Angewandte

Reviews Chemie

International Edition: DOI: 10.1002/anie.201611526

Doped Nanocrystals German Edition: DOI: 10.1002/ange.201611526

Luminescence, Plasmonic, and Magnetic Properties of

Doped Semiconductor Nanocrystals
Narayan Pradhan,* Samrat Das Adhikari, Angshuman Nag,* and D. D. Sarma*

Keywords:
doping · nanocrystals · LSPR ·
manganese doped ·
semiconductor nanocry-
stals

Angewandte
Chemie
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Introducing a few atoms of impurities or dopants in semiconductor From the Contents

nanocrystals can drastically alter the existing properties or even
1. Introduction 7039
introduce new properties. For example, mid-gap states created by
doping tremendously affect photocatalytic activities and surface con- 2. Doping: Placing Impurity Ions
trolled redox reactions, generate new emission centers, show thermo- in the Host Lattice 7040
metric optical switching, make FRET donors by enhancing the excited
state lifetime, and also create localized surface plasmon resonance 3. Electron–Hole Recombination
through Dopant States 7041
induced low energy absorption. In addition, researchers have more
recently started focusing their attention on doped nanocrystals as an 4. Exciton Dissociation through
important and alternative material for solar energy conversion to meet Dopant States 7046
the current demand for renewable energy. Moreover, the electrical and
5. Charge Doping by Heterovalent
magnetic properties of the host are also strongly altered on doping.
Ions for Plasmonic Properties 7047
These beneficial dopant-induced changes suggest that doped nano-
crystals with proper selections of dopant–host pairs may be helpful for 6. Magnetic Impurity Doping 7049
generating designer materials for a wide range of current technological
needs. How properties relate to the doping of a variety of semi- 7. Conclusion and Future
Prospects 7051
conductor nanocrystals are summarized in this Review.

1. Introduction hole has a larger tendency to form a bound state (an exciton)
compared to the bulk system. This exciton can then transfer
Semiconductor nanocrystals, popularly termed as quan- its energy to dopant levels, resulting into electron–hole
tum dots (QDs), provide a unique platform to combine recombination essentially within the dopant site and emitting
beneficially quantum confinement effects, surface related light characteristic of the dopant.[2b] There is also the alternate
phenomena, and the ease and versatility of solution procees- scenario where only the electron or the hole is transferred to
ability.[1] Intentional doping of an impurity atom/ion in such the dopant site, leading to a charge transfer, and the electron–
nanocrystals provides an additional handle to control material hole recombination takes place involving both the dopant
properties.[2] Presently, doped semiconductor nanocrystals are state and host state and therefore, is still influenced by the
considered as an important class of materials with interest nature of the dopant. Such dopant emissions from doped
ranging from fundamental understanding to renewable nanocrystals, intrinsically different from band-edge or exci-
energy applications. Among these, transition-metal ions tonic emissions, have attracted the attention of a large
doped in compound semiconductor nanocrystals are at the community of scientists and technologists in view of their
forefront with diverse synthetic methods available through inherent potential in various applications as well as in terms of
the pioneering work of many groups; the research in this area issues of fundamental importance arising from such studies.
is driven by frequent reports of exciting new properties for For example, such dopant-related luminescence phenomena
such systems over the years.[3] have been utilized for applications in light-emitting diodes
Doping a transition-metal ion in a semiconductor host (LEDs), optical thermometry,[6] and as donors in fluorescence
often introduces a dopant-related energy level within the mid- energy transfer applications.[7] In a recent report on Mn-
gap region of the host. Such mid-gap states lead to drastic doped CdSe nanocrystals, it has been shown that when the
modifications of material properties with the nature of these
mid-gap states dominantly determining the property exhib-
[*] Dr. N. Pradhan, S. Das Adhikari
ited by a doped semiconductor nanocrystal.[3t, 4] For example,
Department of Materials Science
a localized deep trap state bound to the dopant ion, is Indian Association for the Cultivation of Science
responsible for luminescence in Cu-doped ZnSe nanocrystals, Kolkata 700032 (India)
whereas holes in delocalized states are responsible for E-mail: camnp@iacs.res.in
plasmonic properties in Cu2+ doped Cu2S (Cu2-xS) nano- Homepage: http://iacs.res.in/matsc/msnp/
crystals.[5] Dr. A. Nag
Major optical properties of doped semiconductor nano- Department of Chemistry and Centre for Energy Science
crystals with localized defect states have been realized Indian Institute of Science Education and Research, IISER
Pune 411008 (India)
involving excited states induced by photo-absorptions.
E-mail: angshuman@iiserpune.ac.in
When the host nanocrystal absorbs a photon of energy
Prof. D. D. Sarma
greater than its band gap, an electron–hole pair is created.
Solid State and Structural Chemistry Unit
Owing to the enhanced wave-function overlap arising from Indian Institute of Science
the confinement within the quantum dot, the increased Bengaluru 560012 (India)
Coulomb attraction between the photoexcited electron and E-mail: sarma@sscu.iisc.ernet.in

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excitonic energy is lower than the internal Mn d–d transition plasmonics, and 4) doping magnetic ions in diluted magnetic
energy, the Zeeman splitting arising from unpaired d elec- semiconductor (DMS) nanocrystals. These combinations
trons of the dopants lifts the degeneracy of excitonic states, provide an overview of different metal-ion doping for
giving rise to multiple lines in excitonic emission.[8] In inducing different functional properties in semiconductor
a different approach, it has been shown that dopants can nanocrystals.
influence the dissociation of photogenerated excitons,
thereby tailoring photovoltaic[9] and catalytic[10] properties.
Doping of heterovalent ions contribute additional charge 2. Doping: Placing Impurity Ions in the Host
carriers in the form of electrons or holes, moving the Fermi Lattice
level up or down, respectively. For example, when Sn4+ is
doped in In2O3 nanocrystals, electrons are added in the Properties of doped nanocrystals rely on reliable synthetic
delocalized conduction band as a result of the substitution of routes to introduce dopant ions inside the lattice of host
In3+ ions with Sn4+ ions, pushing the Fermi level from within nanocrystals.[2b, 15] These ions can be placed in the host lattice
the band gap into the conduction band. Collective oscillation substituting the existing ions or at interstitial positions of the
of these doped conduction electrons upon photo absorption lattice. Chemistry plays an important role in designing and
yields localized surface plasmon resonance (LSPR) in doped synthesizing doped nanocrystals. Typically, dopants are
nanocrystals.[11] The capability to modulate this LSPR band inserted in the lattice during the host crystal growth or by
with small variations in the density of delocalized electrons partial ion exchange after the growth.[3d, 15b, 16] In general,
gives rise to applications, such as near infrared (NIR)- substitutional dopants have different atomic radii and also
selective smart windows[12] and optical sensing[13] of electro- may be iso- or hetero-valent compared to the host ions that
chemical processes. Apart from electronic, optical, and they replace. In both cases of substitutional and interstitial
optoelectronic properties, efforts are also being made to doping, dopant ions most often induce strain in the crystal
achieve useful magnetic properties by doping transition-metal because of the size mismatch. Thermal annealing is often
ions with unpaired electrons in various compound semi- required for healing these defects. However, thermal anneal-
conductor nanocrystals.[3c, 14] This Review highlights various ing sometimes removes the dopants from the lattice to
recent developments in the field of doped colloidal semi- minimize the energy.[17] This consideration suggests that
conductor nanocrystals. Prior to discussing various properties, doping should be easier to achieve if the dopant ion has
a brief generic overview about the synthesis of these doped a size similar to that of the substituted host ion.[18] For
nanocrystals is provided. Then the properties have been example, Mn2+ is larger than Cd2+ but smaller than Zn2+,
grouped in four categories: 1) electron–hole recombination consequently doping a significant concentration of Mn is
through dopant states, 2) exciton dissociation through dopant difficult in both CdS and ZnS nanocrystals. However, one way
states, 3) electron/hole doping by heterovalent ions for to achieve a reasonably higher Mn doping concentration

Narayan Pradhan Studied Chemistry at Angshuman Nag studied Chemistry from IIT
Ravenshaw University, Cuttack and pursued Guwahati and carried out his Ph.D. degree
his Ph.D. from IIT Kharagpur, India with from SSCU at IISc Bangalore, India with
Prof. T. Pal. He carried out is post-doctoral Prof.D. D. Sarma. He then completed two
research at Ben-Gurion University, Israel terms as a postdoctoral researcher at IISc
with Prof. S. Efrima and University of Bangalore with Prof. C. N. R. Rao and
Arkansas, USA with Prof. X. Peng. He University of Chicago with Prof. Dmitri V.
joined IACS, Kolkata, India in 2007 and is Talapin. In 2012, he Joined at IISER Pune
currently a Professor there. as a Ramanujan Fellow, and then continu-
ing as an Assistant Professor in Chemistry.

Samrat Das Adhikari obtained M. Sc. in D. D. Sarma completed 5-years Integrated

Chemistry from IIT Madras, India and cur- Masters in Physics from IIT Kanpur in 1977,
rently pursuing his Ph.D. at Indian Associa- followed by his Ph.D. from the department
tion for the Cultivation of Science, Kolkata, of Solid State and Structural Chemistry Unit
India as CSIR-NET fellow with Prof. N at IISc Bangalore in 1982 with Prof. C. N.
Pradhan. R. Rao. After postdoctoral stints at IISc and
Kernforschungsanlage Jflich, Germany with
Prof. Maurice Campagna he joined the
faculty of IISc in 1986. Except for a nearly
three year stay at IACS Kolkata as the MLS
Chair Professor of Physics and the founder-
Chairman of Centre for Advanced Materials
during 2006–2009, he has been at IISc since
then.

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(7.5 %) is to tune the lattice parameters by making an alloyed adopting suitable strategies, it has also been possible to
host, such as Zn0.5Cd0.5S nanocrystals, with the lattice achieve high quantum efficiency as well as tunable emission in
parameters same as that of MnS.[18] such systems. Among these, doping of Mn remains the most
In general, doping of colloidal semiconductor nanocrys- investigated one, though many aspects of Mn d–d emission
tals is more difficult to achieve compared to their bulk still remain poorly understood.[2a,b, 3b,g,k, 4, 21] Recently, several
counterparts. However, several highly successful synthetic other transition-metal dopants were also reported showing
methods have been developed over the years to insert tunable dopant state emissions.[16a, 22] Synthesis approaches
dopants into the lattice of nanocrystals using the bottom-up have also been improved leading to precise doping in targeted
approach of colloidal synthesis.[3b,i,m, 15b, 19] Growth doping, positions of host nanocrystals in many cases. Herein, we
which follows the facet energy dependent adsorption as a key summarize all doping processes reported to date in which the
parameter, has remained one of the most successful pathways reaction chemistry plays the major role for facilitating the
for designing doped nanocrystals.[3a, 20] Also, the nucleation specific doping process. One of the easiest processes is the
doping route, in which dopants are used at the nucleation simultaneous introduction of dopant and host precursors in
stage of the host nanocrystals, has gained in popularity.[15b] In the reaction system where co-nucleation is predominant and
the last couple of decades, several Reviews have appeared, the doping and nucleation steps could not be decoupled
discussing the development in doping strategies. Hence, in (Figure 1 a). However, the most successful and widely
herein, we focus instead on the various properties of doped reported doping is the growth doping (Figure 1 b) in which
nanocrystals. the doping process is decoupled from the host nucleation and
dopants are allowed to adsorb on appropriate facets during
the growth stage. To observe emission exclusively from
3. Electron–Hole Recombination through Dopant dopants, dopant ions are allowed to nucleate first (Figure 1 c);
States this approach has been found to be highly successful for both
Mn and Cu doping.[15b] Figure 1 d schematically shows another
3.1. Synthesis Strategies and Optical Properties of Doped process, namely, diffusion-controlled doping.In this process,
Nanocrystals: Recent Progresses dopants are inserted via diffusion into the crystal lattice of
pre-formed host nanocrystals. The successful process was
Optical emissions of transition-metal-doped semiconduc- reported in anion rich systems and was successful for different
tor nanocrystals remain the foremost materials property and shapes and phases of host nanocrystals. Cation exchange is
has been extensively studied for more than two decades. also used for doping when the reaction parameters can be
Highly desirable aspects of dopant emissions are the near- adjusted to allow ion replacement by dopant ions or vice versa
absence of self-absorptions, and high excited-state lifetimes; (Figure 1 e).[23] Cu doping in CdSe has been achieved success-

Figure 1. Schematic representation of the various doping processes a) co-nucleation doping, b) growth doping, c) dopant-nucleation, d) diffusion
doping, e) ion-exchange doping, f) atomically precise doping, g) digital doping. h) Relaxation process of two different types of dopant emissions,
where one uses both dopant and host energy states (left) and other is dependent on the dopant d–d states (right). PL spectra showing i) the
appearance of Cu-dopant emission (green) during doping Cu in ZnSe (blue) hosts, j) increase in Mn d—d emission along with quenching of
excitonic emission during the synthesis of Mn-doped ZnSe nanocrystals, k) Mn d–d emission from Mn-doped CdInS nanocrystals, l) absorption,
PL excitation and PL spectra of Mn-doped Cd12MnSe13 nanoclusters, and m) tunable PL spectra of single-Mn-doped CdZnS nanocrystals.
Figure 1 e,f,i–m are adapted from Ref. [15b, 19g, 23, 25b, 27a], and [27b].

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fully following this approach. While all these synthetic emission from ZnSe and CdInS nanocrystal hosts, respecti-
processes were reported on different-sized host nanocrystals, vely.[15b] However, as stated above, the doping is achieved
recent process on precise control over doping and also digital digitally[15b] and even precisely in a small cluster. Figure 1 l
doping were reported in which transition-metal ion dopants presents a typical case of UV/Vis, photoluminescence excita-
were placed successfully in molecular clusters (Figure 1 f,g) tion (PLE) and photoluminescence (PL) spectra of Mn doped
including (CdSe)13. Hence, unlike a decade ago, the chemical (CdSe)13 crystals. It has been suggested that this Mn d–d
doping of a colloidal semiconductor nanocrystal is now emission is tunable over a much wider wavelength window
largely understood. However, further understanding and than previously observed and this is one of the exciting
better control is still required particularly for achieving high observations on Mn doping.[27b] It was widely established that
levels of homogenous doping. Mn doping largely show non-tunable emission centered at
Development of such doping chemistry has been a key to 2.1 eV or 585 nm. In contrast, Hazarika et al., observed
achieving nanocrystals with desired optical functionalities, multicolor emissions from Mn doped nanocrystals using
mainly through controlling the dopant-related light emission. single particle spectroscopy (Figure 1 m).[27b] A narrow spec-
Broadly, emissions from doped nanocrystals come in two tral width (FWHM) of approximately 70 meV was observed
categories: 1) involving both host- and dopant-induced for single particle spectra, again in a sharp contrast to usual
energy states,[3n, 24] and 2) involving exclusively the dopant Mn d–d emission obtained from ensemble of particles
d–d states.[2a, 20, 21d] While emissions involving host- and exhibiting spectral width of about 250 meV. These results
dopant-induced energy states is tunable by tuning the size suggest that the Mn d–d emission can be tuned in the green-
of the host nanocrystals which shifts the band edges of the red spectral window with narrow spectral widths, however,
host, the emission based on dopant d–d states remains the emission color observed from an ensemble of particles has
independent of the host band gap. Figure 1 h presents the contributions from numerous individual particles emitting at
band positions and the recombination process involving the different energies yielding a broad spectrum in the yellow–
excitonic band of the host and the dopant state. Cu+ and Ag+ orange region.
doped in II–VI semiconductor nanocrystals follow similar At the same time, tuning emission color of single Mn-
mechanistic path where only one dopant state is involved doped nanocrystals is not sufficient for various light-emitting
during the recombination. On the other hand, for dopant applications, and for this purpose, it is essential to achieve
Mn2+, the recombination is via the d–d transition. On such tunable emission color from ensembles of Mn-doped
excitation, there is an energy transfer from the host to Mn nanocrystals. There are some reports of tuning the ensemble
d-states converting the ground state 6A1 of Mn2+ ion into one PL in the orange-red region of the visible spectrum for a given
of the excited atomic multiple states. Eventually the emission combination of host and Mn dopant. For example, it was
takes place via the transition from the lowest excited state, observed that Mn dopants near the surface of Mn-doped CdS
4
T1, of Mn2+ to its ground state, as shown in Figure 1 h nanocrystals experience distorted tetrahedral coordination
schematically. Evidently, this is both a spin and orbitally and emit at lower energy compared to Mn dopants at the core
forbidden transition. Representative photoluminescence of nanocrystals with a perfect tetrahedral coordination.[3g]
spectra of these two types of emissions during their evolution Further, for different hosts, the emissions were observed to
process are shown in Figure 1 i–m. Figure 1 i is a typical case of be tunable from yellow to deep red. This was mostly
a Cu-doped system where during the course of the reaction, established with the change of local environment around
the exciton emission of the host gradually diminishes and that the dopant ions in the crystal lattice or with changing surface
of the dopant appears.[24c] Tunable emission of Cu on doping ligands which could induce the ligand-field splitting. In
in different size of CdSe nanocrystals was also reported.[25] It a recent Review, we discussed the red tuning of Mn emission
has been further observed that other dopants, such as CrIII and citing different state-of-the-art examples.[28] Hazarika et al.
NiII, in Cd-Zn-S nanocrystals can also introduce mid-gap recently showed tuning of Mn d–d emission in the entire
states and provide tunable emissions,[22b,d] though these are visible region from the ensemble of Mn-doped ZnSe/CdSe/
not as widely investigated as dopant Cu. When these dopants ZnSe core/shell/shell nanocrystals by systematic manipulation
are individually doped in Cd-Zn-S host of a fixed size and of strain around the dopant center.[29] Mn was doped in the
identical elemental compositions, different colors are emitted outermost ZnSe shell, and the Mn at the CdSe/ZnSe (outer
suggesting their mid-gap energy states are different.[22d] In shell) interface showed the highest emission energy with
comparison to CuI, all these dopants result high energy a peak at 2.56 eV (485 nm). The emission peak could be tuned
emissions. From the mechanistic study, it was established that in the range of 480–580 nm, by increasing the distance of the
the Cu state remains mostly close to the valence band of the Mn dopant from the CdSe/ZnSe (outer shell) interface.
host and it behaves more like ternary CuInS2 nanocrystals. Interestingly, not only the peak position, but also the PL
However, Liu et al. reported Ag-doped CdSe where they radiative lifetime ranged from nearly 30 ms to about 600 ms
have established the Ag states were close to the conduction with changing Mn emission energy or with the strain around
band. In both cases, the emission process involves both host the Mn dopant.
and dopant states.[26] Further, Peng et al. reported very promising results on the
In comparison to these Cu- or Ag-doped nanocrystals, dopant-concentration effect of Mn doping in ZnSe host.[30]
emission arising from Mn doping has been studied more Keeping the size of the host fixed, Mn content was tuned from
extensively providing interesting new insights. Figure 1 j and 32 to 431 Mn atoms per nanocrystal. Optical absorptions and
1 k presents a typical case of appearance of Mn dopant corresponding emissions with Mn content variations pre-

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Figure 2. a) Optical spectra of Mn-doped ZnSe with variation of Mn content. b) Schematic representation of doped ZnSe nanocrystals with
varying Mn concentration. c) Excited state decay lifetime plots for Mn-doped ZnSe nanocrystals with different Mn content. Inset: lifetime versus
Mn/Zn ratio in ZnSe nanocrystals. d) Decay time versus Mn content in Mn-doped CaZnOS Nanocrystals. Reproduced from Ref. [30] and Ref. [31],
with permission from the American Chemical Society.

sented in Figure 2 a suggest no change in their positions. more than 70 % for Mn doped nanocrystals.[7a] As Mn-doped
Schematic presentations of the doped nanocrystals with nanocrystals can result in intense emission and can be hosted
variation of dopant concentration are shown in Figure 2 b. in nanocrystals free from cadmium, these can be used as
Interestingly, the excited-state lifetime of the Mn emission sensors in conjunction with different fluorescing organic
changes drastically with Mn concentration. For the nano- molecules. This work on Mn-doped nanocrystals as FRET
crystals having average 32 Mn atoms per crystal the lifetime donors is very preliminary and investigations in details are
measured was 850 ms, but with average 431 atoms per crystal it further required.
was reduced to 100 ms. Decay plots for the successive change Mn PL saturation in doped nanocrystals has been first
with changing Mn concentration are presented in Figure 2 c. demonstrated by Cao and co-workers in Mn doped CdS/ZnS
Inset shows the plot of decay time as a function of Mn to Zn nanocrystals.[3h] With an increase in the excitation intensity
ratio. Qualitatively similar, but quantitatively less pro- beyond a threshold, there are enough host excitons to excite
nounced results have also been reported for CaZnOS,[31] all the Mn atoms present in the same nanocrystal by energy
with the excited state decay lifetime decreasing rapidly with transfer leading to a saturation of the Mn PL intensity as
the dopant (Mn2+) concentration, as shown in Figure 2 d. a function of the excitation power. This is easily achieved in
These results show that the excited state decay lifetime of Mn view of the long life-time of the Mn2+ excited states. With any
can be tuned with Mn concentration variation without further increase in the excitation power, the host excitonic
affecting much the emission, whereas Hazarika et al. emission gains in intensity. Figures 3 a–c show the normalized
showed that the excited state decay lifetime of Mn is PL of Mn doped CdS/ZnS with different excitation intensities.
systematically tuned also by the strain field around the Mn While with a low intensity excitation source only Mn emission
emission centers.[29] can be observed (Figure 3 a), for higher intensity excitations,
The longer lifetime of Mn doped nanocrystals made these the excitonic emission emerges prominently and eventually
ideal donors for fluorescence resonance energy transfer becomes dominant as shown in Figures 3 b,c. While in this
(FRET) in pairing with organic dyes and also undoped case, the PL saturation is discussed with complete relaxation
quantum dots.[7] The FRET efficiency has been observed to be of excited Mn to ground state, Taguchi et al.[32] discussed the

Figure 3. a)–c) PL spectra of Mn-doped CdS/ZnS at different excitation power energy. Reproduced from Ref. [3h]. d) Excitation intensity dependent
PL spectra of Mn-doped ZnSe/ZnS/CdS/ZnS nanocrystals. Reproduced from Ref. [33].

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Mn PL saturation via exciton–exciton Auger recombination a material with different but appropriate band gap or
prior to energy transfer to Mn state. Later, Gamelin and co- passivation by strong binding ligands. While these surface
workers[33] studied the excitation power dependent Mn phenomena of nanocrystals are extensively studied for
emission in different host nanocrystals under continuous- undoped quantum dots, recent progress suggests that these
wave (CW) and quasi-CW photoexcitation conditions. Fig- also interfere with the dopant emission of doped nanocrystals.
ure 3 d presents the PL of Mn:ZnSe/ZnS/CdS/ZnS nano- Either for Cu-doped or Mn-doped nanocrystals, the most
crystals at different excitation intensities. While Mn d–d stable emissions were observed for thiol capped nanocrystals
emission was observed to approach saturation at a certain dispersed in organic or in aqueous solvent.[34] Depending on
excitation power level, the intensity of the ZnSe host emission the nature of hosts, surface oxidation indeed affects the
linearly increased with the increase of the excitation power, as dopant emission, for example, Rinehart et al. have shown for
shown in Figure 3 d. Similar results were also obtained from in TOPO-capped Mn-doped ZnSe nanocrystals[35] that the
different host nanocrystals. Irradiation with additional pulse quenched orange-red emission at approximately 600 nm
of light after the energy transfer from host exciton to Mn, that owing to surface oxidation was retrieved by adding NaF2
is, with Mn2+ in an excited state, a nonradiative quenching reducing agent. Figure 4 a shows the successive PL spectra of
process was also observed. These results were explained with the Mn d–d emission during the redox process. These
several possible carrier pathways in Mn doped nanocrys- reducing agents were non-coordinating and these could
tals.[33] enhance the emission with quantum yield as high as 85 %.
The inset in Figure 4 a depicts the mechanism where the
surface states induced non-radiative trap states were elimi-
3.2. Surface States and Redox Brightening/Darkening of Doped nated and the energy transfer facilitated from host exciton to
Nanocrystals Mn d-state, which enhanced the quantum efficiency of the
dopant emission.
Surface states of semiconductor nanocrystals are the Further, Sarkar et al., observed similar effects for both
major obstacles in achieving high efficiencies of band gap Mn- and Cu-doped semiconductor nanocrystals.[34] Intention-
excitonic emission and this has remained a long standing ally oxidizing the surface of freshly prepared doped nano-
problem for light-emitting quantum dots. Typically, these crystals and further treating with reducing agent, the photo-
create uncontrolled mid-gap states which interfere with the darkening as well as photo-brightening were studied. During
photoluminescence process. The most reliable approach these redox processes the PL intensity as well as emission
adopted for eliminating these states are either a shell of decay lifetimes were investigated. Intriguingly, it had been

Figure 4. a) Successive PL spectra showing redox brightening of Mn-doped ZnSe nanocrystals. Inset: the possible photo relaxation pathways in
the doped nanocrystals. Reproduced from Ref. [35], with permission from the American Chemical Society. Successive PL spectra of b) Cu and Al,
and c) Ag and Al co-doped ZnS nanocrystals. Reproduced from Ref. [36] with permission from the Royal Society of Chemistry. d) PL spectra of Cu-
doped and Cu-doped Al co-doped ZnSe nanocrystals. Reproduced from Ref. [37] with permission from the American Chemical Society. e) Energy
transfer mechanism of host exciton to Mn d-states. In this case the excitonic state of the semiconductor host remains well separated from the 4T1
of Mn. f) The excitonic state remains close to the 4T1 of Mn. g),h) Change of PL intensity with temperature variations for Mn:ZnSe/CdSe and
Mn:ZnSe/ZnS/CdS/ZnS host nanocrystals. Reproduced from Ref. [3c] and Ref. [38], with permission from the American Chemical Society.

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noticed that samples with dead emission and stored for this allows one to plan appropriately in order to achieve
months became emissive on surface redox reactions and doped semiconductor nanocrystals with stable and intense
subsequent passivation. This has been observed for both Cu emissions.
and Mn dopant emissions. The experiment was carried out
with amine-capped doped ZnSe where the Cu dopant
emission was in green and Mn was in yellow. Intentional 3.4. Dual Emitting Doped Nanocrystals and Optical
oxidation of these nanocrystals under air and UV-irradiation Thermometry
quenched the emissions of both nanocrystals. Interestingly,
these photo darkened nanocrystals again brightened simply For obtaining the dopant emission, the host emission is
by treatment of alkylthiols. With different supporting experi- typically quenched. This is observed for wide-band-gap
ments, it was concluded that alkylthiols mainly acted as semiconductor hosts where the conduction band (CB)
a reducing agent and the retrieval of the emission is nothing position remains above than the dopant state. Both excitonic
but the redox brightening which is exclusively a surface and dopant emissions are observed from the reaction solution
chemistry. Moreover, these thiols are also found to serve well in steady-state PL measurement in standard fluorometer at
as stable capping agents and the nanocrystals are thus further room temperature which is typically assumed to be due to the
protected from air oxidation. With these examples, it could be mixture of doped and undoped nanocrystals present in such
concluded for doped nanocrystals that surface states can be cases, each emitting their allowed emissive channels.[3a, 15b] For
removed and the intense dopant emission can be regained Mn-doped ZnSe, ZnS, and also CdS nanocrystals, the 4T1 state
even for old samples with suitable surface redox chemistry. of Mn remains well below the conduction band, irrespective
of the size of nanocrystal. A typical case is schematically
shown in Figure 4 e, in which energy transfer occurs only from
3.3. Co-Doping for Stable and Enhanced Dopant Emission excitonic state to the Mn dopant, without much scope for the
reverse energy transfer process from dopant to excitonic
Apart from Mn, Cu is another transition-metal dopant states. However, the case of Mn-doped CdSe nanocrystals is
which can result in a stable and tunable dopant emission.[3- different. For bulk samples, the 4T1 state of Mn remains above
f, 19e, 24b, 39]
However, peculiarly in some hosts the emission is not the excitonic state of CdSe, but with very small sized CdSe
affected by surface states and in some cases the emission is nanocrystals, their energy positions are switched.[6] For the
highly sensitive to photo-oxidation. For Cd-Zn-S alloy hosts, case of CdSe particles having an intermediate size whose
the emission is generally observed bright and stable for both excitonic state remains close to the 4T1 state, a qualitatively
Cu and Mn dopants without any surface-state interferences. different behavior has been observed. In such cases the
However, for wide band-gap semiconductors, such as ZnSe as exciton storage population varies within the host excitonic
well as ZnS, the emission was quenched under exposure to air. state and Mn 4T1 with temperature. As a consequence, the
Literature reports on the origin of Cu-dopant emission have emission switches from one to the other depending on the
mixed predictions as to whether it is from CuI or CuII states, measurement temperature. This has been studied by Vlaskin
though several recent developments agree with the presence et al. for Mn:ZnSe/CdSe nanocrystals[4] and the shell thick-
of CuI.[3i] In presence of a reducing agent (e.g. amine), CuII is ness was designed in such a way that the conduction band was
changed to CuI and hence in the reaction mixture having placed closer but just above the Mn 4T1 state. The arrange-
either CuI or CuII salts, results similar emission. This suggests ments of the band positions for such nanocrystal systems is
Cu most likely retains the oxidation state(I) when doped in depicted in Figure 4 f. On excitation, the population of the
the crystal lattice of the host.[24c]In this case, for stabilizing the exciton in these two states is controlled by temperature. With
emission, trivalent InIII or AlIII or GaIII ions are co-doped in a temperature rise the host exciton emission dominates and
balancing the monovalent CuI for charge neutrality. These ion during cooling this is switched to Mn d–d emission. A typical
pairings also help in retaining Cu inside the nanocrystals. In set of PL spectra during this temperature switching for
the case of ZnS, it was established that under a standard Mn:ZnSe/CdSe is shown in Figure 4 g. The experiment is also
reaction method, it was difficult to dope Cu and this has been extended to nanocrystals with multi-shell structures which
eliminated by co-doping with Al. Not only in CuI doping, co- allow emission stability and aqueous dispersion (Mn:ZnSe/
doping AlIII in AgI-doped nanocrystals also enhances the ZnS/CdS/ZnS, Figure 4 h).[38] In addition, this has also been
stability and also the emission intensity.[36] Figure 4 b,c show studied for alloyed nanorods. In a recent Review, Gamelin
the stable and tunable PL spectra for Cu doped Al co-doped and co-workers[24c] compared such temperature-dependent
and Ag doped Al co-doped ZnS nanocrystals, respectively. PL switching with the energy transfer in quantum-dot dyes
The emission is also observed to be stable and show enhanced and also quantum systems with two distinct emissions
intensity in Cu-doped Al co-doped ZnSe nanocrystals.[37] The separated by a wide energy difference. As such systems are
change in PL intensity under identical condition for doped very sensitive to temperature and can be achieved with pure
ZnSe nanocrystals are presented in Figure 4 d. The placement excitonic and pure dopant emissions, these materials could be
of CuI countering AlIII in the crystal lattice is supported by X- ideal for dual emitting thermosensors.
ray absorption near edge structure (XANES) spectroscopy
for these nanostructures. These results suggest doping heter-
ovalent ions can be performed with co-doping and this
method can be extended to various dopant–host pairs. Also

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4. Exciton Dissociation through Dopant States efficiency obtained was 5.42 % which was one of the highest
for QDSSCs at the time of report. This enhanced efficiency
4.1. Doped Nanocrystals for Photovoltaic Applications for the Mn-doped QDSSC was explained by the exciton
dissociation via Mn d-levels in the mid-gaps. It was suggested
Among different transition-metal-ion doped semiconduc- that “the mid-gap states created by Mn doping cause electrons
tor nanocrystals, Mn:CdS, Mn:CdS/CdSe, and Mn:ZnCdS to get trapped and screen it from charge recombination with
nanocrystals have been explored for designing quantum-dot holes and/or oxidized polysulfide electrolyte”, as schematically
solar cells leading to significant enhancements of efficiencies. shown in Figure 5 b. This suppression of interaction of
Santra and Kamat, studied Mn:CdS and Mn:CdS/CdSe electron redox couples at the QD–electrolyte interface can
nanocrystals with a ZnS coating and observed more than explain the improved solar-cell performance of doped nano-
5 % efficiency.[9] The photoanode was designed by depositing crystals. Ultrafast transient absorption studies on a similar
different monolayers of the doped nanocrystals following the system, namely a composite of Mn-doped CdSe nanocrystals
successive ionic layer adsorption and reaction (SILAR) with bromo pyrogallol red molecules, also showed that Mn
method on a TiO2 substrate, the counter electrode was dopants can act as electron storage centers with the possibility
Cu2S/graphene composites and the electrolyte was sulfide/ of improving QDSSC performance compared to the compo-
polysulfide, to give such efficient quantum-dot-sensitized sites made using undoped nanocrystals.[40] In a recent devel-
solar cells (QDSSC). Comparisons were also made using opment, Zhong and co-workers reported the best QDSSC
undoped nanocrystals which were less efficient than the based on a Mn:CdSeTe QD sensitizer and Mn:ZnS passiva-
doped counterparts. tion with an efficiency of 9.4 %.[41] This result suggests that
The J–V characteristics of these QDSSCs are shown in with proper manipulation in fabricating QDSSCs using doped
Figure 5 a. Both Mn-doped CdS and Mn-doped CdS/CdSe nanocrystals, the efficiency can be further improved.
QDSSC show significant improvement in both short circuit
current and open circuit voltage compared to QDSSCs
prepared using corresponding undoped nanocrystals. This 4.2. Doped Nanocrystals for Catalysis
increase in short circuit current and open circuit voltage
without altering fill factor, has led to the improved overall The exciting size-dependent tunable optical properties of
solar cell efficiency. For the Mn-doped CdS/CdSe film the semiconductor nanocrystals enable the harvesting of solar

Figure 5. a) J–V plots for CdS, CdS/CdSe, and their corresponding Mn-doped nanocrystals. b) Schematic representation of the possible carrier
transportation for enhancing the photovoltaic activity. Reproduced from Ref. [9] with permission from the American Chemical Society. c) Schematic
representation of the reduction of p-nitrophenol using doped and undoped nanocrystals. Reproduced from Ref. [10] with permission from the
Royal Society of Chemistry. d) Schematic representation showing slow and fast transfer of photoelectrons in doped nanocrystals to catalyst and
dopant states, respectively. e) Schematic presentation of Mn-doped CdSeS/ZnS nanocrystals and their band off set. f) Light intensity dependent
rate of hydrogen evolution for doped (RH2d) and undoped (RH2ud) nanocrystals. Reproduced from Ref. [42] with permission from the American
Chemical Society.

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light. As a consequence, these generate photoexcited elec- 5. Charge Doping by Heterovalent Ions for
trons which might transfer to the redox species and trigger Plasmonic Properties
catalytic reactions. Catalysis involving these nanocrystals has
been studied extensively for carrying out different organic Trivalent Boron doping in tetravalent Si is an example of
reactions, water splitting, and also dye reduction/degrada- heterovalent doping, inducing p-type electrical conductivity
tions.[43] From the literature it is revealed that there are through hole doping, whereas, pentavalent phosphorous-
several reports on doped nanocrystals enhancing the photo- doped Si is an n-type semiconductor as a result of electron
catalytic activity. However, a remarkable result reported doping. Such heterovalent doping and the consequent change
recently on Cu-doped and Mn-doped ZnSe nanocrystals in electron or hole doping can be used to tune the Fermi level
suggests that these doped nanocrystals may drastically hinder suitably for various optoelectronic applications, such as a p–
catalytic activities. This has been tested for the catalytic n junction solar cell.[44] Interestingly, in addition to modifying
reduction of 4-nitrophenols.[10] While undoped nanocrystals optoelectronic properties, heterovalent doping in semicon-
efficiently reduce 4-nitrophenol to 4-aminophenol, on doping ductor nanocrystals yields a new property, namely, localized
the reduction is entirely stopped for Mn doping and surface plasmon resonance (LSPR). The process of LSPR in
drastically slowed down for Cu doped nanocrystals. Figure 5 c a nanocrystal is schematically shown in Figure 6 a.In this
shows the schematic presentation of the reduction of 4- Section, we will discuss the prospect of heterovalent doping in
nitrophenol in presence of doped and undoped ZnSe nano- colloidal semiconductor nanocrystals, with emphasis on
crystals. This hindrance of catalysis is explained with long recent studies on such plasmonic properties.
excited-state decay lifetimes of both Mn-doped and Cu-doped The LSPR band can be explain by a modified Drude
nanocrystals. As dopant states are present within the host model, in which both the intensity and energy of the LSPR
crystal, on excitation, the generated charge carriers quickly band increases with an increasing free-carrier density. Noble
move to these states and stay trapped there for a long time metals, such as Au and Ag nanocrystals, with a high density
(Figure 5 d). Hence, the transfer of electrons or holes to the (1022–1023 cm@3) of delocalized electrons exhibit strong LSPR
redox species, necessary for the catalytic activity is hindered, bands in the visible region.[45] This success of noble metal
decreasing catalysis. However, this cannot be considered for nanocrystals has also motivated researchers to investigate
a generic mechanism as different organic compounds have LSPR in nanocrystals of a variety of systems, such as ReO3[46]
LUMO and HOMO positions at different levels and also their and TiN,[47] which show metal-like electrical properties in the
bonding to the nanocrystals may decide the catalytic activ- bulk. In last 7–8 years, LSPR from colloidal-doped semi-
ities. Hence, more systems need to be studied to establish conductor and metal oxide nanocrystals have been explored
a conclusive mechanism. extensively. The underlying idea is to shift the Fermi level by
In recent development, Son and co-workers[42] suggested heterovalent doping, and thereby achieve a high enough
that Mn-doped nanocrystals could enhance photocatalytic density (1020–1021 cm@3) of delocalized carriers, required for
hydrogen production following upconversion of the energy of LSPR. One of the major advantages of doped nanocrystals for
two excitons into the hot charge carriers. This was performed such LSPR is that the carrier density can be controlled easily
in Mn-doped CdSSe/ZnS core/shell nanocrystals where, by the dopant concentration, which in turn provides tunability
unlike the photon upconversion which produced higher- of the LSPR peak from the red to the mid-infrared (mid-IR)
energy photons, the photon energy was converted for region for a variety of systems as summarized in Review
producing hot electrons. This was explained by the long- articles.[48]
lived Mn excited state which acted as the intermediate state Figure 6 b schematically shows different doping strategies
for generating the hot carrier that enhanced the catalytic to generate a high density of delocalized carriers, and their
activity for hydrogen generation. The core/shell structure in corresponding LSPR regions. Copper chalcogenides, such as
which the Mn was doped on the ZnS shell was an advantage as Cu2@xS nanocrystals, yield valence-band holes because of a Cu
there was an energy barrier between the conduction band of deficiency, yielding a doping scenario termed as self-
core and the shell material. This restricted the exciton doping.[49] The density of these valence band holes can be
electron, but the hot electrons were able to overcome this reversibly controlled by employing a reducing or an oxidizing
barrier making the nanocrystals more efficient for catalytic atmosphere, thereby allowing reversible tuning of the LSPR
reduction. A schematic presentation of the band positions of band.[50] Likewise, oxygen vacancies in WO3@x and MoO3@x,
the conduction and valance band of the core, and the hot and interstitial doping of Cs+ in CsWO3 can give rise to
electron are shown in Figure 5 e, the excitation light intensity sufficient electron density in the conduction band.[12, 51]
dependent change in the rate of hydrogen evolution for both On the other hand, bulk and thin films of transparent
doped and undoped nanocrystals is presented in Figure 5 f. conducting oxides (TCO) exhibit a high density of delocalized
Results suggest that doped nanocrystals are much more electrons in the conduction band. As a consequence, nano-
efficient than undoped nanocrystals and this opened the crystals of these materials, listed in Figure 6 b under the
window for making doped nanocrystals as catalysts for extrinsically doped category, exhibit LSPR bands.[11, 52–55]
efficient reductions. Similar to bulk TCOs in which oxygen vacancies promote n-
type doping, the LSPR from TCO nanocrystals is also
dominated by n-type doping. A typical LSPR band from
Sn4+-doped In2O3 (ITO) nanocrystals is shown in Figure 6 c.

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Figure 6. a) Schematic representation of LSPR for a doped semiconductor (or a metal) nanocrystal. The green line represents part of
electromagnetic wave applied on the nanocrystal. b) Schematically representation of the doping of electron or hole in the conduction or valence
band of nanocrystals required to exhibit a rise in the LSPR band for the compounds listed. c) UV/Vis-NIR absorption spectra showing Sn4+-doping
induces a LSPR band in the near-to-mid IR region. d) Tuning of LSPR by mixed cation–anion co-doping in fluorine- and indium-co-doped CdO
(FICO) nanocrystals. This co-doping was achieved by using InF3 as the precursor for both dopants, and an increase in InF3 precursor increases
free-carrier concentrations, and thereby shifts the LSPR to lower wavelengths (higher frequency). Detailed elemental analyses are given in
Ref. [52]. e) To achieve an electrochromic smart window, nanocomposites of WO3@x nanocrystals and amorphous niobium oxide (NbOx) were
prepared. Vis-NIR Transmittance spectra of the composite film with thickness 260 nm on a ITO-coated glass is shown at different switching
potentials (vs. Li/Li + in 0.1 m Li-TFSI/tetraglyme). Right: The corresponding photographs showing bright (4 V), cool (2.3 V), and dark (1.5 V)
mode. f) Schematic representation of the reversible exchange of electrons between LSPR-active doped metal oxide nanocrystals with redox-active
small molecules, bio-macromolecules, and live bacteria. The change in carrier density in the nanocrystals modulates the LSPR band, quantitatively
sensing the redox reactions in the aqueous medium. (a) is reproduced from Ref. [53], (c) is adapted from Ref. [54]. (d)–(f) are reproduced from
Ref. [52], Ref. [12], and Ref. [13] respectively.

For such extrinsically doped plasmonic metal oxide nano- LSPR band in the absorption spectrum. More importantly,
crystals, free carriers mainly originate from cation doping. To the electron density can be modulated by applying an
extend the versatility of doping and tunability of the electrochemical bias voltage, for example, a negative bias
plasmonic band, Murray and co-workers reported cation– increases the electron density in TCO nanocrystals resulting
anion co-doping in the form of F-In co-doped CdO (FICO) in a stronger NIR LSPR, whereas a positive bias decreases the
nanocrystals.[52] Both cation (In3+ substituting Cd2+) and anion electron density diminishing the NIR LSPR, reversibly. Such
(F@ substituting O2@) dopants can donate electrons, and selective modulation of NIR absorption makes these doped
cooperatively tune the LSPR band over a wide spectral range nanocrystals suitable for smart-window applications for air-
(Figure 6 d). Particularly, such a cation–anion co-doping conditioning of buildings, and prospects of such applications
strategy is useful for achieving LSPR at lower wavelengths. have been demonstrated[12, 55c] and reviewed[53] earlier by
Interestingly, these FICO nanocrystals also exhibit the highest Milliron and co-workers. Figure 6 e demonstrates such elec-
quality factor (6.5–12.2) defined as the ratio of LSPR peak trochromic modulation of solar light.[12] A composite of NIR
energy to the spectral width.[52] For a detailed understanding active (LSPR) WO3@x nanocrystal with visible-light active
of the origin of such excellent quality factors, further study of amorphous NiOx was coated on ITO-coated-glass. The film
single-nanocrystal LSPR behavior will be useful. For exam- was then electrochemically biased at different potentials and
ple, Milliron et al. recently showed that the LSPR band of its transmittance was measured. At 4 V (vs. Li/Li +), the
a single-nanocrystal is significantly narrower than that of the electron density of WO3@x nanocrystals decreases and the
nanocrystal ensemble.[56] The broad LSPR of the ensemble LSPR band largely disappears, showing high transmittance
mainly arises from the heterogeneity of dopant incorporation for the solar light in the NIR range, along with visible-light-
in different nanocrystals present in the ensemble. transparent NiOx. This is termed as “bright mode”. When the
Since ITO and other TCO nanocrystals are transparent to potential is reduced to 2.3 V, WO3@x nanocrystals exhibit
visible light, coating of such nanocrystals on glass windows of LSPR absorption in the NIR region, but the film still remains
a buildings allows visible light to enter the building, while transparent to visible-light forming the “cool mode”. At 1.5 V,
restricting the near-IR region of the sunlight because of the WO3@x maintains LSPR absorption in the NIR, and at the

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same time, intercalation of Li+ in NiOx induces visible-light ful till last decade. In more recent years, researchers could
absorption resulting into the “dark mode”. achieve a reasonably good control in doping Mn2+ ions (five
The electron density and hence LSPR of doped nano- unpaired d-electrons) into the lattice of CdSe nanocrystals.[63]
crystals can also be modulated by the absorption of photons This Mn-doped CdSe nanocrystal is presently the workhorse
creating electron–hole pairs, and the subsequent scavenging for realizing the giant sp–d exchange interaction and solo-
of holes in an inert atmosphere, a process termed as photo- tronic properties.
doping.[3u] Clearly, the energy of the LSPR band from doped The first bright exciton of CdSe is a doubly degenerate
nanocrystals is very sensitive to the carrier density and this state with MJ =: 1. When a magnetic field (H) is applied, the
aspect can also be used to sense electron-transfer processes degeneracy lifts (Zeeman splitting), and therefore, left and
optically.[3m, 13] Figure 6 f shows some of these examples, where right circularly polarized light get absorbed at different
LSPR from ITO nanocrystals has been used to track, and energies.[58c, 64] In the case of undoped nanocrystals, there is
quantify electron transfer events in small molecules, proteins, negligible magnetic circular dichroism (MCD) at the first
and live bacteria. However, this research direction has not excitonic band (Figure 7 a,b). In contrast, in Mn-doped CdSe/
been explored enough yet. CdS core/shell nanocrystals (Figure 7 a,b), a strong, inverted,
temperature- and field-dependent Zeeman splitting (EZ) is
observed.[65] In general, EZ = gexmBH + DEspd < SMn > , where
6. Magnetic Impurity Doping the first term corresponds to the minor contribution of the
host with gex & 1, the second term is the major contribution
Doping a magnetic ion into a semiconductor host arising from the sp–d exchange interaction.[65] In this expres-
constitutes an interesting class of material known as diluted sion, mB is Bohr magneton, DEspd represents the magnitude of
magnetic semiconductor (DMS).[57] In DMS, delocalized the sp–d exchange interaction energy, and < SMn > represents
valence-band and/or conduction-band charge carriers of the average spin projection of Mn2+ ions along the applied field
host interact with localized spin of the magnetic dopant, H. DEspd depends on exchange constants, and increases with
therefore, giving rise to interesting spin-based electronic and increasing overlap of the electron/hole wave function of the
optical properties. Such exchange interaction between host- host with the Mn2+ dopant ion. Whereas, < SMn > will depend
carriers (typically s and/or p electron/hole) with magnetic upon temperature and applied field. At 5 K, the EZ saturates
dopant ions (typically d electrons) are often termed as sp–d at @27 meV.
exchange interactions, and modulate magneto–optic and A higher level of doping, achieved by diffusion doping,[64]
magneto–electric properties in bulk and thin films of DMS showed further increase in EZ & @60 meV for colloidal Mn-
materials. Quantum confinement effects of charge carriers doped CdSe nanocrystals. Yu et al. showed similar giant
within a small space of a few nanometers can strengthen such Zeeman splitting by preparing Mn-doped CdSe nanoribbons,
sp–d exchange interaction because of the stronger overlap of in which a high doping level (ca. 10 %) for Mn was
confined charge carriers with dopant d-electrons.[58] Further- achieved.[63a] The spatial confinement of electron/hole wave
more, it might be possible to achieve one magnetic dopant ion functions can be tuned further by making heterostructured
per nanocrystal. Such a situation of a solitary dopant is not systems, such as core/shell nanocrystals. Consequently, over-
only interesting for understanding fundamental processes, but lap of electron/hole wave functions with that of Mn2+, and
also has possibilities for future solotronics–optoelectronics therefore, the strength of the sp–d exchange interaction can
applications.[59] Both these possibilities of larger sp–d also be controlled by using a suitable design of core/shell
exchange interaction, and single-dopant per crystal, are nanocrystals.[58c, 66]
major attributes of DMS nanocrystals, compared to their It has been also shown that photo-excited charge carriers
bulk and thin film counterparts. Interestingly, the size in Mn-doped CdSe nanocrystals interact with Mn2+ yielding
reduction to a nanocrystal may also have an adverse effect large Zeeman splitting even in the absence of an applied
on magnetization arising from the energy shifts as a conse- magnetic field (zero-field sp–d exchange), therefore, yielding
quence of the confinement effect under certain conditions.[60] light-induced spontaneous magnetization.[58d, 67] While mag-
In other words, the effect of the confinement on the wave neto–optic properties of Mn-doped CdSe nanocrystals have
function and on the energy levels of the host may have made significant progress in the last decade, there is a need to
opposing contributions, therefore, leading to an optimal size explore newer systems with different combinations of dopant
for the manifestation of magnetic properties.[60] and host nanocrystals to understand and optimize the extent
In spite of its promises, and reports of Mn-doped ZnS as of the Zeeman splitting. Furthermore, magneto–electric
early as in the year of 1994,[21a] and subsequent reports of properties of DMS nanocrystals are relatively little explored,
other Mn-doped semiconductor nanocrystals,[3a, 61] early mag- the major hindrance is the poor charge transport in nano-
netic studies suggested near absence of any interactions crystal arrays at low temperatures.
between magnetic dopants, such as Mn2+, in II–VI semi- This strengthening of sp–d exchange interaction with
conductor nanocrystal hosts, most probably due to the quantum confinement of charge carriers, and the capability to
absence of any free carriers in presence of such isovalent dope a single magnetic ion in a nanocrystal, have enthused
dopants and the large separation between magnetic ions in researchers to measure sp–d exchange interactions arising
the dilute limit.[62] Thus, the effect of enhanced sp–d exchange from a solitary dopant ion, which will be useful for the
interaction in modulating magneto–optic and magneto–elec- emerging field of solotronics–optoelectronics.[68] Mostly such
tronic properties of DMS nanocrystals were not very success- studies have been carried out on weakly confined systems

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Figure 7. a),b) Large sp–d spin interactions in Mn2+-doped CdSe/CdS core/shell nanocrystals. a) Magnetic circular dichroism (MCD) data for Mn-
doped and undoped samples at an applied magnetic field (B) of 7 T in the Faraday geometry. Inset: Schematic representations of the core/shell
nanocrystals with Mn2+ spins indicated as black arrows. b) Temperature-dependent Zeeman splitting of the 1s exciton (EZ) at different applied
magnetic fields. Black solid lines through the data are the Brillouin function fit. c),d) PL spectra of a single Cd0.9997Mn0.0003 Se/CdS nanocrystal at
4.7 K. c) Schematic representation of the splitting of the excited state of the nanocrystal with a single Mn2+ ion (total spin, S = 5/2), which can
lead to six lines in the PL spectrum. d) PL spectra of two selected nanocrystals: bottom spectrum exhibits six lines corresponding to one Mn2+
ion, whereas the top spectrum shows more than six line because of the presence of more than one Mn2+ doped in that nanocrystal. e),f) Electron-
mediated magnetic coupling in Mn-Sn co-doped In2O3 nanocrystals. e) Schematic representation of Mn2+ providing magnetic spin and Sn4+
providing conduction-band electrons, which mediate interaction between distant Mn2+ ions. A large carrier concentration can be generated by this
Sn4+ doping providing LSPR along with magnetism. f) Magnetization (M) versus applied field (H) plots showing a Mn–Sn co-doped sample
exhibits enhanced magnetization compared to the Mn-doped sample. g) Influence of conduction-band electron density on the spin-lattice
relaxation (SLR) dynamics of Mn-doped ZnO nanocrystals measured using pulsed electron paramagnetic resonance (pEPR) at 4.5 K. Solid line is
a guide to the eye. Inset: Schematic illustration of the relaxation process, where e@CB signifies conduction-band electron, “exch” signifies exchange
interaction. a),b) are adapted from Ref. [65]. c),d) are adapted from Ref. [8]. e),f) are adapted from Ref. [73b]. g) is adapted from ref. [77].

grown using molecular beam epitaxy (MBE).[59,69] Fainblat higher than that observed in MBE grown self-assembled
and co-workers recently prepared colloidal Mn-doped CdSe quantum dots,[70] but is consistent with theoretical predic-
based core/shell nanocrystals with an optimized quantum tions.[71] Such studies on solitary dopant ions have just begun
confinement, where 1s excitonic energy is just less than that of in the field of colloidal nanocrystals, and exciting develop-
Mn d–d transitions, and the statistical probability of doping ments may be expected in the coming years.
one Mn per nanocrystal is high.[8] To study the zero-field sp–d Another related aspect of magnetically doped semicon-
exchange interaction, they measure PL spectra of a single ductor nanocrystals is how the electron or hole of the host can
nanocrystal at a low temperature. Mn2+ with five unpaired promote magnetic coupling between distantly located mag-
electrons (S = 5/2) can have six spin projections : 5/2, : 3/2, netic ions.[72] It has been shown that photo-excited electrons in
and : 1/2. Zero-field sp–d exchange interaction of the conduction band of Mn-doped ZnO nanocrystal can mediate
photogenerated exciton with the Mn2+ ion can therefore ferromagnetic coupling between Mn2+ ions, overcoming the
split the excitonic emission into six peaks as shown schemati- nearest neighbor (Mn-O-Mn) antiferromagnetic super
cally in Figure 7 c. In fact, the lower PL spectrum in Figure 7 d exchange interaction.[72c] Similar carrier-mediated magnetic
arising from single nanocrystal with one Mn2+ ion shows the coupling was later achieved in Mn–Sn and Fe–Sn co-doped
expected six peaks. The upper PL spectrum in Figure 7 d In2O3 nanocrystals, in which conduction-band electrons were
shows more peaks, because of the presence of more than one generated in the ground state by Sn co-doping.[54, 73] Schematic
Mn2+ ion in that nanocrystal. The energy splitting between the in Figure 7 e shows that Sn doping provides free electrons in
two outermost spectral lines of lower PL spectrum is the conduction band, whereas Mn-doping provides magnetic
approximately 35 meV, which is about an order of magnitude spins which interact with each other via those conduction-

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band electrons. Magnetization (M) vs. applied field (H) plot promise in lighting applications, since proper mixing or
in Figure 7 f shows a significant increase in magnetic moment designing of such nanocrystals with multiple de-excitation
to 4.8 mB/Mn2+ at saturation (which is close to the ideal value pathways can lead to intense white light, required for solid-
of 5 mB/Mn2+), after co-doping with Sn. Importantly, a high co- state lighting.
doping level (5–15 %) of Sn can give a sufficient density of The plasmonic band of doped nanocrystals can be
conduction-band electrons to give rise to LSPR, as discussed modulated sensitively with a small change in free carrier
in Section 5.2. Therefore, additional functionality, such as density, which can be caused by chemical, electrochemical, or
magneto–plasmonic properties might arise from such Mn–Sn optical processes. This aspect appears promising and may find
or Fe–Sn co-doped nanocrystalline systems. Viswanatha et al. applications in energy-efficient electrochromic smart win-
studied Fe–Cu co-doped ZnO nanocrystals that do not show dows, understanding redox processes with optical probe, and
LSPR but co-doping promotes ferromagnetic interactions at eventually for sensing redox-active chemical and biological
low temperature.[74] In this case, the nature of the ferromag- species.
netic interaction was explained by double exchange between The other area where such materials are likely to prove
Fe dopants mediated by the Cu dopant. We note that there technologically useful is in photovoltaic applications. Since
are reports of other kinds of magnetic interactions, such as dopants can significantly alter the recombination time of the
charge-transfer-based,[75] and surface-defect-related ones,[76] photogenerated charge carriers, these materials could be
which are not covered herein in detail. explored for photovoltaic applications, enhancing their effi-
We have discussed above that a conduction-band electron ciencies. It has already been shown that doping heterovalent
in a magnetically doped nanocrystal can manipulate spin ions modifies the charge-transport properties, and careful
polarization. To study the influence of such conduction-band selection of dopant and host can provide nano p–n junctions
electrons on the spin relaxation dynamics in n-type Mn-doped within the nanocrystals. Clearly, this helps in charge separa-
ZnO nanocrystals, Gamelin and co-workers used pulsed tion, beneficial to photovoltaic and other applications. It is
electron paramagnetic resonance (pEPR) spectroscopy.[77] As expected that such applications will be increasingly explored
shown in Figure 7 g, Mn2+ spin-lattice relaxation time (T1) in the near future. Additionally, hot electrons can be
decreases sharply with an increasing concentration of con- generated from doped nanocrystals, depending on the inten-
duction-band electrons. This acceleration of spin-lattice sity and nature of the excitation, and this can be relevant in
relaxation is attributed to the new Mn2+ carrier exchange photovoltaic as well as in photocatalysis applications.
coupling pathway for spin relaxation, as schematically shown There is also an increasing trend of making nanocrystals
in the inset of Figure 7 g.[77] multi-functionality through synthetic strategies. For example,
quantum-confined charge carriers in Mn-doped CdSe based
nanocrystals result in giant Zeeman splitting, providing
7. Conclusion and Future Prospects interesting magneto–optic properties. In fact, such Zeeman
splitting has been observed at the level of a single dopant ion
In this Review, we have presented some of the recent in a single nanocrystal, suggesting the possibility of realizing
exciting developments in material properties of metal-ion- solotronics–optoelectronics in future. Similarly, Nanocrystals
doped semiconductor nanocrystals, spanning a diverse range co-doped with magnetic ions and free carriers (plasmonic)
of possible applications, such as in lighting, photovoltaics, might exhibit interesting magneto–plasmonic and magneto–
catalysis, and optoelectronics. Our attempt has been to relate electric properties. However, in most such cases, the future
the synthetic strategy for obtaining the optimized doped challenge will remain to be in the discovery of new doped
nanocrystals for a given property in each category; therefore, systems, with better properties and higher efficiencies, but
the chemistry involved in most cases has been discussed in without any toxic material, such as Pb and Cd; this is indeed
some detail to illustrate how to manipulate specific properties an essential step in developing environmentally benign
via dopant tuning. While synthesis of various doped nano- nanocrystals and will play increasingly crucial role in the
crystals and the doping strategy in general have been largely future.
understood, the connection between the dopant-induced new
material properties and the doping strategy have been
relatively less explored. On the other hand, there is a steady Acknowledgements
supply of reports illustrating new and technologically impor-
tant material properties of such doped nanocrystals and it DST of India (SJF/CSA-01/2010-11, SR/S2/RJN-61/2012) is
appears nearly certain that many more unexpected and acknowledged for funding. N.P., S.D.A., A.N. acknowledge
exciting properties will be unveiled in the near future. The Swarnajayanti, CSIR and Ramanujun fellowships, respec-
important future aspects of these materials are summarized tively.
below.
A great deal of effort has been spent in designing,
understanding, and optimizing the optical properties of such Conflict of interest
nanocrystals. It is clear that next generation light-emitting
devices might be possible using doped nanocrystals owing to The authors declare no conflict of interest.
their highly desirable nearly absent self-reabsorption and also
their often high quantum efficiencies. They also have great

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How to cite: Angew. Chem. Int. Ed. 2017, 56, 7038 – 7054 [12] J. Kim, G. K. Ong, Y. Wang, G. LeBlanc, T. E. Williams, T. M.
Angew. Chem. 2017, 129, 7144 – 7160 Mattox, B. A. Helms, D. J. Milliron, Nano Lett. 2015, 15, 5574.
[13] R. J. Mendelsberg, P. M. McBride, J. T. Duong, M. J. Bailey, A.
Llordes, D. J. Milliron, B. A. Helms, Adv. Opt. Mater. 2015, 3,
1293.
[1] a) C. B. Murray, D. J. Norris, M. G. Bawendi, J. Am. Chem. Soc. [14] a) V. R. Pavle, R. G. Daniel, Phys. Rev. Lett. 2003, 91, 157202;
1993, 115, 8706; b) A. P. Alivisatos, Science 1996, 271, 933; c) X. b) D. A. Schwartz, D. R. Gamelin, Adv. Mater. 2004, 16, 2115;
Peng, T. E. Wilson, A. P. Alivisatos, P. G. Schultz, Angew. Chem. c) K. R. Kittilstved, W. K. Liu, D. R. Gamelin, Nat. Mater. 2006,
Int. Ed. Engl. 1997, 36, 145; Angew. Chem. 1997, 109, 113; d) M. 5, 291.
Nirmal, L. Brus, Acc. Chem. Res. 1999, 32, 407; e) M. A. El- [15] a) S. Sapra, A. Prakash, A. Ghangrekar, N. Periasamy, D. D.
Sayed, Acc. Chem. Res. 2004, 37, 326; f) R. Jin, Angew. Chem. Sarma, J. Phys. Chem. B. 2005, 109, 1663; b) N. Pradhan, D.
Int. Ed. 2008, 47, 6750; Angew. Chem. 2008, 120, 6852; g) G. Goorskey, J. Thessing, X. Peng, J. Am. Chem. Soc. 2005, 127,
Konstantatos, L. Levina, A. Fischer, E. H. Sargent, Nano Lett. 17586; c) S. Sarkar, N. S. Karan, N. Pradhan, Angew. Chem. Int.
2008, 8, 1446; h) X. Peng, Acc. Chem. Res. 2010, 43, 1387.
Ed. 2011, 50, 6065; Angew. Chem. 2011, 123, 6189; d) A. Sahu,
[2] a) D. J. Norris, A. L. Efros, S. C. Erwin, Science 2008, 319, 1776;
M. S. Kang, A. Kompch, C. Notthoff, A. W. Wills, D. Deng, M.
b) N. Pradhan, D. D. Sarma, J. Phys. Chem. Lett. 2011, 2, 2818;
Winterer, C. D. Frisbie, D. J. Norris, Nano Lett. 2012, 12, 2587.
c) R. Buonsanti, D. J. Milliron, Chem. Mater. 2013, 25, 1305.
[16] a) N. S. Karan, D. D. Sarma, R. M. Kadam, N. Pradhan, J. Phys.
[3] a) D. J. Norris, N. Yao, F. T. Charnock, T. A. Kennedy, Nano
Chem. Lett. 2010, 1, 2863; b) S. Acharya, N. Pradhan, J. Phys.
Lett. 2001, 1, 3; b) Y. Yang, O. Chen, A. Angerhofer, Y. C. Cao, J.
Chem. C 2011, 115, 19513; c) J. Eilers, E. Groeneveld, C.
Am. Chem. Soc. 2006, 128, 12428; c) V. A. Vlaskin, R. Beaulac,
de Mello Donega, A. Meijerink, J. Phys. Chem. Lett. 2012, 3,
D. R. Gamelin, Nano Lett. 2009, 9, 4376; d) B. B. Srivastava, S.
1663; d) X. Sun, X. Huang, J. Guo, W. Zhu, Y. Ding, G. Niu, A.
Jana, N. S. Karan, S. Paria, N. R. Jana, D. D. Sarma, N. Pradhan,
Wang, D. O. Kiesewetter, Z. L. Wang, S. Sun, X. Chen, J. Am.
J. Phys. Chem. Lett. 2010, 1, 1454; e) R. Zeng, M. Rutherford, R.
Chem. Soc. 2014, 136, 1706.
Xie, B. Zou, X. Peng, Chem. Mater. 2010, 22, 2107; f) S. Acharya,
[17] G. M. Dalpian, J. R. Chelikowsky, Phys. Rev. Lett. 2006, 96,
D. D. Sarma, N. R. Jana, N. Pradhan, J. Phys. Chem. Lett. 2010, 1,
226802.
485; g) A. Nag, R. Cherian, P. Mahadevan, A. V. Gopal, A.
[18] A. Nag, S. Chakraborty, D. D. Sarma, J. Am. Chem. Soc. 2008,
Hazarika, A. Mohan, A. S. Vengurlekar, D. D. Sarma, J. Phys.
130, 10605.
Chem. C 2010, 114, 18323; h) O. Chen, D. E. Shelby, Y. Yang, J.
[19] a) D. Li, B. L. Clark, D. A. Keszler, P. Keir, J. F. Wager, Chem.
Zhuang, T. Wang, C. Niu, N. Omenetto, Y. C. Cao, Angew.
Chem. Int. Ed. 2010, 49, 10132; Angew. Chem. 2010, 122, 10330; Mater. 2000, 12, 268; b) B. D. Yuhas, D. O. Zitoun, P. J. Pau-
i) B. B. Srivastava, S. Jana, N. Pradhan, J. Am. Chem. Soc. 2011, zauskie, R. He, P. Yang, Angew. Chem. Int. Ed. 2006, 45, 420;
133, 1007; j) H.-Y. Chen, S. Maiti, D. H. Son, ACS Nano 2012, 6, Angew. Chem. 2006, 118, 434; c) I. A. Paul, A. S. Steven, R. G.
583; k) C. Gerard, R. Das, P. Mahadevan, D. D. Sarma, J. Phys. Daniel, J. Am. Chem. Soc. 2007, 129, 9808; d) Y. Yang, O. Chen,
Chem. Lett. 2013, 4, 1023; l) S. Jana, G. Manna, B. B. Srivastava, A. Angerhofer, Y. C. Cao, J. Am. Chem. Soc. 2008, 130, 15649;
N. Pradhan, Small 2013, 9, 3904; m) P. K. Jain, K. Manthiram, e) R. Xie, X. Peng, J. Am. Chem. Soc. 2009, 131, 10645; f) W.
J. H. Engel, S. L. White, J. A. Faucheaux, A. P. Alivisatos, Zhang, Y. Li, H. Zhang, X. Zhou, X. Zhong, Inorg. Chem. 2011,
Angew. Chem. Int. Ed. 2013, 52, 13671; Angew. Chem. 2013, 50, 10432; g) J. Lin, Q. Zhang, L. Wang, X. Liu, W. Yan, T. Wu, X.
125, 13916; n) Z. Zhang, D. Li, R. Xie, W. Yang, Angew. Chem. Bu, P. Feng, J. Am. Chem. Soc. 2014, 136, 4769.
Int. Ed. 2013, 52, 5052; Angew. Chem. 2013, 125, 5156; o) K. P. [20] S. C. Erwin, L. Zu, M. I. Haftel, A. L. Efros, T. A. Kennedy, D. J.
Kadlag, M. J. Rao, A. Nag, J. Phys. Chem. Lett. 2013, 4, 1676; Norris, Nature 2005, 436, 91.
p) X. Liu, M. T. Swihart, Chem. Soc. Rev. 2014, 43, 3908; q) W. [21] a) R. N. Bhargava, D. Gallagher, X. Hong, A. Nurmikko, Phys.
Zhang, Q. Lou, W. Ji, J. Zhao, X. Zhong, Chem. Mater. 2014, 26, Rev. Lett. 1994, 72, 416; b) X. Huang, A. Makmal, J. R.
1204; r) J. S. DuChene, B. C. Sweeny, A. C. Johnston-Peck, D. Chelikowsky, L. Kronik, Phys. Rev. Lett. 2005, 94, 236801; c) N.
Su, E. A. Stach, W. D. Wei, Angew. Chem. Int. Ed. 2014, 53, 7887; Pradhan, D. M. Battaglia, Y. Liu, X. Peng, Nano Lett. 2007, 7,
Angew. Chem. 2014, 126, 8021; s) C. S. Erickson, L. R. Bradshaw, 312; d) R. Beaulac, P. I. Archer, X. Liu, S. Lee, G. M. Salley, M.
S. McDowall, J. D. Gilbertson, D. R. Gamelin, D. L. Patrick, Dobrowolska, J. K. Furdyna, D. R. Gamelin, Nano Lett. 2008, 8,
ACS Nano 2014, 8, 3461; t) A. M. Schimpf, K. E. Knowles, G. M. 1197; e) P. T. K. Chin, J. W. Stouwdam, R. A. J. Janssen, Nano
Carroll, D. R. Gamelin, Acc. Chem. Res. 2015, 48, 1929; u) A. M. Lett. 2009, 9, 745; f) G. Manna, S. Jana, R. Bose, N. Pradhan, J.
Schimpf, S. D. Lounis, E. L. Runnerstrom, D. J. Milliron, D. R. Phys. Chem. Lett. 2012, 3, 2528; g) S. Acharya, S. Sarkar, N.
Gamelin, J. Am. Chem. Soc. 2015, 137, 518; v) A. K. Guria, G. Pradhan, J. Phys. Chem. C 2013, 117, 6006; h) E. Sotelo-
Prusty, B. K. Patra, N. Pradhan, J. Am. Chem. Soc. 2015, 137, Gonzalez, L. Roces, S. Garcia-Granda, M. T. Fernandez-
5123. Arguelles, J. M. Costa-Fernandez, A. Sanz-Medel, Nanoscale
[4] V. A. Vlaskin, N. Janssen, J. van Rijssel, R. Beaulac, D. R. 2013, 5, 9156; i) C. Pu, J. Zhou, R. Lai, Y. Niu, W. Nan, X. Peng,
Gamelin, Nano Lett. 2010, 10, 3670. Nano Res. 2013, 6, 652; j) S. Maiti, H.-Y. Chen, Y. Park, D. H.
[5] N. Liu, M. L. Tang, M. Hentschel, H. Giessen, A. P. Alivisatos, Son, J. Phys. Chem. C 2014, 118, 18226; k) B. Yang, X. Shen, H.
Nat. Mater. 2011, 10, 631. Zhang, Y. Cui, J. Zhang, Sci. Adv. Mater. 2014, 6, 623; l) V. K.
[6] R. Beaulac, P. I. Archer, J. van Rijssel, A. Meijerink, D. R. Sharma, S. Gokyar, Y. Kelestemur, T. Erdem, E. Unal, H. V.
Gamelin, Nano Lett. 2008, 8, 2949. Demir, Small 2014, 10, 4961; m) L. Peng, D. Li, Z. Zhang, K.
[7] a) S. Sarkar, R. Bose, S. Jana, N. R. Jana, N. Pradhan, J. Phys. Huang, Y. Zhang, Z. Shi, R. Xie, W. Yang, Nano Res. 2015, 8,
Chem. Lett. 2010, 1, 636; b) S. Sarkar, A. R. Maity, N. S. Karan, 3316; n) L. R. Bradshaw, K. E. Knowles, S. McDowall, D. R.
N. Pradhan, J. Phys. Chem. C 2013, 117, 21988. Gamelin, Nano Lett. 2015, 15, 1315.
[8] R. Fainblat, C. J. Barrows, E. Hopmann, S. Siebeneicher, V. A. [22] a) S. Jana, B. B. Srivastava, N. Pradhan, J. Phys. Chem. Lett. 2011,
Vlaskin, D. R. Gamelin, G. Bacher, Nano Lett. 2016, 16, 6371. 2, 1747; b) S. Jana, B. B. Srivastava, S. Jana, R. Bose, N. Pradhan,
[9] P. K. Santra, P. V. Kamat, J. Am. Chem. Soc. 2012, 134, 2508. J. Phys. Chem. Lett. 2012, 3, 2535; c) B. Yang, X. Shen, H. Zhang,
[10] S. Sarkar, A. K. Guria, N. Pradhan, Chem. Commun. 2013, 49, Y. Cui, J. Zhang, J. Phys. Chem. C 2013, 117, 15829; d) S. Jana, G.
6018. Manna, B. B. Srivastava, N. Pradhan, Small 2013, 9, 3753.
[11] R. A. Gilstrap, C. J. Capozzi, C. G. Carson, R. A. Gerhardt, C. J. [23] S. L. White, J. G. Smith, M. Behl, P. K. Jain, Nat. Commun. 2013,
Summers, Adv. Mater. 2008, 20, 4163. 4, 3933.

7052 www.angewandte.org T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2017, 56, 7038 – 7054
 Angewandte
Reviews Chemie

[24] a) R. V. D. Chen, G. L. Ong, R. Xie, M. Balasubramaninan, X. [47] G. V. Naik, J. L. Schroeder, X. J. Ni, A. V. Kildishev, T. D. Sands,
Peng, J. Am. Chem. Soc. 2009, 131, 9333; b) R. Viswanatha, S. A. Boltasseva, Opt. Mater. Express 2012, 2, 478.
Brovelli, A. Pandey, S. A. Crooker, V. I. Klimov, Nano Lett. [48] a) G. V. Naik, V. M. Shalaev, A. Boltasseva, Adv. Mater. 2013, 25,
2011, 11, 4753; c) K. E. Knowles, K. H. Hartstein, T. B. Kilburn, 3264; b) J. A. Faucheaux, A. L. D. Stanton, P. K. Jain, J. Phys.
A. Marchioro, H. D. Nelson, P. J. Whitham, D. R. Gamelin, Chem. Lett. 2014, 5, 976; c) S. D. Lounis, E. L. Runnerstrorm, A.
Chem. Rev. 2016, 116, 10820. Llordes, D. J. Milliron, J. Phys. Chem. Lett. 2014, 5, 1564; d) A.
[25] a) K. E. Knowles, H. D. Nelson, T. B. Kilburn, D. R. Gamelin, J. Comin, L. Manna, Chem. Soc. Rev. 2014, 43, 3957; e) T. M.
Am. Chem. Soc. 2015, 137, 13138; b) L. Yang, K. E. Knowles, A. Mattox, X. C. Ye, K. Manthiram, P. J. Schuck, A. P. Alivisatos,
Gopalan, K. E. Hughes, M. C. James, D. R. Gamelin, Chem. J. J. Urban, Adv. Mater. 2015, 27, 5830; f) B. Tandon, A. Ashok,
Mater. 2016, 28, 7375. A. Nag, Pramana 2015, 84, 1087.
[26] J. Liu, Q. Zhao, J.-L. Liu, Y.-S. Wu, Y. Cheng, M.-W. Ji, H.-M. [49] J. M. Luther, P. K. Jain, T. Ewers, A. P. Alivisatos, Nat. Mater.
Qian, W.-C. Hao, L.-J. Zhang, X.-J. Wei, S.-G. Wang, J.-T. Zhang, 2011, 10, 361.
Y. Du, S.-X. Dou, H.-S. Zhu, Adv. Mater. 2015, 27, 2753. [50] I. Kriegel, C. Y. Jiang, J. Rodriguez-Fernandez, R. D. Schaller,
[27] a) J. Yang, R. Fainblat, S. G. Kwon, F. Muckel, J. H. Yu, H. D. V. Talapin, E. da Como, J. Feldmann, J. Am. Chem. Soc. 2012,
Terlinden, B. H. Kim, D. Iavarone, M. K. Choi, I. Y. Kim, I. Park, 134, 1583.
H.-K. Hong, J. Lee, J. S. Son, Z. Lee, K. Kang, S.-J. Hwang, G. [51] a) K. Manthiram, A. P. Alivisatos, J. Am. Chem. Soc. 2012, 134,
Bacher, T. Hyeon, J. Am. Chem. Soc. 2015, 137, 12776; b) A. 3995; b) Q. Huang, S. Hu, J. Zhuang, X. Wang, Chem. Eur. J.
Hazarika, A. Layek, S. De, A. Nag, S. Debnath, P. Mahadevan, 2012, 18, 5283.
A. Chowdhury, D. D. Sarma, Phys. Rev. Lett. 2013, 110, 267401. [52] X. C. Ye, J. Y. Fei, B. T. Diroll, T. Paik, C. B. Murray, J. Am.
[28] N. Pradhan, ChemPhysChem 2016, 17, 1087. Chem. Soc. 2014, 136, 11680.
[29] A. Hazarika, A. Pandey, D. D. Sarma, J. Phys. Chem. Lett. 2014, [53] E. L. Runnerstrom, A. Llordes, S. D. Lounis, D. J. Milliron,
5, 2208. Chem. Commun. 2014, 50, 10555.
[30] C. Pu, J. Ma, H. Qin, M. Yan, T. Fu, Y. Niu, X. Yang, Y. Huang, F. [54] B. Tandon, G. S. Shanker, A. Nag, J. Phys. Chem. Lett. 2014, 5,
Zhao, X. Peng, ACS Cent. Sci. 2016, 2, 32. 2306.
[31] J.-C. Zhang, L.-Z. Zhao, Y.-Z. Long, H.-D. Zhang, B. Sun, W.-P. [55] a) M. Kanehara, H. Koike, T. Yoshinaga, T. Teranishi, J. Am.
Han, X. Yan, X. Wang, Chem. Mater. 2015, 27, 7481. Chem. Soc. 2009, 131, 17736; b) T. Wang, P. V. Radovanovic, J.
[32] S. Taguchi, A. Ishizumi, Y. Kanemitsu, J. Phys. Soc. Jpn. 2010, 79, Phys. Chem. C 2011, 115, 406; c) R. Buonsanti, A. Llordes, S.
063710. Aloni, B. A. Helms, D. J. Milliron, Nano Lett. 2011, 11, 4706;
[33] L. R. Bradshaw, A. Hauser, E. J. McLaurin, D. R. Gamelin, J. d) T. R. Gordon, T. Paik, D. R. Klein, G. V. Naik, H. Caglayan,
Phys. Chem. C 2012, 116, 9300. A. Boltasseva, C. B. Murray, Nano Lett. 2013, 13, 2857; e) E.
[34] S. Sarkar, B. K. Patra, A. K. Guria, N. Pradhan, J. Phys. Chem. Della Gaspera, A. S. R. Chesman, J. van Embden, J. J. Jasieniak,
Lett. 2013, 4, 2084. ACS Nano 2014, 8, 9154; f) M. K. Hamza, J. M. Bluet, K.
[35] J. D. Rinehart, A. L. Weaver, D. R. Gamelin, J. Am. Chem. Soc. Masenelli-Varlot, B. Canut, O. Boisron, P. Melinon, B. Masenelli,
2012, 134, 16175. Nanoscale 2015, 7, 12030.
[36] S. Sarkar, A. K. Guria, B. K. Patra, N. Pradhan, Nanoscale 2014, [56] R. W. Johns, H. A. Bechtel, E. L. Runnerstrom, A. Agrawal,
6, 3786. S. D. Lounis, D. J. Milliron, Nat. Commun. 2016, 7, 11583.
[37] S. Gul, J. K. Cooper, P.-A. Glans, J. Guo, V. K. Yachandra, J. [57] a) J. K. Furdyna, J. Appl. Phys. 1988, 64, R29; b) T. Dietl, Nat.
Yano, J. Z. Zhang, ACS Nano 2013, 7, 8680. Mater. 2010, 9, 965.
[38] E. J. McLaurin, V. A. Vlaskin, D. R. Gamelin, J. Am. Chem. Soc. [58] a) G. Bacher, A. A. Maksimov, H. Schomig, V. D. Kulakovskii,
2011, 133, 14978. M. K. Welsch, A. Forchel, P. S. Dorozhkin, A. Chernenko, S.
[39] a) G. K. Grandhi, R. Tomar, R. Viswanatha, ACS Nano 2012, 6, Lee, M. Dobrowolska, J. K. Furdyna, Phys. Rev. Lett. 2002, 89,
9751; b) S. Brovelli, C. Galland, R. Viswanatha, V. I. Klimov, 127201; b) P. I. Archer, S. A. Santangelo, D. R. Gamelin, J. Am.
Nano Lett. 2012, 12, 4372; c) G. K. Grandhi, K. Swathi, K. S. Chem. Soc. 2007, 129, 9808; c) D. A. Bussian, S. A. Crooker, M.
Narayan, R. Viswanatha, J. Phys. Chem. Lett. 2014, 5, 2382. Yin, M. Brynda, A. L. Efros, V. I. Klimov, Nat. Mater. 2009, 8, 35;
[40] T. Debnath, P. Maity, S. Maiti, H. N. Ghosh, J. Phys. Chem. Lett. d) R. Beaulac, L. Schneider, P. I. Archer, G. Bacher, D. R.
2014, 5, 2836. Gamelin, Science 2009, 325, 973.
[41] J. Wang, Y. Li, Q. Shen, T. Izuishi, Z. Pan, K. Zhao, X. Zhong, J. [59] J. Kobak, T. Smolenski, M. Goryca, M. Papaj, K. Gietka, A.
Mater. Chem. A 2016, 4, 877. Bogucki, M. Koperski, J. G. Rousset, J. Suffczynski, E. Janik, M.
[42] Y. Dong, J. Choi, H.-K. Jeong, D. H. Son, J. Am. Chem. Soc. Nawrocki, A. Golnik, P. Kossacki, W. Pacuski, Nat. Commun.
2015, 137, 5549. 2014, 5, 3191.
[43] a) X. Chen, S. Shen, L. Guo, S. S. Mao, Chem. Rev. 2010, 110, [60] S. Sapra, D. D. Sarma, S. Sanvito, N. A. Hill, Nano Lett. 2002, 2,
6503; b) D. B. Ingram, S. Linic, J. Am. Chem. Soc. 2011, 133, 605.
5202; c) J. B. Priebe, M. Karnahl, H. Junge, M. Beller, D. [61] N. Feltin, L. Levy, D. Ingert, M. P. Pileni, Adv. Mater. 1999, 11,
Hollmann, A. Brueckner, Angew. Chem. Int. Ed. 2013, 52, 11420; 398.
Angew. Chem. 2013, 125, 11631; d) G. Manna, R. Bose, N. [62] D. D. Sarma, R. Viswanatha, S. Sapra, A. Prakash, M. Garcia-
Pradhan, Angew. Chem. Int. Ed. 2014, 53, 6743; Angew. Chem. Hernandez, J. Nanosci. Nanotechnol. 2005, 5, 1503.
2014, 126, 6861; e) R. Marschall, Adv. Funct. Mater. 2014, 24, [63] a) J. H. Yu, X. Y. Liu, K. E. Kweon, J. Joo, J. Park, K. T. Ko, D.
2421; f) H. Song, Acc. Chem. Res. 2015, 48, 491. Lee, S. P. Shen, K. Tivakornsasithorn, J. S. Son, J. H. Park, Y. W.
[44] a) D. Mocatta, G. Cohen, J. Schattner, O. Millo, E. Rabani, U. Kim, G. S. Hwang, M. Dobrowolska, J. K. Furdyna, T. Hyeon,
Banin, Science 2011, 332, 77; b) M. S. Kang, A. Sahu, C. D. Nat. Mater. 2010, 9, 47; b) V. A. Vlaskin, C. J. Barrows, C. S.
Frisbie, D. J. Norris, Adv. Mater. 2013, 25, 725; c) A. Stavrinadis, Erickson, D. R. Gamelin, J. Am. Chem. Soc. 2013, 135, 14380.
A. K. Rath, F. P. G. de Arquer, S. L. Diedenhofen, C. Magen, L. [64] C. J. Barrows, V. A. Vlaskin, D. R. Gamelin, J. Phys. Chem. Lett.
Martinez, D. So, G. Konstantatos, Nat. Commun. 2013, 4, 2981. 2015, 6, 3076.
[45] a) U. Kreibig, M. Vollmer, Optical Properties of Metal Clusters, [65] W. D. Rice, W. Y. Liu, T. A. Baker, N. A. Sinitsyn, V. I. Klimov,
Vol. 25, Springer, Berlin, 1995; b) M. A. El-Sayed, Acc. Chem. S. A. Crooker, Nat. Nanotechnol. 2016, 11, 137.
Res. 2001, 34, 257. [66] S. Delikanli, M. Z. Akgul, J. R. Murphy, B. Barman, Y. Tsai, T.
[46] K. Biswas, C. N. R. Rao, J. Phys. Chem. B 2006, 110, 842. Scrace, P. Y. Zhang, B. Bozok, P. L. Hernandez-Martinez, J.

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Christodoulides, A. N. Cartwright, A. Petrou, H. V. Demir, ACS Wang, X. Y. Yang, T. Yao, J. F. He, Z. H. Sun, F. C. Hu, Z. Y. Wu,
Nano 2015, 9, 12473. Z. Xie, S. Q. Wei, J. Am. Chem. Soc. 2014, 136, 1150.
[67] H. D. Nelson, L. R. Bradshaw, C. J. Barrows, V. A. Vlaskin, [73] a) G. S. Shanker, B. Tandon, T. Shibata, S. Chattopadhyay, A.
D. R. Gamelin, ACS Nano 2015, 9, 11177. Nag, Chem. Mater. 2015, 27, 892; b) B. Tandon, A. Yadav, A.
[68] P. M. Koenraad, M. E. Flatte, Nat. Mater. 2011, 10, 91. Nag, Chem. Mater. 2016, 28, 3620.
[69] M. Goryca, T. Kazimierczuk, M. Nawrocki, A. Golnik, J. Gaj, P. [74] R. Viswanatha, D. Naveh, J. R. Chelikowsky, L. Kronik, D. D.
Kossacki, P. Wojnar, G. Karczewski, Phys. Rev. Lett. 2009, 103, Sarma, J. Phys. Chem. Lett. 2012, 3, 2009.
087401. [75] S. S. Farvid, T. Sabergharesou, L. N. Huffluss, M. Hegde, E.
[70] L. Besombes, Y. Leger, L. Maingault, D. Ferrand, H. Mariette, J. Prouzet, P. V. Radovanovic, J. Am. Chem. Soc. 2014, 136, 7669.
Cibert, Phys. Rev. Lett. 2004, 93, 207403. [76] A. Sundaresan, R. Bhargavi, N. Rangarajan, U. Siddesh, C. N. R.
[71] A. K. Bhattacharjee, Phys. Rev. B 2007, 76, 075305. Rao, Phys. Rev. B 2006, 74, 161306.
[72] a) J. M. D. Coey, M. Venkatesan, C. B. Fitzgerald, Nat. Mater. [77] A. M. Schimpf, J. D. Rinehart, S. T. Ochsenbein, D. R. Gamelin,
2005, 4, 173; b) J. Philip, A. Punnoose, B. I. Kim, K. M. Reddy, S. J. Phys. Chem. Lett. 2015, 6, 1748.
Layne, J. O. Holmes, B. Satpati, P. R. Leclair, T. S. Santos, J. S.
Moodera, Nat. Mater. 2006, 5, 298; c) S. T. Ochsenbein, Y. Feng, Manuscript received: November 25, 2016
K. M. Whitaker, E. Badaeva, W. K. Liu, X. S. Li, D. R. Gamelin, Revised manuscript received: January 18, 2017
Nat. Nanotechnol. 2009, 4, 681; d) W. W. Zheng, G. F. Strouse, J. Accepted manuscript online: February 2, 2017
Am. Chem. Soc. 2011, 133, 7482; e) W. S. Yan, Q. H. Liu, C. Version of record online: May 23, 2017

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