pubs.acs.

org/JPCL Letter

Intraband Transitions of Nanocrystals Transforming from Lead

Selenide to Self-doped Silver Selenide Quantum Dots by Cation
Exchange
Rajesh Bera, Dongsun Choi, Yoon Seo Jung, Haemin Song, and Kwang Seob Jeong*
Cite This: J. Phys. Chem. Lett. 2022, 13, 6138−6146 Read Online

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ABSTRACT: In search of heavy metal-free mid-IR active colloidal materials, self-

doped silver selenide colloidal quantum dots (CQDs) can be an alternative
offering tunable mid-IR wavelength with a narrow bandwidth. One of the
challenges in the study of the intraband transition is developing a method to widen
the intraband transition energy range as well as reducing the toxicity of the
materials. Here, we present AgxSe (x > 2) CQDs exhibiting an intraband transition
up to 0.39 eV, produced by the cation exchange (CE) method from PbSe CQDs.
The major electronic transition efficiently changes from the SWIR band gap of
PbSe CQDs to the mid-IR intraband transition of the AgxSe CQDs by the CE. The
intraband exciton is verified by examining the absorption and emission of the CE
AgxSe CQDs as well as their applications on electrochemical mid-IR luminescence
and mid-IR intraband photodetectors.

R ecently, mid-infrared (mid-IR) colloidal quantum dots

(CQDs) have attracted significant attention due to their
optical and electrical features that can be used for various
applications such as thermoelectricity, infrared optoelectronics,
and the food industries.1−5
Conventionally, the infrared industries have widely used
HgCdTe, InSb, and other II−V infrared superlattices as a
source of narrow gap semiconductors, made by epitaxial or
single-crystal growth methods with high manufacturing
costs.6,7 The preceding precursor chemistry has realized the
colloidal synthesis of low-dimensional infrared nanocrystals
where one can easily tune the optical and electrical properties.8
Furthermore, by virtue of manipulating the stoichiometry and
surface dipole of the nanocrystals, higher electronic transitions
such as intraband transitions are now available for mid-IR
infrared optoelectronics.9,10 The unique character of the self-
doped nanocrystal is the stand-alone intraband transition
explicitly separated from the interband transition, allowing one
to utilize the target frequency without an additional optical
filter.
The steady-state intraband transitions were first found from
the mercury chalcogenide quantum dots.3,11 The toxicity of the
Hg-based self-doped CQDs motivates the development of new
methods for achieving the intraband transition in non-Hg-
based CQDs. In 2018, Jeong and his co-workers proved a
steady-state intraband transition (1Se-1Pe) of Ag2Se nanocryst-
als synthesized by the colloidal hot injection method, which is
tunable in frequency with varying the size of the nanocrystals.12
In addition, the localized surface plasmon resonance (LSPR)
values in Ag2Se CQDs were reported in 2020, which elongated
the intraband transition wavelength further.13 There have been
other reports presenting the intraband photosensitive proper-
ties of the Ag2Se CQDs as well.14−17
Not only elongating but also shortening the wavelength of
the intraband transitions is imperative. The higher frequency
intraband transition advantages are the distinct excitonic
feature, well-separated energy states leading to the greater
Stokes shift, and relatively lower dark current in intraband QD
solid devices. So far, a intraband transition over 0.37 eV (3000
cm−1) for the Ag2Se CQDs has yet to be reported. This is
attributed to the difficulty of achieving small size self-doped
Ag2Se CQDs with high carrier density, which is essential for
realizing the intraband transitions.
To avoid the synthetic issues, the modification is required to
synthesize the smaller self-doped Ag2Se CQDs. The post-
synthetic cation exchange (CE) method was carefully chosen
because of its advantages such as room-temperature reaction
and controllability of the size, shape, composition, and
crystalline structure.18
Alivisatos and his co-workers demonstrated the reversible
cation exchange of a wide range of nanocrystals.19 The CE
from Pb2+ to Cd2+ in PbSe nanocrystals was reported by
Received: April 21, 2022
Accepted: June 22, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acs.jpclett.2c01179

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The Journal of Physical Chemistry Letters pubs.acs.org/JPCL Letter

Figure 1. (A) Schematic of the cation exchange from the PbSe CQDs template to self-doped Ag2Se CQDs at room temperature. (B) FTIR
absorption spectra of the cation-exchanged product with time. (C−E) TEM images and size distributions (in insets) of the cation-exchanged AgxSe
CQDs after the CE reaction from PbSe CQDs (C, small ∼3.9 ± 0.5 nm; D, medium ∼5.2 ± 0.4 nm; E, large ∼6.3 ± 0.4 nm). (F) X-ray diffraction
(XRD) patterns of the small, medium, and large cation-exchanged Ag2Se CQDs at room temperature. (G) Temperature-dependent XRD patterns
of small Ag2Se CQDs (∼3.9 ± 0.5 nm).

Casavola et al. and generated the heterostructure PbSe/CdSe
in cubic, star, and rod shapes,20 while Eychmüller and his co-
workers succeeded in transforming CdSe nanoplatelets (NPLs)
to PbSe NPLs via cation exchange.21 However, all reports
restricted the scope to the stoichiometric nanocrystals showing
the band gap transition only without any study on the steady-
state intraband transitions which were realized only after
2014.22,23
Here, we present the CE method to produce self-doped
AgxSe (x > 2) exhibiting a steady-state intraband transition up
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to ∼3184 cm−1 (0.39 eV, 3.1 μm). The presence of an
intraband exciton is confirmed by measuring the intraband
photoluminescence and photocurrent. Furthermore, the infra-
red spectro-electrochemical measurement revealed tunable
mid-IR intraband photoluminescence sensitive to external
electrochemical potential.
The template materials, rock salt PbSe CQDs with three
different sizes, 4.13 ± 0.3 nm, 5.3 ± 0.5 nm, and 6.3 ± 0.6 nm,
were synthesized by the hot injection method (Figures S1 and
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S2). The cation exchange from Pb2+ to Ag+ was performed in
nonpolar solvents (hexane−toluene) (Figure 1A−B).
Figure 1C−E shows the TEM images of the cation-
exchanged AgxSe CQDs (relatively small, ∼3.9 ± 0.4 nm;
medium, ∼5.3 ± 0.5 nm; and large sized AgxSe ∼6.3 ± 0.5
nm). The energy-dispersive X-ray spectroscopy (EDS) analysis
of the TEM image and high-angle annular dark-field scanning
transmission electron microscopy (HAADF-STEM) infer the
cation-exchanged Ag2Se rather than the formation of an alloy
or core−shell structure (Figures S3 and S4). The elemental
composition of Ag2Se CQDs, determined by the inductively
coupled plasma−atomic emission spectroscopy (ICP-AES)
experiment, provides the ratio of Ag/Se (∼3). A small amount
of Pb atoms (<2%) was found in both EDS (Ag:Se:Pb =
0.8:0.18:0.02) and ICP-AES data (Ag:Se:Pb = 0.76:0.22:0.02),
indicating the residual Pb ion after the CE.
The cation-exchanged small CQDs exhibit two broad peaks
at 35.68° and 44.45° (=2θ) corresponding to the (200) and
(211) planes, of which the interplanar distances (d) are 0.251
and 0.203 nm, respectively (Figure 1F-a). The fast Fourier
transform (FFT) analysis of the HR-TEM image offers the
interplanar distance (d) of 0.252 nm for the (200) plane,
showing consistency with the XRD pattern result (Figure S5).
This FFT result reflects the cubic crystal structure of the small
AgxSe CQD (a = b = c = 0.498 nm) at room temperature,
which is well-matched with the reported value.24 Surprisingly,
additional peaks at 2θ = 30.69°, 33.79°, 40.15°, and 44.6°
along with a strong peak at 36.15° were observed in the large
AgxSe CQDs (6.3 ± 0.5 nm). These strong peaks are assigned
to the (201), (211), (221), (202), and (220) planes of the
tetragonal phase,24,25 which suggests the transformation of the
cubic phase with an increase of the nanocrystal size.
The crystal phase transformation of AgxSe CQDs is
examined by the temperature-dependent XRD experiment
(T-XRD).13,24 The peaks of the small AgxSe CQDs do not
change by increasing the temperature from room temperature
(RT) (brown) to 338 K (red, Figure 1G). On the other hand,
by lowering the temperature to 81 K, the peak at 36.05° at RT
shifts to a higher angle of 36.31° along with the generation of
additional peaks at 30.66°, 33.74°, and 44.75° (Figure 1G).
The corresponding planes of 2θ angle can be assigned to 201
(30.66°), 211 (33.74°), 220 (36.37°), and 202 (44.75°). Based
on Bragg’s law (nλ = 2d sin θ), the interplanar distances (d) of
the respective planes are calculated and tabulated in Table S1.
While the previous literature suggested that the lattice
parameters should be a = b ≠ c where a = b = 0.706 and c =
0.498 nm for the tetragonal structure, a significant deviation is
observed in calculating the lattice parameters under the
assumption that the (220) plane represents the d value of
0.247 nm at 36.31°.24,25 Saito et al. presented the interplanar
distance (d = 0.249 nm) of the (002) plane from the electron
diffraction.26 Since it is comparable to our extracted d value
(0.247 nm) from the XRD data, the plane (002) is considered
for the 0.247 nm spacing to obtain a lattice parameter of c =
0.494 nm, which is very close to the reported value (0.498 nm)
elsewhere. Therefore, it is reasonable to conclude that the
small AgxSe forms a tetragonal structure having lattice
parameters a = b = 0.672 nm and c = 0.494 nm (Table S2)
at low temperature while it forms stable cubic AgxSe with the
calculated lattice constant (a) of 0.499 nm at high temperature.
Compared to the small CQDs (2r < 4 nm) exhibiting broad
XRD patterns, it is more apparent to assign the planes for the
large size AgxSe CQDs (2r > 5.5 nm). The d values of 0.261
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and 0.283 nm from the HR-TEM image are indexed to the
(201) and (211) planes of tetragonal AgxSe, which are close to
the 0.267 and 0.291 nm values, respectively, extracted from the
XRD data (Figure S5 and Table S3).
It was observed that the tetragonal phase at 298 K
transforms into the cubic phase with increasing the temper-
ature to 338 K (Figure S6) while the most intense peak, 2θ =
36.10°, at RT shifts to the higher angle of 36.47° (002) by
lowering the temperature (Figure S6). Additionally, we
observed the volume contraction (ΔV) for the small sized
AgxSe. The starting PbSe CQD has ∼0.229 nm3 (a = 0.612
nm) volume per unit cell, and the final product has 0.124 nm3
while maintaining the same phase.
The CE reaction between the template CQD and the
incoming cation occurs depending upon a few thermodynamic
and kinetic parameters. The probable CE mechanism is as
follows:27
PbSe (s) + 2Ag + → Ag 2Se (s) + Pb2 + (1)
In contrast, the lattice energy (ΔHLattice) value of PbSe
(3144 kJ/mol) is larger than that of Ag2Se (2686 kJ/mol),
suggesting an unfavorable CE reaction.28,29 Even when the
bond dissociation energy (BDE) is taken into account instead
of the lattice energy, the Pb−Se bond has a higher value of 302
kJ/mol than that of the Ag−Se bond of 210 kJ/mol, which
would hinder the CE process as well. In addition, the CE
process is also unfavorable in terms of entropy, as two Ag+ ions
are desolvated and one Pb2+ ion is solvated, considering that
the nanocrystal size is constant before and after the CE.18,30
However, the solubility product (Ksp) values of PbSe (1 ×
10−37) and AgxSe (1 × 10−54) infer that the CE might be
possible based on eq 2.18
ln K sp = −ΔG°/RT (2)
where R and T are the gas constant and temperature,
respectively.
Since the AgNO3−oleylamine (OLA) complex in toluene
(5.9 × 10−2 M) is used for the CE precursor, it is assumed that
Pb2+ ions bind with OLA when relatively softer Ag+ ions bind
with Se ion in host CQDs based on the absolute hardness (η)
values of Pb2+ (8.46) and Ag+ (6.96).31,32 Trioctylphosphine
(TOP), a soft base compared to OLA, does not allow Ag+ ions
to exchange with the Pb2+ ions (Figure S7).
To note, we achieved completely cation-exchanged nano-
crystals whereas Beard and his co-workers presented the Ag+
doped PbSe CQDs by replacing the Pb(oleate)2 from the PbSe
surface.33 In previous literature, the CE mechanism was
described theoretically and microscopically by several
groups.18,19,23,27,34,35 Ott et al. proposed a microscopic model
focusing on the CdSe to Ag2Se transformation.34 Jain and his
co-workers also reported the CE mechanism of a single CdSe
nanocrystal with Ag ion and revealed a cooperative transition
rather than a diffusion-limited cation-by-cation exchange,
which was further confirmed by a stochastic reaction
model.23 Considering all, we also hypothesize that at the
early stage of the process, the incorporation of Ag+ ion into the
PbSe lattice activates the nanocrystal for further Ag+ ion
doping. The incorporation of Ag+ ions continues until a critical
doping concentration is reached. Then, the PbSe is ready to
take up available Ag+ ion, resulting in a cascade of Ag ion
incorporation events and an abrupt phase transition probably
from the initial doped PbSe to Ag2Se. As we used a higher
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Figure 2. (A) Wide scan of XPS spectra of small AgxSe CQDs (3.9 nm) and the individual elements (B) Ag, (C) Se, (D) Pb, (E) O, and (F) N.

Figure 3. Normalized absorbance and PL infrared spectra of the cation-exchanged AgxSe CQDs. The diameter of the nanocrystals is (A) 3.9 nm
(B) ∼ 5.3 nm (C) ∼ 6.3 nm. (D) Differential absorption spectra of AgxSe nanocrystals under different electrochemical potentials (In the inset,
schematic of electronic transitions under reducing and oxidizing electrochemical potential). (E) Change in the absorption of the intraband (red
sphere) and band gap transitions (green star) at different electrochemical potentials. (F) Infrared emission spectra of AgxSe CQDs under negative
(−0.2 V, reducing) and (G) positive (0.2 V, oxidizing) electrochemical potentials.

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The Journal of Physical Chemistry Letters
concentration of Ag precursor (5.9 × 10−2 M), the fully cation-
exchanged AgxSe is generated in the present study rather than
doped PbSe. The underlying process during CE from PbSe to
Ag2Se would be similar as explained before for the CdSe to
Ag2Se transformation.
Moreover, the lattice mismatch between the reactant and
product is quite large at the interface, which may accelerate the
pealing of the surface of the PbSe CQDs. Surprisingly, we
could realize the self-doping of Ag2Se during the cation
exchange procedure (Figure 1B). The gradual bleaching of the
interband transitions and increment of the intraband transition
were explicitly observed during the CE process. We also found
that the CE can proceed under ambient conditions (Figure S8)
and that the products are air-stable (Figure S9).
To figure out the surface environment of the CQDs, 1H
NMR spectroscopy has also been performed before and after
the CE reaction. The native oleic acid ligands (X-type ligand)
are bonded to the PbSe CQDs, which is confirmed by the
characteristic chemical shift of the vinylic proton (-CHCH-)
at ∼5.36 ppm (Figure S10A).36 The broadness of the NMR
peak in Ag2Se CQDs is attributed to the restricted motion of
the molecules as they are bonded to the surface of the
CQDs.36,37 After the ligand exchange with 1-octanethiol, the
width of the vinylic proton peak at ∼5.36 ppm was significantly
reduced and shifted, suggesting the detachment of native
ligands from the surface (Figures S10 and S11).38,39 The XPS
survey scan and narrow scan of individual elements in QCDs
provide the characteristic binding energy peaks of N (1S) and
O (1S), originating from the oleylamine and oleic acid ligands,
respectively. In addition, typical peaks of Ag (3d) and Se (3d)
along with a weak Pb (4f) peak are observed in the XPS
spectra of cation-exchanged AgxSe CQDs (Figure 2).22,40 It is
noted that a small amount of Pb is present in the sample which
may be the byproduct of CE, although the elemental analysis
in XPS is qualitative.
Subsequently, the spectroscopic characterization was
performed to investigate the optical properties of the cation-
exchanged AgxSe CQDs. Figure 3A−C shows the normalized
absorbance and photoluminescence spectra of the AgxSe
CQDs. Surprisingly, the small sized AgxSe CQDs show
steady-state intraband transitions at 2600 cm−1, which have
never been reported for the self-doped AgxSe CQDs that are
synthesized by the hot injection method. Furthermore, this CE
method even makes it possible to realize a higher intraband
frequency over 0.37 eV (3000 cm−1) for the very small AgxSe
CQDs as shown in Figure S12. This is indeed one advantage to
employing this CE method to expand the frequency range of
the intraband transition. The medium and large sized AgxSe
CQDs exhibit the intraband transition at 2169 and 1995 cm−1,
respectively.
The intraband Stokes shift of cation-exchanged AgxSe is also
observed and is reduced with an increase of the CQD size. In
the present study, we achieved the smallest (<4 nm) self-doped
AgxSe CQDs, which show a 0.07 eV Stokes shift (Figure
S12B). Surprisingly, in contrast to the case where the self-
doped AgxSe CQDs with a center frequency of 1900 cm−1
show the quantum plasmon resonance feature in the previous
report, all cation-exchanged products here show mid-IR
emission at a similar frequency.13 This infers that the cation-
exchanged AgxSe CQDs have a lower carrier density.
The spectroelectrochemistry (SEC) method allows one to
confirm the intraband transition by changing the Fermi level.
In Figure 3D, the 1Se-1Pe intraband transition gradually
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increases at the frequency ∼2000 cm−1 whereas the band gap
transition is bleached at ∼5800 cm−1 under negative potential
(red). In our system, the negative potential corresponds to the
reduction of CQDs and enrichment of the electron density in a
nanocrystal while the oxidation potential gives a reverse effect.
The simultaneous change of both the intraband and band gap
transitions explicitly confirms the origin of the mid-IR
absorption peak of the CE AgxSe CQDs. The simultaneous
response under various electrochemical potentials would not
occur if the mid-IR absorption feature were not the intraband
transition. In other words, the simultaneous change appears
only because both the intraband transition and the band gap
transition share the 1Se state.
Under the oxidizing potential, the optical change is relatively
very small, suggesting that the number of electrons at 1Se at 0
V determined by the reference (Pt) is close to zero. To note,
the number of electrons of AgxSe CQDs in solution is different
from that of the CQD film at 0 V in the electrochemical cell.
Over 0.8 V, neither the band gap transition nor the intraband
transition significantly changes (Figure 3E). By reducing the
nanocrystal, the intensity of the intraband transition peak
explicitly enhances and the band gap transition shows a bleach.
Below −0.6 V, a plateau appears, confirming the fully occupied
1Se state with electrons. It is worth noting that, at the same size
of nanocrystals, the degree of n-type character or carrier
density in CQDs synthesized by the hot injection method is
higher than that of the CQDs obtained from the CE method.
In many cases, the presence of Ag(0) in AgxSe increases the
carrier concentration in each CQD as observed in previous
research.12,13
The intensity of the intraband PL and band gap PL of the
AgxSe CQDs can also be tuned by changing the Fermi level of
the solid CQD film. We have designed an infrared electro-
chemical cell with the three-electrode system and aligned it
with our home-built mid-IR fluorometer to collect the infrared
PL of the AgxSe CQDs under various electrochemical
potentials (Scheme 1). Under negative (reduction) potential
(−0.2 V), only the intraband emission appeared in Figure 3F.
In contrast, the recombination through the band gap transition
was also observed along with the intraband transition under
positive potential (0.2 V), inferring that the electron
Scheme 1. Schematic of the Infrared Spectro-
electrochemistry Method to Measure the Mid-IR Intraband
Photoluminescence of the Cation-Exchanged AgxSe CQD
Solid under Various Electrochemical Potentials
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Figure 4. Intraband transitions of ∼3.9 nm AgxSe at room temperature (RT) and 78 K of (A, B) ∼5.3 nm, (C, D) ∼6.3 nm, and (E, F) AgxSe
CQDs. (G) Change of the higher energy (1Se-1Pe3) transition energy with the temperature variation of AgxSe CQDs (small, squares; medium,
triangles; large, circles) and (H) change of the temperature coefficient (dE/dT) with the size of the CQDs.
population in the 1Se level successfully reduced, causing the
band gap emission (Figure 3G).
Interestingly, asymmetric absorption peaks of relatively large
CQDs have appeared, which shows larger oscillator strength at
lower frequency. Guyot-Sionnest and his co-workers observed
peak splitting of the intraband transition in a certain size of
CdSe QDs.41 Also, they reported peak splitting of HgTe
CQDs, which originates from spin−orbit coupling and the
asymmetry of the nanocrystals.42 Generally, spin−orbit
coupling is frequently observed in the case of the heavy
metal−telluride binary nanocrystal rather than the analogous
metal−selenide or metal−sulfide nanocrystal. Thus, spin−orbit
coupling is not presumed to be major effect in our case.
Recently, we reported peak splitting of AgxSe CQDs at room
temperature, which is rationalized by the change of the
nanocrystal structure from a cubic to a tetragonal structure
with an increase of the nanocrystal size.13
For further understanding of the splitting phenomena in
AgxSe CQDs, the absorption features of nanocrystals with
different sizes are carefully investigated. A single broad
absorption peak of small CQDs (3.9 ± 0.4 nm) was fitted
with three Gaussian fit functions (Figure 4A). It consists of
three different transitions, occurring between the lowest
conduction band state (1Se) and the second-lowest states
(1Pe), namely 1Se-1Pe1, 1Se-1Pe2, and 1Se-1Pe3. The energy
spacings (ΔE) between the 1Pe states are 27 and 25 meV
based on the fit function of the small CQDs in Figure 4A
(Table S4). For the medium and large sized CQDs, the
absorption spectra were fitted into two and three distinct
Gaussian fit functions, and this reveals that the peaks are
separated by 47 meV for medium CQDs and 31.4 and 16.1
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meV for large CQDs (Figure 4C, E and Tables S5 and S6). To
note, one of the 1Pe states, farthest to the right, is separated
distinctly from the other two closely spaced 1Pe states (Figure
4A, C, E) at room temperature. Surprisingly, the small AgxSe
CQDs show three well-defined peaks at 78 K, separated from
each other by 47 and 43 meV (Figure 4B). The medium and
large CQDs exhibit the same at 78 K (Figure 4D, F). The
structural distortion and asymmetry nature accelerate the
major splitting of the degenerate 1Pe (1Pe1, 1Pe2, and 1Pe3)
states. Noticeably, the 1Pe3 state among the three fine
structures of the 1Pe energy level has a greater degree of
splitting toward higher frequency (Figures S13−S15).
Figure 4G exhibits the change of the highest transition
energy (1Se-1Pe3) with temperature variation in different sized
CQDs. The experimental data are fitted linearly to extract the
slope, which is assigned as the temperature coefficient (dE/
dT).43 The temperature coefficient of a band gap transition is
known to be dependent on the nanocrystal size.44 In this study,
we investigated the temperature coefficients of the intraband
transitions for the self-doped nanocrystals. The extracted
coefficients are −(3.19 ± 0.23) × 10−4, −(1.59 ± 0.14) ×
10−4, and −(1.09 ± 0.08) × 10−4 V/K for the small (∼3.9
nm), medium (∼5.3 nm), and large (∼6.3 nm) CQDs,
respectively (Figure 4H). It is the first time to observe that the
small size self-doped AgxSe CQDs have a greater negative
coefficient than the large size ones, suggesting that the 1Pe
states of small CQDs have a larger split in energy compared to
large QDs upon lowering the temperature.
Considering further use of the CE AgxSe CQDs, it is
essential to estimate the energy levels of CE-Ag2Se CQDs for
designing devices. Lhuillier and his co-workers found out the
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Figure 5. (A) Estimated electronic states of AgxSe CQDs. (B) Current−voltage characteristics of small AgxSe CQDs under dark and light (QCL at
2800 cm−1) conditions at room temperature (in inset ITO substrate). (C) Schematic of the photodetector device (ITO/AgxSe QD/Au). (D)
Infrared photocurrent for the device with structure ITO/AgxSe QD/Au in the presence and absence of an IR globar source at different
temperatures (78, 150, 250, and 298 K) under 0 V bias potential (change of photocurrent (Ion − Ioff) vs temperature (K) in inset). (E) Normalized
on−off current at t = 0 at different temperatures.

Fermi energy level at 4.3 eV with respect to vacuum based on
ultraviolet photoemission spectroscopy.14 Cyclic voltammetry
(CV) is also an important tool by which one can easily
estimate the energy level of the respective CQDs.45 Figure S16
shows cyclic voltammograms for the CE AgxSe CQDs having
oxidation and reduction peaks of small, medium, and large size.
As the self-doped AgxSe CQDs are n-type, the oxidation peak
corresponds to the 1Se state of the conduction band. The
reduction peak appears due to the filling of the 1Pe state in the
conduction band. In accordance with that, the calculated 1Se
and 1Pe energy states of small size AgxSe CQDs are −4.53 eV
and −4.21 eV, respectively. For the medium sized AgxSe, the
calculated 1Se and 1Pe energy states are −4.55 eV and −4.3 eV,
respectively. Interestingly, we could not find a distinct
reduction peak for the large sized AgxSe. Therefore, the 1Pe
state is extracted by combining both electrochemical data and
the optical absorption peak. The 1Se and 1Pe states are
calculated to lie at −4.59 eV and −4.38 eV, respectively. The
energy levels of the 1Se and 1Pe states are schematically
represented in Figure 5A.
Finally, we verified the mid-IR photoresponse of the CE
AgxSe CQDs. The mid-IR quantum cascade laser (3.7 μm, 20
mW) selectively activated the 1Se-1Pe intraband transition. The
calculated responsivity (R) of the device at 0.5 V is 21 mA/W
at RT (298 K, Figure 5B). Additionally, we fabricated a vertical
device with sapphire/ITO/AgxSe CQD/Au to measure the
linear current−voltage characteristic (I−V) curve (Figures 5C
and S17C). The photocurrent generated by the IR globar light
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source (22 mW/cm2) clearly shows temperature-dependent
characteristics. The photocurrent of the AgxSe sample
increases with increasing temperature (Figure 5D, inset).
Interestingly, the response time shows a similar value (∼300
ms) at each temperature (Figure 5E). The current−voltage
characteristic and the on−off feature of the device in the
presence of a Ge filter have also been measured (Figure S17D).
The photogenerated charge carrier density in the device at
various temperatures in the presence of a Ge filter has been
calculated and plotted with temperature (Figure S18). The
highest photogenerated carrier density of 0.2 × 1018/cm3 at
250 K was achieved due to the intraband transition upon
excitation. Therefore, the cation-exchanged AgxSe CQDs can
be applied as an infrared active material for mid-IR-based
optoelectronics.
In conclusion, we have demonstrated the CE methods to
synthesize n-type self-doped AgxSe CQDs with various sizes.
The size of the AgxSe CQDs is efficiently tuned depending
upon the size of the starting material of the PbSe CQDs. The
CE AgxSe CQDs exhibits the steady-state intraband transition,
inferring that the self-doping is successfully achieved by this
CE method performed at RT. The structure and energy levels
of the CE AgxSe CQDs were identified using XRD and cyclic
voltammetry. The optical properties, emerging of the steady-
state intraband transitions and bleaching of the band gap
transition, were thoroughly analyzed using FTIR spectroscopy
and infrared spectroelectrochemistry. The splitting of the
intraband transition is also examined in combination with the
https://doi.org/10.1021/acs.jpclett.2c01179
J. Phys. Chem. Lett. 2022, 13, 6138−6146
The Journal of Physical Chemistry Letters
XRD result. Furthermore, we demonstrated the electro-
chemical potential sensitive mid-IR intraband PL and the
band gap PL of the CE AgxSe CQDs, which enabled the
successful control of the two-color mid-IR emission. Lastly, we
demonstrated the use of intraband transitions for mid-IR
photodetection applications. The I−V characteristics and on−
off infrared photocurrent were successfully measured from
different device structures at various temperatures.
The CE method we present here offers an opportunity to
expand the range of the intraband transition energy to a value
that has not been accessed. This will facilitate the exploitation
of colloidal AgxSe quantum dots with a wide spectral range
from NIR to mid-IR.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpclett.2c01179.
Details of the experiment, characterization methods,
additional TEM images, XRD data, FFT analysis, d value
calculation, stability check, temperature-dependent FT
IR absorption spectra, Gaussian fittings, cyclic voltam-
metry, I−V curve of the device, and NMR spectra
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
Kwang Seob Jeong − Department of Chemistry, Korea
University, Seoul 02841, Republic of Korea; Center for
Molecular Spectroscopy and Dynamics, Institute for Basic
Science (IBS), Korea University, Seoul 02841, Republic of
Korea; orcid.org/0000-0003-3246-7599;
Email: kwangsjeong@korea.ac.kr
Authors
Rajesh Bera − Department of Chemistry, Korea University,
Seoul 02841, Republic of Korea; Center for Molecular
Spectroscopy and Dynamics, Institute for Basic Science (IBS),
Korea University, Seoul 02841, Republic of Korea;
orcid.org/0000-0001-8542-4985
Dongsun Choi − Department of Chemistry, Korea University,
Seoul 02841, Republic of Korea
Yoon Seo Jung − Department of Chemistry, Korea University,
Seoul 02841, Republic of Korea
Haemin Song − Department of Chemistry, Korea University,
Seoul 02841, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpclett.2c01179
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
K.S.J. thanks Hionsuck Baik (Korea Basic Science Institute,
Seoul Center, Korea) for helping us in measuring the HAADF-
STEM of the CQDs. This work was supported by a National
Research Foundation of Korea (NRF) grant funded by the
Korean government (MIST) (NRF-2021R1A2C2092053 and
NRF-2019M3D1A1078299).
6145
■
pubs.acs.org/JPCL Letter
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