PERSPECTIVE

pubs.acs.org/JPCL

Advances in Light-Emitting Doped Semiconductor Nanocrystals

Narayan Pradhan*,† and D. D. Sarma*,‡
†
Department of Materials Science and Centre for Advanced Materials, Indian Association for the Cultivation of Science, Jadavpur,
Kolkata 700032
‡
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012

ABSTRACT: Insertion of just a few impurity atoms in a host semiconductor nanocrystal can
drastically alter its phase, shape, and physical properties. Such doped nanomaterials now
constitute an important class of optical materials that can provide efficient, stable, and tunable
dopant emission in visible and NIR spectral windows. Selecting proper dopants and inserting
them in appropriate hosts can generate many new series of such doped nanocrystals with
several unique and attractive properties in order to meet current challenges in the versatile field
of luminescent materials. However, the synthesis of such doped nanomaterials with a specific
dopant in a predetermined host at a desired site leading to targeted optical properties requires
fundamental understanding of both the doping process as well as the resulting photophysical
properties. Summarizing up to date literature reports, in this Perspective we discuss important
advances in synthesis methods and in-depth understanding of the optical properties, with an emphasis on the most widely
investigated Mn-doped semiconductor nanocrystals.

I nvestigation of semiconductor nanocrystals has constituted

one of the most active, cross-disciplinary research areas for
over two decades now.1 5 In contrast to their metallic counter-
parts, semiconductor nanocrystals exhibit more pronounced
quantum confinement effects.2,6,7 This is because the leading
electron and hole states of a semiconductor, appearing at the top
edge of the valence band and the bottom edge of the conduction
band, respectively, are strongly affected by a variation in the
particle size. This effect allows a near-continuous tuning of the
bandgap of a semiconductor material by changing its size in the
nanometric size regime; the corresponding changes in its optical
properties are often spectacular. While a wide variety of applica-
tions in diverse fields, such as catalysis,8,9 optoelectronics,10 photo-
voltaics,11 drug delivery,12 and diagnostics,12 have been discussed in
the literature, optical properties of semiconductor nanocrystals
continue to remain the main thrust of fundamental research and
its most imminent technological utilization.
A very active subfield in this area involves modification of
properties of semiconductor nanocrystals by incorporating opti-
cally active dopants, typically transition metal ions, inside the
lattice of the host semiconductor.13 The range of photolumines-
cent colors that can be achieved by this method with the use of
two typical transition metal ions, namely, Mn and Cu, are shown
in Figure 1. The key feature of the dopant emission is that its
energy is red-shifted with respect to the bandgap energy of the
host. Therefore, dopant emission is not absorbed by the host
material, minimizing the vexing issue of self-absorption. Such
doped luminescent materials also often exhibit an improved
photo and thermal stability and provide a viable route to avoid
toxic materials in several potential applications being pursued in
this field.14,15 In the following, we review the present status of this
highly active field. We begin by describing the most important
doping strategies adopted for synthesizing such samples with
specific references to the degree of quantum efficiencies achieved
so far. Then we discuss in detail some of the main challenges in
this field of research and ways to address several of these issues.
Finally, we present some of the more important investigations to
understand optical properties of these systems at a microscopic
level. While we primarily discuss the case of Mn-doping in group
II VI semiconductor nanocrystal hosts, the doping strategy
discussed here can be easily generalized for other dopants as well.
The key feature of the dopant
emission is that its energy is red-
shifted with respect to the bandgap
energy of the host. Therefore, dop-
ant emission is not absorbed by the
host material, minimizing the vex-
ing issue of self-absorption.
One of the earliest reports of a Mn-doped semiconductor
nanocrystal system was from Bhargava et al.,16 based on a Mn:
ZnS system achieving an 18% quantum yield (QY) of photo-
luminescence (PL). In this case, nanocryastalline ZnS was first
synthesized using diethylzinc and hydrogen sulfide gas and later
mixed with diethylmanganese in an organic solvent to obtain the
Received: August 19, 2011
Accepted: October 13, 2011
Published: October 13, 2011

r 2011 American Chemical Society 2818 dx.doi.org/10.1021/jz201132s | J. Phys. Chem. Lett. 2011, 2, 2818–2826
The Journal of Physical Chemistry Letters PERSPECTIVE

doped nanocrystals. Finally, these nanocrystals were coated with
methacrylic acid to passivate the surface and improve the QY.
A few years later, Norris et al.17 reported Mn-doped ZnSe
nanocrystals with a 22% QY in a high-temperature colloidal synthetic
protocol. Mn and Zn precursors were loaded in the reaction flask
under Argon flow, and a Se source was injected at a high temperature
to get Mn-doped ZnSe nanocrystals. Under optimal synthesis
conditions, Mn emission dominates the PL spectrum, although a
substantial excitonic emission persists, as shown in Figure 2a. With a
continued growth of the system, the excitonic emission is found to
move to a lower energy, reflecting the growth of nanocrystals with
time. Mn emission wavelength does not show any shift with the
growth time, establishing independence of this emission with respect
to the host particle size. There is a clear increase in the intensity of
Mn emission at 585 nm with a concomitant decrease in the excitonic
emission intensity, suggesting either a larger fraction of nanocrystals
being doped or other competing decay channels being suppressed
with increasing reaction time.
Using a different synthetic route, Peng et al18 could achieve a
QY of about 50% from Mn-doped ZnSe nanocrystals, underlining
the very subtle nature of the doping process. In this synthesis
technique, named nucleation doping, dopant selenide clusters
are first formed, and host semiconductors are grown on them. This
method ensures that most of the host nanocrystals are doped and
Figure 1. Schematic presentation of the range of tunable emission of
different doped semiconductor nanocrystals. Cu-doped InP can extend
its tunability until 1100 nm (ref 47) but here we have restricted our data
to mostly the visible spectrum.
gives rise to nearly pure dopant emission alone (Figure 2b). Since
the host is specifically nucleated and grown on the dopant chalco-
genide nucleation centers, there is little possibility of having
undoped host nanocrystals in this method.
While all these doped nanocrystals with high QY are synthe-
sized keeping dopants in the host lattice, Cao et al.19 reported
intense (QY > 50%) Mn dopant emission by placing dopant ions
in a shell of a core/shell structured nanocrystal. A typical syn-
thetic procedure of such structures is shown in Figure 2c, where
Mn ions are incorporated in a ZnS shell layer on top of a core of
CdS nanocrystals. Cao et al. excited this system with a photon
energy corresponding to the bandgap of the core CdS region.
Since the excitation energy is lower than the bandgap of the ZnS
shell layer, the primary excitation is necessarily within the CdS
part of the core shell structure. The corresponding emission
spectrum, shown in Figure 2c, clearly shows the emission due to
Mn2+ ions at ∼600 nm, in addition to the excitonic emission
within the CdS core at about 420 nm. With appropriate synthetic
conditions, the Mn emission can be optimized, as shown in
Figure 2c, yielding QY higher than 50% in this method.
Apart from these synthetic protocols, several other methods
have been reported that lead to intense and stable Mn dopant
emission.20 25 Recently Karan et al.22 developed a generic doping
strategy where Mn (and even Cu) dopants can be doped in most
of the usual group II VI semiconductor nanocrystal hosts. Using
manganese oxide nanocrystals as the dopant source and following
growth doping strategy, different hosts such as ZnS, ZnSe, ZnSeS,
CdSeS, and CdZnS have been doped, and highly efficient (QY
30 40%) dopant emission has been obtained by this method.
There have also been reports of single source precursors to obtain
different doped nanocrystals.24,25 Thus, it appears evident that
there is a wide variety of synthetic strategies to choose from in
order to achieve highly emitting doped nanocrystals. Some of
these synthetic strategies have been shown to be scalable for syn-
thesis of large amount of samples with QY > 50%.21 While most
studies report doping of spherical host nanocrystals, there are
specific examples of doping Mn in one-dimensional (1D) shaped
rods26 and wires20 and two-dimensional (2D) shaped discs.27
Having discussed various ways of synthesizing doped semi-
conductor nanocrystals with high emission QYs, we now discuss
some intriguing aspects of such systems. Among these, the most

Figure 2. Successive PL spectra obtained during different doping processes. (a) Representation of the introduction of the dopant to the reaction system
along with host precursors, (b) representation of the introduction of the dopant before nucleation of the host, and (c) representation of the introduction
of the dopant in the shell of a core shell structured nanocrystal. All PL spectra are recorded with an excitation wavelength of 350 nm. These results are
obtained following the synthetic approach presented in references 17, 18, and 19.

2819 dx.doi.org/10.1021/jz201132s |J. Phys. Chem. Lett. 2011, 2, 2818–2826

The Journal of Physical Chemistry Letters
prominent one has been the unexpected difficulty in achieving a
sizable doping level in such semiconductor nanocrystals. It is
known that the quantum efficiency for Mn emission is the highest
for an isolated Mn2+ ion in a nanocrystal host and an increasing
Mn concentration reduces the quantum efficiency per Mn2+
dopant due to Mn Mn interactions.28 This favors doping in the
dilute limit. However, doping being a statistical process, an
average Mn concentration, which would be sufficient to place
one single Mn2+ ion in each nanocrystal host, will generally leave
some nanocrystal hosts undoped, while introducing multiple Mn
ions in some other nanocrystals, thereby reducing the quantum
efficiency. Therefore, there is a trade-off between the need to
dope all nanocrystals and the need to keep the doping level at the
minimum to obtain the maximum efficiency.28 Hence it is
important to study the net quantum efficiency of such doped
systems as a function of Mn concentration up to a reasonably
high Mn content, besides such investigations being relevant to
exploring interesting magnetic properties as well. In this context,
we note that most synthetic routes discussed above, with the
exception of ref 28, achieve low levels of doping, reporting
typically in the range of 1 2% or lower Mn content. This
difficulty appears to be unique to the nanometric regime, since
corresponding bulk systems, such as bulk ZnS or CdS solids, can
be easily doped up to large dopant concentrations (>10%).29 The
origin of this drastic difference in one’s ability to dope Mn ions up
to a high concentration in nanocrystals compared to the bulk has
been debated in the literature. In several publications, the possibility
of the doped state being a metastable one and Mn having a sizable
diffusion coefficient in the host material at typical synthetic tem-
peratures, making facile surface segregation of Mn ions possible,
have been discussed.13,30 The essential idea in this explanation is that
Mn-doped nanocrystals can easily eject the dopant to the surface,
thereby achieving its lowest energy configuration. However, there
have been reports14,28 where doped Mn exhibited remarkable
stability even at a reasonably high temperature, suggesting that the
metastability of doped nanocrystals may not be the only cause of low
levels of dopant concentrations generally achieved.
In an alternate explanation, it has been argued31 that the Mn
diffusion coefficient in these semiconductor host materials is, in
fact, small and, therefore, doping cannot be achieved by Mn2+
ions diffusing into an already formed nanocrystal, even if the
doped state is the lowest energy state in contrast to the previous
discussion. According to this work, doping of nanocrystals
proceeds primarily via adsorption of Mn2+ ions on the surface
of the semiconductor nanocrystals, thereafter being buried by
further growth of the nanocrystal. Therefore, the extent of
doping is believed to be controlled by the ability of Mn2+ ions
to adsorb on specific crystal facets available in the growing
nanocrystal. Detailed quantum mechanical calculations evince
that Mn2+ ions preferentially adsorb on {011} facets of the zinc
blende structure, while the wurtzite phase does not offer any
suitable surface for Mn2+ adsorption. This fact was related to the
remarkable paucity of doped nanocrystals in the wurtzite phase in
contrast to a large number of reports of doped semiconductor
nanocrystals in the zinc blende phase.
More recently, it has been noted that the Mn2+ ionic size (0.85
Å) is considerably different than those of Cd2+ (0.95 Å) and Zn2+
(0.75 Å).28 Thus, a Mn2+ ion substitutionally doped at the place
of Zn2+ or Cd2+ invariably causes local strains. It is interesting to
note here that the ionic size of Mn2+ is smaller than that of Cd2+,
but larger than that of Zn2+. Thus, a cationic solid solution of Cd
and Zn in the form of Zn1 xCdxS allows one to tune the average
2820
PERSPECTIVE
Figure 3. (a) Plot of the amount of dopant Mn incorporated in Znx-
Cd1 xS alloyed nanocrystals with variation of composition. (b) Simu-
lated EPR patterns of tetrahedrally and octahedrally coordinated Mn2+
ions in a semiconductor host nanocrystals. These data are obtained from
refs 28 and 37.
cationic size available to accommodate Mn dopant ions. It has been
shown28 that the maximum incorporation of Mn2+ ion as a function
of the stoichiometry, x, in Zn1 xCdxS indeed tracks the average
lattice mismatch (Figure 3a). This approach also allows one to
incorporate up to nearly 8% Mn for the optimal value of x (∼0.5),
this being the highest amount of Mn inclusion into a group II VI
semiconductor nanocrystal so far. These results would suggest that
the main cause of the difficulty in incorporating Mn in these
semiconductor nanocrystal hosts is the strain associated with
doping,28 as also suggested in ref 32. Another interesting as-
pect of the results reported in ref 28 is that the composition
(Cd0.5Zn0.5S) accommodating the highest concentration of
Mn dopant exists in the wurtzite phase, undermining earlier
suggestions of this crystallographic phase being inappropriate
and rather detrimental for Mn doping. This result also indi-
cates that the adsorption of Mn2+ may not be the determin-
ing step in the doping process, in contrast to the suggestion
provided in ref 31.
As already described, doping of Mn is typically carried out
by introducing Mn2+ ions into the reaction solution during a
suitable stage of the synthesis. The complex process of incor-
poration of Mn in the semiconductor nanocrystal host at the
simplest level involves a large number of steps: (i) diffusion of all
reactants in the solution to reach the growing nanocrystals; (ii)
adsorption of reactant species onto the surfaces of these nano-
crystals; (iii) their incorporation through atomic rearrangements
at the surfaces; (iv) possible diffusion of various species
toward or away from the core of the host; and (v) further
growth of nanocrystal hosts via diffusion-controlled Ostwald
ripening process33 or more complex growth patterns.34,35 It
would be naive to expect such a labyrinthine, multistep process
to give rise to complete homogeneous doping of nanocrystals.
Inhomogeneity of doping was first investigated specifically in
ref 36 establishing that Mn2+ ions systematically prefer to be
doped in larger hosts within a given size distribution of the
host nanocrystals.
Mn2+ ions systematically prefer to
be doped in larger hosts within a
given size distribution of the host
nanocrystals.
dx.doi.org/10.1021/jz201132s |J. Phys. Chem. Lett. 2011, 2, 2818–2826
The Journal of Physical Chemistry Letters
Figure 4. Schematic presentation of the electronic energy level
diagram and excitation-de-excitation process (a,b) within an inde-
pendent particle approximation. (c,d) The same processes depicted
in a and b, respectively, but within a total energy diagram, as explained
in the text. Æ1æ represents the total energy of the ground state of the
system, while Æ2æ represents that of the system with an electron hole
excitation.
Besides the systematic inhomogeneity of doping discussed
above, a dopant ion, such as Mn2+, can locate itself at a number of
inequivalent sites, such as in the core region or close to (or even
at) the surface, in addition to being accommodated substitution-
ally or at an interstitial position being tetrahedrally or octahed-
rally coordinated. It is reasonable to expect that properties of
Mn2+ ions will depend on its location in the host. Therefore, it
becomes important to know the exact location of Mn in the
system. This can be most easily determined by electron para-
magnetic resonance (EPR), also known as electron spin resonance
(ESR), spectroscopy. This method has been used by a large
number of groups over the years to probe the location of
Mn dopant ions in the host nanocrystal. A typical result is
shown in Figure 3b. Such narrow line-widths are characteristic
of isolated Mn2+ ions, since dipolar interactions between
nearby Mn Mn ions are known to give rise to very broad
EPR signals.17,37 In Figure 3b, the spectrum with g = 2.002 and
a hyperfine splitting of 69 G is characteristic of Mn2+ in
tetrahedral symmetry, suggesting Mn substitution in the core
of the host. Similarly, the other spectrum in Figure 3b with
g = 2.003 and a hyperfine splitting of 95 G is characteristic
of Mn2+ in a distorted octahedral geometry typical of a near-
surface isolated Mn2+ ion.17,37
As previously mentioned, the largest effort in the investigation
of semiconductor nanocrystals is aimed at obtaining and utilizing
2821
PERSPECTIVE
a range of spectacular optical properties. The basic mechanism of
PL of an undoped nanocrystal is shown in Figure 4a,b. On
absorption of sufficiently high-energy photons, electrons from
occupied levels are excited to unoccupied levels, conserving the total
energy of the system and generating electron hole pairs; a few
among the very large number of possible pair formation for a
given photon energy are shown in Figure 4a. These highly excited
electrons and holes quickly decay nonradiatively by coupling to
the vibronic states and occupy the lowest unoccupied level
(bottom of the conduction band in the language of solid state
physics or the lowest unoccupied molecular orbital (LUMO) in
the language of molecular orbital theory) and the highest
occupied level (top of the valence band or the highest occupied
molecular orbital (HOMO)), respectively, giving rise to the
situation shown in Figure 4b. Then the electron and the hole
recombine, as indicated by the vertical green arrow in Figure 4b,
giving rise to the emission of a photon. This process is often
termed as the band gap or the excitonic PL, depending on the
relative importance of the electron hole Coulomb interaction
strength in a given case. In Figure 4a,b, we have represented the
excitation and the deexcitation processes in terms of a single
particle description that is valid and convenient only in cases
where the electron electron interactions can be effectively
ignored, as in the case of undoped semiconductor nanocrystals.
This is, however, not a valid approximation in the case of
transition metal ion-doped systems, since Coulomb interactions
within the transition metal 3d manifold is strong. In such a
situation, it is more convenient to talk in terms of the total energy
of the system instead of the electronic level energies shown in
Figure 4a,b. In this alternate description, the ground state of the
undoped system is a unique energy state, as shown by a hori-
zontal energy level, Æ1æ, in Figure 4c, depicting the total energy
diagram. However, the electron hole excited state of the system
has a continuum of energies (marked Æ2æ), as shown at a higher
energy in the same figure. The photoabsorption process takes the
system from the ground state to an excited state energy according
to the energy conservation principle, as marked by the vertical
arrow in Figure 4c. The advantage of this total energy represen-
tation becomes evident when we compare panels a and c of
Figure 4, both representing an identical situation of photoexcita-
tion of an electron hole pair in a semiconductor. In Figure 4a,
this process has been represented by only three distinct possibi-
lities, while the photoabsorption process can be (and indeed is)
realized in nearly infinite number of different ways while conser-
ving the energy. In Figure 4c, the same process has a unique
representation, as shown, since all possible photoexcited states
have exactly the same total energy, determined by the excita-
tion/photon energy. This excited state quickly decays nonra-
diatively to the lowest energy excited state (see Figure 4c) via
coupling to the vibronic states. The lowest energy excited state,
corresponding to an electron and a hole in the lowest conduc-
tion band and in the highest valence band, respectively,
eventually makes a radiative transition to the ground state, as
marked by the vertical green arrow in Figure 4d, giving rise to
the PL. It should be noted here that Figure 4a,b is exactly equi-
valent to Figure 4c,d.
We first note that the Mn2+ 3d5 ion in a tetrahedral crystal field
can exist in different multiplet states. At the usual crystal field
strength, multiplets with the two lowest energies are given by
6
A1 and 4T1 states. Presence of a doped Mn2+ ion in a host
semiconductor, the ground state system comprises the ground
state of the host nanocrystal (no electron hole excitation) along
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The Journal of Physical Chemistry Letters
Figure 5. Total energy diagram of (a) the excitation and (b) the de-
excitation processes in Mn-doped nanocrystals, as discussed in the
text. Æ1æ represents the ground state of the nanocrystal with Mn2+ in
6
A1 state. Æ2æ represents that of the host with an electron hole
excitation and the Mn2+ in the 6A1 state. Æ3æ represents the total
energy of Mn2+ in the 4T1 state but the host without any electron
hole excitation. States corresponding to Æ1æ, Æ2æ, and Æ3æ can be thought
of as (host + Mn), (host* + Mn) and (host + Mn*), respectively, where
the * denotes an excited state.
with the ground state multiplet configuration of Mn state, 2+
which is the 6A1 state. The total energy of this ground state is
shown (Æ1æ) in Figure 5a. The total energy spectrum of the
electron hole excited host along with the Mn in the 6A1 state are
shown as the continuum of energies, marked Æ2æ, in the same
panel. However, the lowest energy excited state in this system,
Æ3æ, is a multiplet excitation of the Mn2+ state from the 6A1 state
to the 4T1 state in the absence of any electron hole pair in the
host, as shown in Figure 5a. The photoabsorption process with
sufficiently high energy photons primarily causes electron hole
excitations in the system, as shown in Figure 5a. This excited state
(Æ2æ) decays nonradiatively in a very short (typically sub-
picosecond) time-scale to the lowest energy excited host state,
as shown in Figure 5b, as much as in the case of the undoped
system (see Figure 4c,d). In contrast to the case of the undoped
system, however, the doped system can nonradiatively decay
further by transferring the excitation energy of the electron
hole pair to excite the ground state multiplet 6A1 state of the
Mn2+ ion to its excited 4T1 state, thereby making a transition
from the lowest energy of Æ2æ to the sharp energy level of Æ3æ,
as indicated by the blue vertical arrow in Figure 5b. This energy
transfer process is also very rapid, occurring within a time-
scale of a few picoseconds (psec). Eventually, the excited
Mn2+ 4T1 state decays radiatively to the ground state config-
uration of the 6A1 state (Æ3æ f Æ1æ), as shown by the vertical
orange arrow in Figure 5b, and giving rise to the dopant
emission, red-shifted (at a lower energy) compared to the
bandgap or the excitonic emission.
It is well-known that surface as well as defect states in semi-
conductor nanocrystals can give rise to PL signals, significantly red-
shifted with respect to the bandgap emission. Such PL signals arise
from excited states associated with the population of electrons
and/or holes in the surface and other defect states with a total
energy lower than the electron hole excitation in the host, as
shown in Figure 6a. It should be noted that these excited surface/
defect states may be reached via charge (electron or hole) or
energy transfer. It is clearly convenient to represent such transi-
tions between these states in terms of the total energy diagram
adopted here. In this form, it is not necessary to distinguish be-
tween different cases (electron/hole/energy transfer), and, there-
fore, the same diagram can represent in a compact way all possible
surface state-related emissions. These excited states involving
surface or other defect states, decay radiatively to the ground state
2822
PERSPECTIVE
Figure 6. Schematic representation of the total energy diagram of Mn
doped ZnS nanocrystals in presence of surface/defect states: excitation
and deexcitation processes for (a) undoped and (b) doped nanocrystals.
This figure is adopted from ref 38.
(see Figure 6a), giving rise to the red-shifted emission with respect
to the bandgap emission. If such systems also contain any dopant,
such as Mn ions, there is a competition between the decay chan-
nels involving the surface states and those via the dopant states as
illustrated in Figure 6b, leading to both surface and dopant state
emissions. However, Mn excited states are not only populated by
the energy transfer from bandgap excitations, but may also be
populated via the decay of excited surface states,38 as indicated
by the diagonal blue arrow in Figure 6b. This allows even
insufficiently passivated nanocrystals with substantial surface
states to primarily exhibit the narrow dopant emission under
optimized conditions.
The basic difference in the various emission processes men-
tioned above gives rise to large differences in the corresponding
emission lifetimes. The lifetime of the band-edge emission is
controlled by the dipolar overlap of the wave functions for the
top of the valence band (HOMO) and the bottom of the
conduction band (LUMO) states, with lifetimes typically in the
range of 1 30 nanoseconds (nsec). The Mn emission in Mn-
doped systems correspond to a d d transition within the Mn 3d
multiplet; this is both a spin and orbitally forbidden transition in
the ionic limit, therefore, leading to a very long lifetime in the
range of several hundreds of microseconds. It should be noted,
however, that there are other processes involved at various
steps of the excitation and emission processes; those influence
different aspects of the emission features, such as the quantum
efficiency, tunability, and line-width, finally observed in an
emission experiment. Specifically, it is important to note that
the time-scale for the energy transfer from the host to the Mn
d-states is much faster than the Mn d-emission lifetime; it is
typically in the range of a few psec.38 If this transfer rate is not fast,
much of the de-excitation process will be via other channels, such
as the excitonic emission or involving decay via surface states; thus,
the fast transfer rate is absolutely crucial for a large Mn emission
quantum efficiency. We note that the emission decay lifetime
involving the surface states appears typically at about a few nsec or
less, and is, therefore, faster than the bandgap deexcitation, in most
systems. This indicates why it becomes important to passivate
surface states very effectively in order to obtain a high intensity
band-edge emission. In contrast, the energy transfer to Mn
d-states competes effectively with that to the surface states.
This fact, along with the possibility of a further energy transfer
from the surface states to Mn d-states (Figure 6b), makes the
dx.doi.org/10.1021/jz201132s |J. Phys. Chem. Lett. 2011, 2, 2818–2826
The Journal of Physical Chemistry Letters
Mn-emission less susceptible to the presence of surface states
of higher energy.
Mn emission in Mn-doped systems
correspond to a d d transition
within the Mn 3d multiplet; this is
both a spin and orbitally forbidden
transition in the ionic limit, there-
fore, leading to a very long lifetime
in the range of several hundreds of
microseconds.
The above discussion of relative intensities of various emission
features, namely, arising from deexcitations involving the band-
gap, surface, or defect states and doped states, can be understood
more quantitatively by noting that these are determined by
corresponding transition probabilities. These transition prob-
abilities are inversely related to the lifetimes discussed in the
previous paragraph. For example, the ratio of intensities of
bandgap and Mn emissions in a doped system is basically the
ratio of probabilities for de-excitations via the bandgap recombi-
nation and the energy transfer process to Mn2+ from the host, in
the absence of any other process. Thus, this intensity ratio is
given by the inverse of the ratio of the bandgap deexcitation
lifetime (∼1 30 nsec) and the time-scale (∼ a few psec) of the
energy transfer from the host to the Mn d-states. Therefore, the
bandgap emission is expected to be almost completely quenched
in presence of Mn-doping; this indeed happens at a low enough
temperature for properly doped systems. However, in real
systems, at higher temperatures many different pathways exist
for the deexcitation process in addition to the bandgap recombi-
nation and via the energy transfer to Mn followed by the Mn d-d
transition. The final emission intensities observed are a result of
all these competing factors. Moreover, the intensity ratio, speci-
fically of the bandgap and Mn d emissions, has often been
reported to be strongly temperature dependent and in general
increasing with increasing temperature.24,39 Thus, the relative
intensity of the bandgap emission at room temperature may not
be a proper indicator of the efficiency of Mn doping in every
system, and one needs to perform PL experiments at a very low
temperature (<10 K) in order to understand the intrinsic
branching ratio between the bandgap recombination and the
deexcitation via the Mn d states.
We note that most reports with ZnS, CdS, ZnSe, and CdSe
host materials indicate that Mn emission appears at about
585 nm, independent of the size, shape, and the nature of the
host material, whereas bandgap emissions are known to be sen-
sitively dependent on all these factors. Even PL emission from
other transition metal ions, such as Cu, doped into semiconduc-
tor nanomaterials shows considerable tunability for a given host
as a function of the size of the host particles18 (see Figure 1), in
sharp contrast to the case of Mn emission. The dependence of
the bandgap emission on nanocrystal size naturally appears due
to the shifting of conduction and valence state energies due to
quantum confinement as a function of the host size. Emission
2823
PERSPECTIVE
from Cu-doped semiconductor nanomaterial hosts is known to
involve both Cu d and host levels, thereby exhibiting the
sensitivity to the nature and the size of the host particles.40 In
contrast, Mn emission is essentially a Mn d d transition, whose
energy is dominated by the Coulomb direct and exchange
interaction strengths within the Mn d multiplets and the strength
of the crystal field. In view of the essentially atomic-like Mn
d-states, compared to the s,p states of the host material, it is
understandable that Mn d-states are less affected by such quan-
tum confinement effects in the typical size regimes investigated,
explaining the relative insensitivity of the Mn emission on the size
or the nature of the host.
There are several anomalous behaviors of Mn emission from
doped systems that need some elaboration here. For example, the
above simplistic description would suggest that there should be
no tunability of the Mn emission from such systems; in reality, a
limited range of tuning has been reported (see Figure 1).
Specifically, Peng et al.14 reported tuning of the Mn emission
over 570 610 nm in ZnSe by treating thiol on post-synthesized
nanocrystals. Subsequently, Nag et al.41 reported tuning of Mn-
emission over 575 620 nm, establishing the tunability of Mn
emission close to 50 nm. While this tunability cannot be attri-
buted to any quantum confinement effect, as argued above, ref 41
has suggested on the basis of quantitative estimates from first
principles calculations that subtle changes in the crystal-field effect
are responsible for tuning of the Mn emission in these cases.
The width of the emission line is an important criterion in
various applications, since it determines the color purity. More-
over, a narrow emission provides high intensity at a given wave-
length, rather than spreading the quantum efficiency over a wide
range of wavelengths. The width of an emission line depends on a
number of factors. While we may ignore lifetime effects alto-
gether for having a negligible effect on observed line-widths in
most cases, the most important contribution to the emission
width for bandgap emission comes from the size distribution of
the sample, due to the sensitive dependence of the emission
energy on the size of the nanocrystal. This also forms the basis of
the often-used approach of obtaining a rough estimate of the size
distribution of a nanocrystal assembly from the width of the
emission14 or the absorption spectra.42 Since Mn d-emission is
insensitive to the size of the host nanocrystal, it should be
insensitive to the size distribution of the host, thereby leading
one to expect a very narrow, atomic-like Mn d d emission.
However, almost all reports indicate a much larger width of Mn
d-emission in the range of 50 nm, in contrast to the much
narrower width expected for an atomic-like d d transition. This
surprising observation has been interpreted24 as a large width
contributed by the vibronic coupling of the local structure around
the dopant ion with the emission process. It has also been
suggested41 that a part of the Mn emission width may in fact
arise from a variation of the crystal field symmetry and strength
experienced by different Mn ions in an assembly of nanocrystals
due to its various Mn location in the host, thereby essentially giving
rise to overlapping emission signals with shifted emission maxima.
Therefore, more experiments are required to resolve the origin of
the unusually large width of Mn emission in such systems.
One of the important applications of such brilliantly emitting
semiconductor nanocrystals is perceived to be in the field of
lighting. Specifically, it is possible to generate the desired hue of
the white light by combining nanocrystals emitting primary
colors. Various factors favor the use of nanomaterials compared
to the other existing materials, such as the possibility of achieving
dx.doi.org/10.1021/jz201132s |J. Phys. Chem. Lett. 2011, 2, 2818–2826
The Journal of Physical Chemistry Letters
very high quantum efficiency for the emission and a low scatter-
ing of the generated light. Thus, there have been various attempts
to combine different nanomaterials with distinct emission prop-
erties to generate white light.43 Such an approach, however,
has the serious drawback of self-absorption where a part of the
emitted light is reabsorbed by other components in the system
with lower bandgaps. There have been several attempts to
circumvent this problem by using emission from doped materi-
als, since the red-shifted, lower energy emission of a doped
material cannot be absorbed by the host due to its larger bandgap.
One of the obvious choices to generate white light should be
to mix various Cu-doped nanomaterials, as emission involving
Cu d-states can cover the entire visible spectrum (Figure 1) and
also possesses minimum self-absorption. An alternate approach
to obtain white light has been to allow a certain proportion of
surface state emissions to mix with the Mn emission by control-
ling the relative efficiency of the respective decay processes.44
More recently, this approach of mixing Mn dopant emission with
the surface state emission has also been exploited in the context
of producing white light by electroluminescence.45 With proper
hosts, these doped nanocrystals can be considered as heavy metal
free light emitters that have the potential for implementations in
solid state lighting as environmental friendly materials and in
diagnostic applications as noncadmium labels.
One of the obvious choices to gen-
erate white light should be to mix
various Cu-doped nanomaterials, as
emission involving Cu d-states can
cover the entire visible spectrum
and also possesses minimum self-
absorption.
In recent times, there has been an increasing interest in using
Cu as an effective dopant for generating tunable and intense
emission.18,40,46,47 We have touched upon Cu-doped systems
only briefly, since this doped system is still relatively in its
infancy compared to advances made in every aspect of Mn-doped
semiconductor nanocrystals. However, several results with Cu-
doped systems indicate that there may be various new, unex-
plored systems associated with exciting properties. Apart from
optical properties, it has been observed recently that dopants can
control the shape and phase of the parent host nanocrystals27
adding new dimensions to materials synthesis. Similarly, doping
can be used to alter many other physical properties of the host.
For example, depending on the nature of the dopant and the
host, doping can enhance the conductivity of the parent host
material, turn a nonmagnetic host in to a magnetic material, can
give rise to multifunctional nanomaterial, and materials suitable
for optical thermometry, clearly indicating a very luminous future
ahead for such systems both in terms of fundamental studies and
present-day and future applications.
The dopant emission has several significant advantages over
the excitonic emission obtained from undoped quantum dots.
As stated above, the large energy difference between the host
2824
PERSPECTIVE
absorption and the dopant emission minimizes the self-absorp-
tion of emission; this makes these doped nanocrystals ideal
materials for a wide range of device applications. Several visible
light-emitting doped materials are also free from toxic, heavy
metals, making these environmental friendly. In contrast, the
most commonly used nanocrystal materials with PL in the visible
region of the electromagnetic spectrum invariably contains Cd, a
well-known toxic component. In addition, the photostability and
thermal stability of the dopant emission in both aqueous as well
as nonaqueous dispersion14,15 make such systems particularly
attractive compared to undoped systems, since undoped nano-
crystals require more complicated internal structures, such as to
cover them with another high bandgap material, in order to
achieve a significant level of stability. Moreover, these photo-
stable and various color-emitting cadmium-free doped nano-
crystals can also be used in biolabeling, replacing photosensitive
organic dyes often used to date. Hence, the optically active doped
nanocrystals are efficient emitters with several advantages and
may be implemented as sources of light-emitting dispersed
material for a wide variety of applications.
In summary, we have primarily presented here the impor-
tant advances in synthetic techniques and photophysical
properties of Mn-doped semiconductor nanocrystals, although
some mention has been made for other transition metal dopants
as well. We have also discussed in some detail the importance and
the future prospects of these transition metal-doped semi-
conductor nanocrystals.
’ AUTHOR INFORMATION
Corresponding Authors
*E-mail: camnp@iacs.res.in (N.P.); sarma@sscu.iisc.ernet.in
(D.D.S).
’ BIOGRAPHIES
Narayan Pradhan is an Assistant Professor in the Department
of Materials Science and also an associate of the Centre for
Advanced Materials, “Indian Association for the Cultivation of
Science” Jadavpur, Kolkata, India. His major research interests
are the synthesis, surface functionalization, and photophysical
properties of colloidal semiconductor and transition metal-
doped semiconductor nanomaterials. See http://www.iacs.res.
in/matsc/msnp/ for further details.
D. D. Sarma is a Professor in the Solid State and Structural
Chemistry Unit, Indian Institute of Science, Bangalore, India.
Additionally, he is a Honorary Professor at Jawaharlal Nehru
Research Centre for Advanced Scientific Research, Bangalore;
Distinguished Scientist of Council of Scientific and Industrial
Research, being primarily associated with its Network of Insti-
tutes for Solar Energy; and Guest Professor of Physics at Uppsala
University, Sweden. His research interests are in the areas of
strongly correlated electron systems and semiconductor nano-
crystals. The main emphasis of his group is on understanding the
electronic, optical, and magnetic properties of such materials. See
http://sscu.iisc.ernet.in/DDSarma/ for details.
’ ACKNOWLEDGMENT
DST and CSIR of India are acknowledged for funding. D.D.S.
acknowledges J. C. Bose, and N.P. acknowledges LNJ Bhilwara
for fellowships.
dx.doi.org/10.1021/jz201132s |J. Phys. Chem. Lett. 2011, 2, 2818–2826
The Journal of Physical Chemistry Letters
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