Superior optical gain in zinc selenide colloidal nanocrystals induced by

Coulomb-correlated electron-hole plasma

Zhigao Huang1#, Hanchen Shen1#, Yiming Wu2, Yuting Wu1, Weigao Xu3, Xie Zhang4*, Yue
Wang1*
1
College of Materials Science and Engineering, Nanjing University of Science and
Technology, Nanjing 210094, China

2
Institute of Flexible Electronics (Future Technologies), Xiamen University, Xiamen 361005,
China

3
Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing, China

4
School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an
710072, China

#
These authors contributed equally: Zhigao Huang, Hanchen Shen.

* Authors to whom correspondence should be addressed, electronic email:

ywang@njust.edu.cn; xie.zhang@nwpu.edu.cn

1
ABSTRACT
Colloidal semiconductor nanocrystals (NCs) have been recognized as the promising
solution-processable gain media, however, the lasers with state-of-the-art performance
exclusively originate from the cadmium- and lead-based NCs. Herein, we for the first time
unravel that the high-quality heavy-metal-free ZnSe/ZnS NCs show superior optical gain and
lasing performance when the sizes locate beyond quantum confinement regime. Corroborated
by the comprehensive transient spectroscopy, we reveal that the optical gain in the large
ZnSe/ZnS NCs originates from the novel Coulomb-correlated electron-hole plasma (C-EHP)
instead of the high-order multi-exciton recombination. Thanks to the formation of four-level
system and the suppression of Auger recombination, the C-EHP renders low gain threshold
(9.4 μJ/cm2), high gain coefficient (>6500 cm-1) and long gain lifetime (~4 ns). Such desirable
gain properties compete well with those of the classic CdSe NCs and enable the construction
of a high-performance laser device. This work represents significant progress toward the
development of solution-processable non-heavy-metal nanocrystal lasers.

KEYWORDS: Non-heavy-metal nanocrystals, zinc selenide, optical gain, electron-hole

plasma, Auger recombination

2
INTRODUCTION
Colloidal semiconductor nanocrystals (NCs) are recognized as the promising candidates
for developing the next-generation solution-processable laser devices owing to their chemical
flexibility, spectral tunability, solution-processability and exceptional optical properties.1-3
The past decade has witnessed an impressive progress in NC-based optoelectronic devices,
including the electrically driven amplified spontaneous emission (ASE) diodes and the
optically pumped continuous-wave sub-wavelength lasers.4, 5 However, the state-of-the-art
NC lasers are exclusively constructed from the cadmium (Cd) and lead (Pb) based NCs. With
the strict restrictions of heavy metals, these NCs may face challenges to enter the consumer
market in the future.6
To meet the purpose of sustainable development, a number of non-heavy-metal NCs
have been explored as the alternative gain media, including the AgInS2, Ag2Se and InP.7-9
Nevertheless, none of them could exhibit the comparable gain performance to those of the
classic CdSe analogs in terms of gain threshold, gain coefficient and gain lifetime, due to the
tendency of defect formation in the ternary NCs and the high-fold degeneracy of the optical
transition in the III-V NCs.6, 10 In this regard, the II-VI ZnSe NC can be envisaged as the
promising candidate for heavy-metal-free light-emitters since it possesses the similar band
structure to that of CdSe. However, the previously fabricated ZnSe NCs typically show poor
photoluminescence quantum yields (PLQY) due to the presence of rich defects, such as
stacking faults and surface oxidation states, which plagues the optoelectronic aspirations.11-13
The recent advance in controlling the nucleation and shelling processes makes the
high-quality ZnSe NCs available.14, 15 Thanks to the merits endowed by quantum confinement,
most of the studies on ZnSe NCs are currently focused on those with dimensions comparable
to or much smaller than the exciton Bohr radius.16, 17
In such a system, the elementary
photoexcitation is dominated by the excitons, and the optical gain has been attributed to the
biexciton and even high-order exciton recombination.18 However, these quantum-confined
NCs usually suffer from the severe and fast nonradiative Auger recombination, which has
been recognized as the main gain dissipating channel in semiconductor NCs.2 Taking
CdSe-based NCs as the example, tremendous efforts have been devoted to tackling the Auger
loss by engineering complicated nano-heterostructures toward improved gain performance,

3
exemplified by the development of giant quasi-type-II CdSe/CdS NCs19, the
compositionally-graded CdSe/CdZnSe/ZnS NCs20 and the CdSe core-shell nanoplatelets21.
Nevertheless, such strategy has not yet been feasible for ZnSe NCs due to the less mature
synthetic techniques and limited shelling options.15 As a consequence, it is imperative to find
new scheme for developing high-performance optical gain and lasers from non-heavy-metal
NCs.
In this work, we for the first time unravel that the heavy-metal-free ZnSe/ZnS NCs
without any deliberate heterostructure engineering exhibit superior optical gain performance
that is comparable to those of the classic CdSe analogs, including the low gain threshold (9.4
μJ/cm2), high gain coefficient (>6500 cm-1) and long gain lifetime (~4 ns). Corroborated by
the systematic wavelength and power dependent transient spectroscopy, we disclose that the
desirable gain performance is enabled by a new gain mechanism of Coulomb-correlated
electron-hole plasma (C-EHP), rather than the high-order multi-exciton recombination.
Specifically, the C-EHP forms the four-level gain system which facilitates the built-up of
population inversion at low carrier density and the nonradiative Auger recombination is
significantly suppressed by virtue of the screening effect. Taking advantage of the preferable
optical gain, the high-performance vertical cavity surface emitting laser (VCSEL) device
featuring a low pump threshold and directional emission output is demonstrated. This work
opens a new avenue toward the development of high-performance solution-processable lasers
from the eco-friendly colloidal NCs.

RESULTS AND DISCUSSIONS

A series of ZnSe/ZnS NCs with different sizes are synthesized following a recipe slightly
modified from the literature (see Supplementary Material Note 1 for synthesis details).14, 22
The NCs exhibit the high PLQY of 84%-90%, indicating the high quality of the samples. The
transmission electron microscope (TEM) images illustrate the size ranges from 4 to 16 nm
(Fig. 1a and S1). It is noted that all of the samples possess a similar shell thickness of ~1 nm
controlled by the shelling process. The absorption and emission spectra from the ZnSe/ZnS
NC series are shown in Fig. 1b and c, respectively. It could be seen that as the NC size
increases, the band-gap energy reduces from the violet (~3.1eV) to a near-bulk range of 2.80

4
eV. Accordingly, the small and large NCs are termed based on their sizes relative to the
exciton Bohr diameter a0 of ~7.2 nm (Fig. S3).
To examine the potential of the high-quality ZnSe/ZnS NCs for gain media, the ASE
characterization is performed through the stripe pumping configuration (see Supplementary
Material Note 1 for synthesis details). Fig. 1d depicts the pump fluence-dependent PL spectra
from the large ZnSe/ZnS NCs with diameter of 10 nm and those for the small analogs are
shown in Fig. S5. It is found that the relatively broad spontaneous emission with full-width of
half maximum (FWHM) of 12 nm dominates under low pump intensities and a narrow peak
with FWHM of 4 nm emerges under high pump fluences, indicating the achievement of ASE
(Fig. 1e). The plot of the integrated PL intensity as a function of pump fluence shows a
representative threshold-like behavior, further confirming the development of ASE, and the
threshold is derived to be ~10.2 μJ/cm2 (Fig. 1e). Note that the logarithmic coordinate is
adopted in Fig. 1d to highlight the transition from spontaneous emission to ASE since the
linear one (inset in Fig. 1d) can only display the ASE and the weak spontaneous emission is
covered up. To the best of our knowledge, this threshold is the lowest one for the
heavy-metal-free NCs and it is even comparable to those of the classic CdSe NCs with
deliberate heterostructure engineering (Fig. S6 and Table S1).2, 7-9, 13
The model gain
coefficient is further derived by the variable stripe length (VSL) measurement.23 As shown in
Fig. 1f, a high model gain coefficient of ~5000 cm-1 is determined at the fluence of 167.5 µJ
cm−2. In contrast, the ASE thresholds for the small ZnSe/ZnS NCs with strong confinement
regime are much higher (~110 μJ/cm2, Fig. S5), indicating the benefits of large ZnSe/ZnS
NCs for light amplification applications.
To understand the seemingly unusual ASE behavior, the femtosecond transient
absorption (TA) spectroscopy was exploited. Fig. 2a-b depicts the pseudocolor TA map and
the corresponding spectra of the representative ZnSe/ZnS NCs with size of 10 nm at pump
fluence of 6.3 μJ/cm2 (corresponding to the carrier density of n0 ~ 2.1×1018 cm-3, see carrier
density calculation in Supplementary Material Note 2). The TA spectra are dominated by a
broad bleaching band, consisted of the heavy hole (HH) and light hole (LH) transitions. With
the rising of carrier densities, the amplitude of the bleaching band (Δα) greatly increases to
overtake the intrinsic absorbance (α0), indicating the achievement of optical gain (Fig. S7).

5
Quantitatively, the optical gain g in NCs is derived by the negative nonlinear absorbance
(α=α0+Δα<0).24 Fig. 2c plots the carrier density-dependent nonlinear absorption spectra. It is
found that the net gain appears at low carrier density of ~3.2×1018 cm-3 (corresponding to
fluence of 9.4 μJ/cm2), and the gain coefficient at the fluence of 187.2 µJ cm−2 (6.4×1019 cm-3)
is derived to be ~ 5400 cm-1, which are consistent with the ASE results. Remarkably, the gain
coefficient could reach up to a high value of >6500 cm-1 with the further increase of carrier
density. In contrast, for the quantum-confined ZnSe/ZnS NCs with sizes (4-6 nm) smaller than
the Bohr radius, the gain occurs at a varied and higher carrier density range of
8.5×1018-2.5×1019 cm-3, which corresponds to the much higher pump fluences of 40-100
μJ/cm2 (Fig. S8a-b). Interestingly, the varied carrier density thresholds in the small ZnSe/ZnS
NCs point to a nearly constant <N0> of ~ 1.6 (the average electron-hole pairs per NC, <N0>),
which is consistent to the biexcitonic gain character.22
In stark contrast, the large ZnSe/ZnS NCs are found to share a nearly-constant carrier
density of 2.8×1018 cm-3 regardless of the size and the excitation wavelength (Fig. 2d). Such a
size-independent density threshold is similar to the gain characteristics in bulk
semiconductors, where the optical gain is derived from an unbound electron-hole plasma
(EHP).25-27 However, the persistent excitonic feature above the threshold density (Fig. 2c) is
inconsistent with the traditional unbound EHP behavior, where the exciton resonance is fully
destroyed by the screening of Coulomb interaction.28, 29 Similar absorption peaks have also
been found in other large NCs and their oscillator strengths monotonously decrease as the size
increases (Fig. S10), confirming that they arise from the remaining excitonic absorption. In
general, there are two possible origins for the remaining excitonic signature. One is known as
the Mahan exciton, resulting from the interaction between the electron-hole pairs and electron
gas.30 The presence of Mahan exciton would enhance the continuum absorption and blue-shift
the HH exciton peak, while these characters are not observed in our experiment. The other is
the so-called Coulomb-correlated EHP (C-EHP, also known as the non-degenerate EHP),
where the electron-hole pairs in the plasma behave collectively and exhibit long-range
correlations.31-33 To verify the C-EHP gain in our case, we tentatively apply the C-EHP model
to describe the nonlinear gain spectra 𝑔(ℏ𝜔):27
𝑔(ℏ𝜔) = 𝛼(ℏ𝜔) × (𝑓𝑐 − 𝑓𝑣 ) (1)

6
where 𝛼(ℏ𝜔) denotes the absorption, 𝑓𝑐 and 𝑓𝑣 are the Fermi occupation factors for the
conduction and valence bands, respectively (see more details in Supplementary Material Note
3). As shown in Fig. 3a, this model well reproduces the evolution from net absorption to net
gain across the band-gap transitions, providing strong evidence for the C-EHP gain in the
large ZnSe/ZnS NCs. Importantly, compared to the unbound EHP with an inherent three-level
transition scheme, the C-EHP could create the four-level system and achieve a low-threshold
population inversion.31 Specifically, the stimulated emission from the C-EHP is coupled to the
plasmon resonance, resulting in a plasmon-phonon interactive state (Fig. 3b) and relaxing the
inversion criterion by:32

𝐸𝑒𝐹 (𝑛0 ) − 𝐸ℎ𝐹 (𝑛0 ) ≥ 𝐸𝑔 (𝑛0 ) − ℏ𝜔𝑝 (2)

𝐹 (𝑛 )
where 𝐸𝑒,ℎ 0 is the quasi-Fermi levels of the electron or hole, 𝐸𝑔 (𝑛0 ) is the band-gap

𝑛0 𝑒 2
energy. The plasmon frequency 𝜔𝑝 is approximated by 𝜔𝑝 = √ , where 𝜀𝑟 and 𝑚𝑟 are
𝜀0 𝜀𝑟 𝑚𝑟

the effective dielectric constant and reduced mass, respectively. Here, the model involving
Coulomb interaction is adopted to extract the gain-related parameters and it derives a
theoretical gain threshold of ~2.5×1018 cm-3 (Fig. 3c, see Supplementary Material Note 4 for
details).28 This threshold agrees well with the experimental value and is far smaller than that
of the unbound plasma (>1019 cm-3), contributing to the low-threshold optical gain from the
C-EHP. It is worth noting that different from the bulk semiconductors with quasi-infinite
dimension, the sizes of the large NCs are close to the Debye screening length 𝜆𝑆 (Fig. S13).
It means that the charged carriers in the plasma undergo correlated motions within the
restricted range defined by the Debye length, which leads to the long-range correlations and,
hence, the formation of C-EHP.
Importantly, the Auger loss, known as the main gain dissipating channel in
semiconductor NCs, is found to be greatly suppressed in the large ZnSe/ZnS NCs as reflected
by the long gain lifetime of ~4 ns (Fig. 4a). To quantitatively investigate the Auger
recombination, the pump fluence-dependent carrier decay is fitted by the rate equation (Fig.
4b).34 It is found that the carrier recombination under high excitation intensities follows the
third-order behavior (see more details in Supplementary Material Note 5):
𝑑𝑛
= −𝑘3 𝑛3 (3)
𝑑𝑡
7
where k3 is the third-order Auger coefficient. The k3 is determined to be a constant of 5×10-29
cm6/s at the relatively low-density range (< 1019 cm-3) (inset in Fig. 4c). Interestingly, with
further increasing the carrier density, the Auger coefficient exhibits orders-of-magnitude
reduction to 9×10-32 cm6/s (Fig. 4c), thus confirming the greatly suppressed Auger loss. Such
phenomenon can be understood by analyzing the microscopic dependence of the Auger
coefficient on carrier density from a computational perspective. In the wide-bandgap ZnSe
semiconductors, Auger recombination occurs via a phonon-assisted indirect process that can
be evaluated by:35, 36
2𝜋 1 1 2
𝑘3 = 2 ∑ 𝑓1 𝑓2 (1 − 𝑓3 )(1 − 𝑓4 ) (𝑛𝜈𝐪 + ± ) |𝑀1234;𝑣𝑞 | 𝛿(𝜖𝟏 + 𝜖𝟐 − 𝜖𝟑 − 𝜖𝟒
𝑛03 ħ 2 2
𝟏𝟐𝟑𝟒,𝑣𝒒

∓ ħ𝜔𝜈𝒒 ) (4)

where 𝑓𝑖 (𝑖 = 1,2,3,4) are the Fermi occupation factors of the electron/hole states involved in

the Auger event (Fig. 4d), 𝑛𝜈𝐪 are the phonon occupation numbers for the band v at

wavevector q, 𝜔𝑣𝑞 are the phonon frequencies, 𝑀1234;𝑣𝑞 and 𝜖𝑖 are the matrix elements and

eigenvalues of the states, respectively. With the derivation above, it can be seen that the major
dependence of the Auger coefficient on carrier density is through the matrix elements
𝑀1234;𝑣𝑞 (see more details in Supplementary Material Note 5).37 𝑀1234;𝑣𝑞 have the

contribution mainly from the screened Coulomb interactions (𝑊), which reads:
1
𝑊(𝒓1 , 𝒓2 ) = 𝑊(𝒓1 − 𝒓2 ) ≡ ̃ (𝐪)𝑒 𝑖𝐪⋅(𝒓1 −𝒓2)
∑𝑊
𝑉
𝒒
2
1 1 4𝜋𝑒
= ∑ 𝑒 𝑖𝒒⋅(𝒓1 −𝒓2 ) (5)
𝑉 𝜀(𝐪) 𝑞 2 + 𝜅 2
𝐪

where 𝑉 is the cell volume, 𝜀(𝐪) is the dielectric function in reciprocal space, 𝜅 is the
inverse Debye screening length (1/𝜆𝑆 ). As shown in Fig. S13, 𝜅 undergoes a tremendous
enhancement as the carrier density increases, which reduces 𝑊 and the Auger transition
matrix elements. As a consequence, the Auger coefficient decreases abruptly under high
carrier densities, contributing to the long-lasting (4 ns) optical gain.
In contrast, as shown in Fig. S14, the Auger rate of the quantum-confined NCs
monotonously increases with carrier density, and the gain lifetime is determined to be only 50
ps, which will surely bring severe Auger loss. These results rationalize the much-improved

8
gain performances from the large ZnSe/ZnS NCs compared to those of the strongly confined
analogs.
Taking advantage of the superior gain from ZnSe/ZnS NCs beyond the confinement
regime, the VCSEL device is constructed. To do so, the large ZnSe/ZnS NCs of 10 nm is
spin-coated onto a distributed Bragg reflector (DBR) that is highly reflective around the blue
spectral regime (Fig. 5a). Then, the other DBR reflector is brought upside-down to contact
well with the NC film following our previously developed method.38 Finally, the device is
fixed with glue. Fig. 5b presents the evolution of PL spectra from the device as a function of
pump intensity. It is seen that the multiple sharp PL peaks appear under low pump fluence
(<8.2 μJ/cm2). These comb-like peaks are not the lasing emission, in fact, it is the modulated
spontaneous emission by the cavity effect as has been reported for the VCSELs.38 With the
further increase of pump intensity (>13.6 μJ/cm2), the discrete peaks with wavelength close to
the stimulated emission spectra grow nonlinearly, while the others saturate in intensity.
Simultaneously, the dramatic narrowing of the PL linewidth to ~0.4 nm is observed,
indicating the achievement of lasing action (Fig. S15a). The plot of the PL intensity as a
function of the pump fluence shows the typical threshold behavior, revealing the lasing
threshold to be ~9.8 μJ/cm2 (Fig. S15b). Moreover, Fig. 5a shows the photograph of the output
beam from the device. The directional emission beam is clearly observed far (~50 cm) from
the device when the pump fluence is above the threshold. This is the most convincing
evidence for the development of lasing action in our device.
CONCLUSION
In conclusion, we demonstrate the superior optical gain from eco-friendly ZnSe/ZnS
NCs induced by the non-excitonic interaction. Thanks to the formation of four-level system
and the suppression of Auger recombination, the novel C-EHP gain renders low threshold,
high coefficient and long lifetime, which competes well with those of the classic CdSe NCs.
These results present a new paradigm of eco-friendly NC-based gain media and pave a new
direction to develop solution-processable optical amplifiers and lasers.

SUPPLEMENTARY MATERIAL
See the supplementary material for more information on experimental details, TEM

9
images, TA and optical gain spectra of ZnSe/ZnS NCs with different NC size, calculation of
carrier density, estimation of chemical potentials and Debye screening length.

AUTHOR DECLARATIONS
Corresponding Author
*E-mail: ywang@njust.edu.cn; xie.zhang@nwpu.edu.cn

Author Contributions
Z.H. and H.S. contributed equally to this work.

Notes
The authors declare no competing interests.

ACKNOWLEDGMENT

This work is supported by the National Natural Science Foundation of China (62274090 and
11904172). The work is supported by “the Fundamental Research Funds for the Central
Universities”, No.30923010101.

10
 FIGURES

a b c
Size
4 nm
6 nm
7 nm

Absorption (a.u.)
8 nm
9 nm

10 nm
12 nm
14 nm
16 nm

340 380 420 460

Wavelength (nm)
d e f
104
77.4
PL intensity (´103)

8 12 100 5000 cm-1 167.5 mJ/cm2

57.8
34.9 mJ/cm2

Normalized intensity (a.u.)

34.9
21.5
4

PL intensity (a.u.)
PL intensity (a.u.)

12.5 10
FWHM (nm)

6.8 10-1
3 2.9 420 cm-1
10 0 8
(mJ/cm2) 420 450 480
Wavelength (nm)
Threshold 10-2
6
10.2 mJ/cm2

4
10-3
102 0.00 0.05 0.10 0.15 0.20 0.25 0.30
420 440 460 480 500 1 10 100
Strip length (mm)
Wavelength (nm) Pump fluence (mJ/cm2)

FIG 1. (a) TEM and UV lamp-irradiated fluorescent images of the ZnSe/ZnS NCs. (b-c)
Absorption and PL spectra of the ZnSe/ZnS NCs as a function of the NC size. (d) Pump
intensity-dependent PL spectra from thin film of the ZnSe/ZnS NCs (size: 10 nm) via the
stripe pumping configuration. Inset: PL spectra in the linear coordinate. (e) Plot of the FWHM
and integrated intensity of the PL peaks as a function of pump fluence. (f) Integrated PL
intensity with the change of stripe length while retaining the pump fluence at 34.9 µJ cm−2
and 167.5 µJ cm−2, respectively.

11
a b 2
Light hole Heavy hole a0 Size: 10 nm
0
103 (LH) (HH) n0~ 2.1´1018 cm-3
-2
0
-4
-6 mOD
102 0 ps
-2
Time (ps)

1 ps

DmOD
5 ps
101 10 ps
-4
20 ps
50 ps
100 -6 Light hole 100 ps
Size: 10 nm (LH) 500 ps
n0~ 2.1´1018 cm-3 1000 ps
Heavy hole (HH)
10-1 -8
400 420 440 460 480 400 420 440 460 480
Wavelength (nm) Wavelength (nm)
c d 1020
Size: 10 nm 6 n0 (´10 19 -3
cm ) Small NCs Large NCs
g (´103 cm-1)

12
0.2 350 nm excitation
a0 0.3 380 nm excitation
0 0.6 400 nm excitation
Da+a0 (´104 cm-1)

9
0.9
420 nm excitation
1.7
n0 (cm-3)

-6 1019
450 465 480 2.6
6
Wavelength (nm) 3.4
4.3
6.4
3 2.8´1018
8.5

1018
0 a0

380 400 420 440 460 480 500 2 6 10 14 18

Wavelength (nm) Size (nm)

FIG 2. (a) Pseudocolor TA image of the ZnSe/ZnS NCs with size of 10 nm and n0~ 2.1×1018
cm-3. (b) Corresponding spectral distributions at indicated delay times. (c) Nonlinear
absorption spectra (α=Δα+α0) at 1 ps for different carrier densities. Inset: Zoom on the
band-edge part, showing the transition from absorption to net gain. (d) Evolution of gain
threshold as functions of the NC size and excitation wavelength.

12
FIG 3. (a) Theoretical fits to the experimental gain spectra based on the C-EHP gain model.
Inset shows the fitted gain spectra by varying the carrier density. (b) Schematic depiction of
the gain transition from the exciton to the C-EHP as the NC size increases. (c) Modulations of
the Fermi energy, electron-hole pair chemical potential and transient band-gap energies as a
function of carrier density.

13
FIG 4. (a) Net gain map of the ZnSe/ZnS NCs with size of 10 nm at the carrier density of n0 ~
1.1×1020 cm-3. (b) Carrier density-dependent TA kinetics at the lowest HH transitions. The
curves are fitted by the third-order Auger component. (c) Evolution of the Auger coefficient as
a function of carrier density. (d) Schematic depiction of the indirect Auger recombination and
carrier screening processes at the high carrier density.

14
FIG 5. (a) Schematic configuration and photographs of the VCSEL. The scale bars are 5 cm.
(b) Lasing spectra of the VCSEL with large ZnSe/ZnS NCs as the optical gain layer.

15
REFERENCES
1. R. R. Cooney, S. L. Sewall, D. M. Sagar and P. Kambhampati, "Gain control in
semiconductor quantum dots via state-resolved optical pumping," Phys. Rev. Lett. 102 (12),
127404 (2009).
2. Y.-S. Park, J. Roh, B. T. Diroll, R. D. Schaller and V. I. Klimov, "Colloidal quantum dot
lasers," Nat. Rev. Mater. 6 (5), 382-401 (2021).
3. J. Chen, W. Du, J. Shi, M. Li, Y. Wang, Q. Zhang and X. Liu, "Perovskite quantum dot
lasers," InfoMat 2 (1), 170-183 (2019).
4. N. Ahn, C. Livache, V. Pinchetti, H. Jung, H. Jin, D. Hahm, Y.-S. Park and V. I. Klimov,
"Electrically driven amplified spontaneous emission from colloidal quantum dots," Nature
617 (7959), 79-85 (2023).
5. F. Fan, O. Voznyy, R. P. Sabatini, K. T. Bicanic, M. M. Adachi, J. R. McBride, K. R. Reid,
Y.-S. Park, X. Li, A. Jain, R. Quintero-Bermudez, M. Saravanapavanantham, M. Liu, M.
Korkusinski, P. Hawrylak, V. I. Klimov, S. J. Rosenthal, S. Hoogland and E. H. Sargent,
"Continuous-wave lasing in colloidal quantum dot solids enabled by facet-selective epitaxy,"
Nature 544 (7648), 75-79 (2017).
6. L. Liu, B. Bai, X. Yang, Z. Du and G. Jia, "Anisotropic Heavy-Metal-Free Semiconductor
Nanocrystals: Synthesis, Properties, and Applications," Chem. Rev. 123 (7), 3625-3692
(2023).
7. Y. Mi, A. Jiang, L. Kong, J. Wang, H. Guo and S.-N. Luo, "Amplified Spontaneous
Emission and Lasing from Zn-Processed AgIn5S8 Core/Shell Quantum Dots," ACS Appl.
Mater. Inter. 15 (15), 19330-19336 (2023).
8. C. Liao, L. Tang, L. Wang, Y. Li, J. Xu and Y. Jia, "Low-threshold near-infrared lasing at
room temperature using low-toxicity Ag2Se quantum dots," Nanoscale 12 (42), 21879-21884
(2020).
9. S. Gao, C. Zhang, Y. Liu, H. Su, L. Wei, T. Huang, N. Dellas, S. Shang, S. E. Mohney
and J. Wang, "Lasing from colloidal InP/ZnS quantum dots," Opt. Express 19 (6), 5528-5535
(2011).
10. H. Liu, P. Chen, Y. Cui, Y. Gao, J. Cheng, T. He and R. Chen, "InP Semiconductor
Nanocrystals: Synthesis, Optical Properties, and Applications," Adv. Opt. Mater. 11, 2300425

16
(2023).
11. J. Min, Y. Zhang, Y. Zhou, D. Xu, C. S. Garoufalis, Z. Zeng, H. Shen, S. Baskoutas, Y. Jia
and Z. Du, "Size Engineering of Trap Effects in Oxidized and Hydroxylated ZnSe Quantum
Dots," Nano Lett. 22 (9), 3604-3611 (2022).
12. T. Kim, K.-H. Kim, S. Kim, S.-M. Choi, H. Jang, H.-K. Seo, H. Lee, D.-Y. Chung and E.
Jang, "Efficient and stable blue quantum dot light-emitting diode," Nature 586 (7829),
385-389 (2020).
13. Y. Wu, W. Cai, Z. Huang, Y. Ren, Y. Wu and Y. Wang, "An All‐Colloidal and Eco‐
Friendly Quantum‐Dot Laser," Laser Photonics Rev. 2301167 (2024).
14. M. Gao, H. Yang, H. Shen, Z. Zeng, F. Fan, B. Tang, J. Min, Y. Zhang, Q. Hua, L. S. Li,
B. Ji and Z. Du, "Bulk-like ZnSe Quantum Dots Enabling Efficient Ultranarrow Blue
Light-Emitting Diodes," Nano Lett. 21 (17), 7252-7260 (2021).
15. Z. Long, M. Liu, X.-g. Wu, K. Gu, G. Yang, Z. Chen, Y. Liu, R. Liu and H. Zhong, "A
reactivity-controlled epitaxial growth strategy for synthesizing large nanocrystals," Zhong,
Nat. Synthesis (2023).
16. S. Lin, J. Li, C. Pu, H. Lei, M. Zhu, H. Qin and X. Peng, "Surface and intrinsic
contributions to extinction properties of ZnSe quantum dots," Nano Research 13 (3), 824-831
(2020).
17. X. Lin, Z. Chen, Y. Han, C. Nie, P. Xia, S. He, J. Li and K. Wu, "ZnSe/ZnS Core/Shell
Quantum Dots as Triplet Sensitizers toward Visible-to-Ultraviolet B Photon Upconversion,"
ACS Energy Lett. 7 (3), 914-919 (2022).
18. P. Kambhampati, "Multiexcitons in semiconductor nanocrystals: a platform for
optoelectronics at high carrier concentration," J. Phys. Chem. Lett. 3 (9), 1182-1190 (2012).
19. F. Di Stasio, A. Polovitsyn, I. Angeloni, I. Moreels and R. Krahne, "Broadband amplified
spontaneous emission and random lasing from wurtzite CdSe/CdS “giant-shell” nanocrystals,"
ACS Photonics 3 (11), 2083-2088 (2016).
20. X. Li, J. Du, G. Zhao, B. Zhang, C. Livache, N. Ahn, Y. Jia, M. Li, Y. Chen, J. Zhu, J.
Guo, V. I. Klimov and K. Wu, "Two-Color Amplified Spontaneous Emission from
Auger-Suppressed Quantum Dots in Liquids," Adv. Mater. 36 (7), 2308979 (2024).
21. Y. Altintas, K. Gungor, Y. Gao, M. Sak, U. Quliyeva, G. Bappi, E. Mutlugun, E. H.

17
Sargent and H. V. Demir, "Giant alloyed hot injection shells enable ultralow optical gain
threshold in colloidal quantum wells," ACS nano 13 (9), 10662-10670 (2019).
22. Z. Huang, Q. Sun, S. Wang, H. Shen, W. Cai and Y. Wang, "Broadband Tunable Optical
Gain from Ecofriendly Semiconductor Quantum Dots with Near-Half-Exciton Threshold,"
Nano Lett. 23 (9), 4032-4038 (2023).
23. S. Wang, J. Yu, M. Zhang, D. Chen, C. Li, R. Chen, G. Jia, A. L. Rogach and X. Yang,
"Stable, Strongly Emitting Cesium Lead Bromide Perovskite Nanorods with High Optical
Gain Enabled by an Intermediate Monomer Reservoir Synthetic Strategy," Nano Lett. 19 (9),
6315-6322 (2019).
24. C. D. Sonnichsen, T. Kipp, X. Tang and P. Kambhampati, "Efficient Optical Gain in
CdSe/CdS Dots-in-Rods," ACS Photonics 6 (2), 382-388 (2018).
25. F. Logue, P. Rees, J. Heffernan, C. Jordan, J. Donegan, J. Hegarty, F. Hiei and A.
Ishibashi, "Effect of Coulomb enhancement on optical gain in (Zn, Cd) Se/ZnSe multiple
quantum wells," Phys. Rev. B 54 (23), 16417 (1996).
26. K. Asano and T. Yoshioka, "Exciton–Mott Physics in Two-Dimensional Electron–Hole
Systems: Phase Diagram and Single-Particle Spectra," J. Phys. Soc. Japan 83 (8) (2014).
27. C. F. Klingshirn, Semiconductor optics. (Springer Science & Business Media, 2012).
28. M. A. M. Versteegh, T. Kuis, H. T. C. Stoof and J. I. Dijkhuis, "Ultrafast screening and
carrier dynamics in ZnO: Theory and experiment," Phys. Rev. B 84 (3) (2011).
29. A. Chernikov, C. Ruppert, H. M. Hill, A. F. Rigosi and T. F. Heinz, "Population inversion
and giant bandgap renormalization in atomically thin WS2 layers," Nat. Photonics 9 (7),
466-470 (2015).
30. T. Palmieri, E. Baldini, A. Steinhoff, A. Akrap, M. Kollár, E. Horváth, L. Forró, F. Jahnke
and M. Chergui, "Mahan excitons in room-temperature methylammonium lead bromide
perovskites," Nat. Commum. 11 (1) (2020).
31. A. P. Schlaus, M. S. Spencer, K. Miyata, F. Liu, X. Wang, I. Datta, M. Lipson, A. Pan and
X. Y. Zhu, "How lasing happens in CsPbBr(3) perovskite nanowires," Nat. Commun. 10 (1),
265 (2019).
32. C. Klingshirn, R. Hauschild, J. Fallert and H. Kalt, "Room-temperature stimulated
emission of ZnO: Alternatives to excitonic lasing," Phys. Rev. B 75 (11) (2007).

18
33. O. Homburg, P. Michler, R. Heinecke, J. Gutowski, H. Wenisch, M. Behringer and D.
Hommel, "Biexcitonic gain characteristics in ZnSe-based lasers with binary wells," Phys. Rev.
B 60 (8), 5743-5750 (1999).
34. K. Wei, X. Zheng, X. Cheng, C. Shen and T. Jiang, "Observation of ultrafast exciton–
exciton annihilation in CsPbBr3 quantum dots," Adv. Opt. Mater. 4 (12), 1993-1997 (2016).
35. X. Zhang, J.-X. Shen and C. G. Van de Walle, "Anomalous Auger Recombination in
PbSe," Phys. Rev. Lett. 125 (3), 037401 (2020).
36. E. Kioupakis, D. Steiauf, P. Rinke, K. T. Delaney and C. G. Van de Walle,
"First-principles calculations of indirect Auger recombination in nitride semiconductors,"
Phys. Rev. B 92 (3), 035207 (2015).
37. X. Zhang, J. X. Shen and C. G. Van de Walle, "First‐Principles Simulation of Carrier
Recombination Mechanisms in Halide Perovskites," Adv. Energy Mater.10 (13), 1902830
(2020).
38. Y. Wang, X. Li, V. Nalla, H. Zeng and H. Sun, "Solution‐processed low threshold vertical
cavity surface emitting lasers from all‐inorganic perovskite nanocrystals," Adv. Funct. Mater.
27 (13), 1605088 (2017).

19
TOC

20