetrical photoluminescence emission peaks with full-
width at half-maximum (FWHM) values of 20–30 nm for high-quality colloidal QDs;
(iii) large Stokes shifts that minimise self-absorption; and (iv) exceptionally high
molar extinction coefficients, which are orders of magnitude larger than those of
conventional organic fluorophores [2].
Electronically, quantum dots exhibit a high density of states near the band
edges, single-electron charging effects, and pronounced Coulomb blockade at low
temperatures. The degeneracy of the first excited state (1S_e − 1S_3/2 transition)
gives rise to the characteristic first exciton absorption peak visible in UV-Vis spectra,
and the energy of this peak serves as a reliable indicator of mean particle size
through empirical calibration curves [3].

2.4 Photoluminescence and Exciton Dynamics

Photoluminescence (PL) in quantum dots arises from radiative recombination
of photogenerated electron–hole pairs, collectively termed excitons. When a QD
absorbs a photon with energy greater than the band gap, an electron is promoted to
the conduction band, leaving a hole in the valence band. The resulting exciton
relaxes rapidly (within picoseconds) to the band-edge state through phonon

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emission, and subsequently recombines radiatively on a nanosecond timescale,
emitting a photon whose energy corresponds to the band-gap [1].
Exciton dynamics in QDs are governed by several competing recombination
pathways. Band-edge (excitonic) emission produces the characteristic narrow PL
peak. Trap-state emission, arising from surface defects and dangling bonds, yields
broader, red-shifted emission and reduces quantum yield. Multi-exciton
recombination—particularly Auger recombination—becomes significant at higher
photon flux and results in non-radiative energy dissipation [2].
The photoluminescence quantum yield (PLQY), defined as the ratio of emitted
photons to absorbed photons, is a critical figure of merit. Bare core QDs typically
exhibit PLQYs of 10–30%, whereas optimised core–shell structures (e.g., CdSe/ZnS)
can exceed 90% [3]. Surface passivation—either through inorganic shells or organic
ligand exchange—is the primary strategy for suppressing non-radiative trap-state
recombination and achieving high PLQY. Photoluminescence blinking, the stochastic
switching between emissive and non-emissive states observable in single QDs, has
been attributed to Auger ionisation and charge trapping, and remains an active area
of research [1].

2.5 Types of Quantum Dots

2.5.1 Semiconductor Quantum Dots
Semiconductor quantum dots, particularly those based on Group II–VI (CdSe,
CdS, CdTe, ZnS, ZnSe) and Group III–V (InP, InAs) binary compounds, represent
the most extensively studied and technologically mature class of QDs [1]. Their high
crystallinity, well-characterised surface chemistry, and compatibility with established
colloidal synthesis routes make them the reference system against which other QD
types are benchmarked.
Colloidal synthesis via the hot-injection method—injection of organometallic
precursors into a coordinating solvent at elevated temperature—enables precise
control over size, shape, and composition. CdSe QDs synthesised by this approach
display PLQY values above 85% when overcoated with a ZnS or ZnSe shell [2].
Despite their outstanding performance, cadmium-based QDs raise significant
environmental and regulatory concerns due to the toxicity of cadmium ions,
motivating substantial research into heavy-metal-free alternatives such as InP,
silicon, and copper indium sulfide (CIS) QDs [3].

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2.5.2 Carbon Quantum Dots
Carbon quantum dots (CQDs) are a class of zero-dimensional carbon
nanomaterials, typically less than 10 nm in diameter, consisting of an amorphous or
nanocrystalline carbon core decorated with diverse surface functional groups
including hydroxyl, carboxyl, and amine moieties [2]. First discovered serendipitously
in 2004 during the purification of single-walled carbon nanotubes, CQDs have
attracted intense research interest owing to their low toxicity, earth-abundant
composition, chemical inertness, and facile synthesis from a broad range of
precursor materials [1].
The photoluminescence mechanism of CQDs remains incompletely
understood and is the subject of ongoing investigation. Proposed mechanisms
include quantum confinement in sp² carbon domains, surface-state emission from
oxidised functional groups, and molecular fluorophore emission from discrete small-
molecule species formed during synthesis. The excitation-dependent emission
behaviour characteristic of many CQD preparations—whereby the emission
maximum shifts with excitation wavelength—is often attributed to a heterogeneous
distribution of surface emissive sites [3].

2.5.3 Graphene Quantum Dots

Graphene quantum dots (GQDs) are nanoscale fragments of graphene,
typically 1–20 nm in lateral dimension and one to a few atomic layers thick, in which
quantum confinement and edge effects open a band gap in otherwise semimetallic
graphene [2]. They may be conceptualised as a structural bridge between CQDs
(which have a predominantly amorphous or sp³-hybridised core) and extended
graphene sheets, retaining the in-plane hexagonal carbon lattice of the latter while
exhibiting the discrete electronic structure of the former.
GQDs are synthesised by both top-down approaches (e.g., chemical oxidation
and exfoliation of graphite or graphene oxide, followed by hydrothermal cutting) and
bottom-up approaches (e.g., solution-phase pyrolysis of polycyclic aromatic
hydrocarbons) [3]. Compared to CQDs, GQDs tend to display stronger quantum
confinement due to their well-defined, crystalline sp² carbon structure. Edge
functional groups play a dominant role in governing PL behaviour: zigzag edges
introduce mid-gap states that can produce near-infrared emission, while armchair
edges promote blue emission [1]. GQDs also exhibit remarkable photostability and
resistance to photobleaching, making them attractive for bioimaging applications.

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2.5.4 Perovskite Quantum Dots
Perovskite quantum dots (PQDs), particularly those based on lead halide
perovskites of general formula APbX₃ (A = Cs, methylammonium; X = Cl, Br, I or
mixed halides), have emerged as a transformative class of luminescent
nanomaterials following their first report in 2015 [3]. Their defining characteristics
include defect-tolerant crystal structures, extremely narrow emission linewidths
(FWHM < 20 nm), near-unity photoluminescence quantum yields achievable without
complex core–shell engineering, and facile compositional tuneability of emission
across the entire visible spectrum via halide substitution.
The defect tolerance of perovskites—a consequence of their ionically bonded
structure in which common point defects create only shallow trap states that do not
efficiently quench luminescence—fundamentally distinguishes them from
conventional II–VI QDs and partially explains their remarkable as-synthesised
quantum yields [1]. However, PQDs face significant challenges related to (i) moisture
and oxygen sensitivity, which leads to rapid degradation under ambient conditions;
(ii) the toxicity of lead, motivating research into lead-free alternatives (e.g., Sn² ⁺,
Bi³⁺, and double perovskites); and (iii) ion migration under operational conditions in
devices [2]. Encapsulation strategies and compositional engineering are active
research frontiers aimed at improving the long-term stability of PQD-based light-
emitting and photovoltaic devices.

2.6 Green Synthesis and Sustainable Quantum Dots

Conventional QD synthesis typically relies on high-boiling-point organic
solvents, toxic organometallic precursors, and energy-intensive conditions, raising
concerns about environmental impact and large-scale manufacturability. The field of
green synthesis seeks to address these challenges by developing aqueous-phase,
low-temperature, and biologically-derived synthesis routes that minimise hazardous
chemical inputs while retaining the desired nanoscale properties [3].
Hydrothermal and microwave-assisted methods in aqueous media have
demonstrated success for CQDs, GQDs, and ZnS-based semiconductor QDs. A
particularly active area involves the use of biomass-derived precursors—fruit peels,
agricultural waste, plant extracts, and amino acids—as both carbon sources and
surface-passivating agents for CQD synthesis [2]. These one-pot approaches
frequently yield fluorescent nanoparticles with satisfactory quantum yields and
inherently biocompatible surface chemistries, well suited for biosensing and
bioimaging without further functionalisation.

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 For semiconductor QDs, the replacement of cadmium and lead with non-toxic
alternatives (ZnS, InP, CIS, AgInS₂) represents a key axis of sustainable
development. Aqueous synthesis of InP QDs using non-pyrophoric phosphorus
sources and bio-derived reducing agents has been demonstrated, though achieving
the size monodispersity and PLQY of organic-phase syntheses remains challenging
[1]. Life-cycle assessment studies indicate that shifting to water-based, low-
temperature, and heavy-metal-free synthesis pathways can substantially reduce the
ecotoxicological footprint of QD manufacturing, supporting the principles of green
chemistry advocated by Anastas and Warner [3].
In summary, the fundamentals of quantum dots encompass a rich intersection
of quantum physics, inorganic chemistry, and materials science. The quantum
confinement effect underpins the size-tuneable optical properties that make QDs
uniquely versatile, and the expanding diversity of QD types—from semiconductor to
carbon-based and perovskite materials—continues to open new application spaces.
Increasing emphasis on green synthesis reflects the broader imperative to develop
nanomaterials in a sustainable and environmentally responsible manner.

References
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semiconductor crystallites: The size dependence of the lowest excited electronic
state. Journal of Chemical Physics, 80(9), 4403–4409.
[Link]
[2] Alivisatos, A. P. (1996). Semiconductor clusters, nanocrystals, and quantum dots.
Science, 271(5251), 933–937. [Link]
[3] Resch-Genger, U., Grabolle, M., Cavaliere-Jaricot, S., Nitschke, R., & Nann, T. (2008).
Quantum dots versus organic dyes as fluorescent labels. Nature Methods, 5(9), 763–
775. [Link]
[4] Xu, X., Ray, R., Gu, Y., Ploehn, H. J., Gearheart, L., Raker, K., & Scrivens, W. A. (2004).
Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube
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