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High-Q, Low-Threshold Monolithic Perovskite Thin-Film
Vertical-Cavity Lasers
Songtao Chen, Cheng Zhang, Joonhee Lee, Jung Han, and Arto Nurmikko*
Organometal halide perovskites (CH3NH3PbX3, where X = Cl,
Br, I) have made exceptionally rapid progress in optoelectronics
in the past couple of years, catapulted mainly by their photo-
voltaic application promise, while potential for light emitters
is now also under intense scrutiny.[1,2] With low-cost solution-
based synthesis of high-quality thin films and optimized elec-
tron-/hole-transporting layers, organometallic perovskite solar
cell has achieved certified efficiency of 22.1%.[3] On the light-
emitter side, early endeavors have led to exploratory perovskite
light-emitting diodes (LEDs) in the near-infrared (NIR), red,
and green[4] with preliminary work on assessing prospects for
lasing now under way. At the higher levels of electronic excita-
tion for reaching optical gain, most experiments have deployed
ultrashort (fs) optical pumping to report amplified spontaneous
emission (ASE) from polycrystalline perovskite (CH3NH3PbI3)
films.[5,6] Furthermore, evidence for optically pumped single-
crystal perovskite laser action has been presented with
nanowire,[7–9] microdisk,[10] and microplatelet[11] structures, fab-
ricated either by solution growth or chemical vapor deposition
method. This evidence has primarily been presented based on
observed spectral narrowing nonlinear light input–output char-
acteristics. Similar criteria have been applied to report random
lasing[12] and whispering-gallery mode emission.[13] Initial steps
toward proper laser device structures based on perovskite gain
media have been recently taken using optical microresonators
in vertical cavity,[14] distributed feedback gratings,[15,16] and 2D
photonic crystals[17,18] geometries. Most of these experiments
were confined to transient regime, and/or lack the important
evidence of well-defined spatially coherent laser output such as
Gaussian beam modes. Most critically, key characteristics such
as optical gain dynamics and the perovskite material degrada-
tion under high electronic and photon densities remain largely
unexplored, yet essential in gauging the realistic opportunities
and challenges ahead toward practical and competitive perovs-
kite lasers.
S. Chen, Dr. J. Lee
School of Engineering
Brown University
Providence, RI 02912, USA
C. Zhang, Prof. J. Han
Department of Electrical Engineering
Yale University
New Haven, CT 06511, USA
Prof. A. Nurmikko
School of Engineering and Department of Physics
Brown University
Providence, RI 02912, USA
E-mail: Arto_Nurmikko@brown.edu
DOI: 10.1002/adma.201604781
Adv. Mater. 2017, 29, 1604781 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Here, we focus on fundamental prerequisites for advancing
perovskite laser prospects by designing a monolithic ver-
tical microcavity configuration where a thin perovskite
(CH3NH3PbI3) film is embedded within a high-quality factor
optical resonator (Q ≈ 1100) formed by wide-bandgap semicon-
ductor reflectors. In addition to achieving laser action with high
temporal and spatial coherence (such as low-divergence circular
Gaussian beam outputs), these structures have enabled us to
study dynamics of optical gain and phase transition from spon-
taneous emission to laser regime, while addressing the critical
issue of device degradation. Importantly, these outcomes have
been achieved under relatively modest optical pumping which
may be realistically reached by electrical injection in the future.
As described below, the new type of hybrid perovskite vertical-
cavity surface-emitting laser (PeVCSEL) is microfabricated with
a morphologically highly uniform perovskite thin (≈300 nm)
film placed between two high-reflectivity (≈99.5%) distributed
Bragg reflectors (DBRs). The DBRs, in turn, deploy recently
developed gallium nitride semiconductor process innovations
where nanoporous-GaN (NP-GaN) provides the low-index layers
to a NP-GaN/GaN (electrically conducting) multilayer stack.[19]
Under pulsed optical excitation, we achieve an encouragingly
low lasing threshold (≈7.6 µJ cm−2), lower or comparable than
some of the best values reported not only in perovskite material
family, but also in other non-epitaxial material systems such
as colloidal nanoplatelets,[20] quantum dots,[21,22] and organic
polymers.[23]
This new perovskite VCSEL device has enabled us to study
gain dynamics on timescales of excitation that are much longer
than typically reported ultrashort pulse (fs) experiments in the
perovskite literature. Under ultrashort pulse conditions, stim-
ulated emission takes place by extremely fast gain switching
mechanism and bypasses most issues associated, for example,
with competing nonradiative recombination. In contrast, we
have operated our lasers up to the nanosecond quasi-steady
state regime. These new types of PeVCSEL investigative devices
have enabled us to study device degradation, and achieve device
lifetimes beyond other early results.[9,17,24] Our degradation
work, we suggest, is also of relevance to current questions of
longevity in perovskite solar cells, opening another avenue to
study microscopic mechanisms of degradation. In broader
terms, we note how the epitaxial single-crystal-based VCSELs
have long been the gold standard in semiconductor laser
technologies of high-end III–V inorganic compounds.[25–28]
Generically, VCSEL devices have advantages of compactness,
low lasing threshold, circular beam surface emitting modes,
and are compatible with microfabrication as 2D laser arrays.
We fabricated perovskite thin films using a customized solu-
tion-based spin-casting method enabled by the toluene-dripping
process to induce perovskite crystallization (see Experimental
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a) b)
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Intensity (a.u.)

(110)

(220)
(310)
(202)
(211)

(224)
(314)
(312)
(112)

(404)
10 15 20 25 30 35 40 45 50
2θ (degree)
500 nm d) 100

c) 2.5

Normalized intensity
Abs. coeff. ( µm )
-1

2.0
10-1

PL (a.u.)
1.5
1.0
0.5
0.0 10-2
660 690 720 750 780 810 840 0 2 4 6 8 10 12 14 16 18 20
Wavelength (nm) Time (ns)

Figure 1. Characterization of perovskite polycrystalline solid thin films. a) Scanning electron microscopy image of surface morphology of a CH3NH3PbI3
thin film on the GaN-based DBR substrate. b) Indexed X-ray diffraction pattern of a perovskite thin film, reflecting polycrystalline nature of the film
and confirming a single-phase sample with tetragonal crystal structure at room temperature. c) Linear absorption (abs.) coefficient (coeff.) and
photoluminescence (PL) measured from an ≈300 nm perovskite film. The PL spectrum is obtained from the film deposited on the DBR substrate.
d) Time-correlated single-photon counting measurement of the perovskite thin film (on the DBR substrate) spontaneous emission lifetime. Sample is
photoexcited by pulsed excitation with λ = 408 nm, τpulse ≈ 68 ps, 2.5 MHz repetition rate, and energy density 0.9 µJ cm−2. The blue line is experimental
data and orange line is the single exponential decay fitting, which yields PL lifetime of 5.3 ± 0.4 ns.

Section). Careful and subtle fabrication optimization on pre-
cursor solvent selection, molar ratio of precursors, toluene-
dripping timing protocol, thermal annealing temperature
and duration, and treatment of substrate surface (to make it
hydrophilic) were conducted to ensure the high optical quality
of our perovskite polycrystalline thin films. The scanning elec-
tron microscopy image in Figure 1a shows the close packing
of randomly oriented crystalline micrograins as a void-free
continuous film on the DBR substrate. The indexed X-ray dif-
fraction pattern in Figure 1b confirms the presence of a pure
CH3NH3PbI3 phase with tetragonal lattice structure, matching
reported single crystal powder measurements and theoretical
crystal structure calculations.[29,30] As for the near-band-edge
electronic states, previous work including high-magnetic-field
measurements shows that the exciton (electron–hole) Coulomb
binding energy of CH3NH3PbI3 is only a few milli-electron-volts
(meV).[31,32] Upon interband excitation at room temperature the
unstable excitons dissociate to a (Coulomb-correlated) elec-
tron–hole plasma.[33] Figure 1c shows the absorbance spectrum
of our perovskite films near the optical bandgap at room tem-
perature. A distinct absorption edge appears at 760 nm while
no ground state excitonic peak can be identified. The absorp-
tion coefficient of the densely packed perovskite film reaches
values on the order of 104 cm−1, comparable to near band edge
values in conventional III–V single crystal epitaxial thin film
material such as GaAs. Thus, most (≈80%) of the pump laser
light used in our experiments (λ = 532 nm) was absorbed by
the film. The photoluminescence (PL) spectrum shows a full
width half maximum (FWHM) of 50.1 nm (105.8 meV), red-
shifted (7 nm, 13.6 meV) with respect to the absorption edge.
This may be caused by self-absorption due to the finite film
thickness and the lattice relaxation process. The refractive index
of the perovskite thin films was measured to be n ≈ 2.6 within
the 760–800 nm spectral range as determined by variable angle
spectroscopic ellipsometry (Figure S1, Supporting Informa-
tion). The PL lifetime (Figure 1d) under a low pumping condi-
tion 0.9 µJ cm−2 (corresponding to estimated bulk equivalent
carrier density ρ = 6.1 × 1016 cm−3) was measured in transient
experiments as τsp = 5.3 ± 0.4 ns. This value is comparable with
other reported results for polycrystalline perovskite films,[34]
yet shorter than those reported for large area perovskite single
crystals.[35,36] The unpassivated surface and grain boundaries in
the microcrystallites of our films may indeed contribute to non-
radiative recombination. However, as shown below, at higher
levels of photoexcitation (ρ > 1017 cm−3) this does not inhibit
readily achievable robust stimulated emission. By comparing
the spontaneous emission intensity under same pump condi-
tions with CdSe-based red commercial colloidal QDs (from QD
Vision Inc. with calibrated internal quantum efficiency 90%),
we extract the quantum efficiency of our CH3NH3PbI3 film to
be ≈30% within the carrier density range ρ = 1017–1018 cm−3.
Given their stringent requirements of high optical gain and
very low losses, VCSELs are challenging semiconductor device
configurations due to their short optical path length—and thus
also a testbed for a serious laser material candidate. Net optical
gain must be reached under practically realistic electronic exci-
tation conditions of the active medium while the microcavity
must be designed to minimize optical losses, yet provide a
useful output from the device. A most common configuration is
a planar Fabry–Perot microcavity where planar high-reflectivity
(>99%) multilayer stacks of DBRs are part of a continuous epi-
taxial growth process. Such in situ complete VCSEL synthesis

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substrate. An inductively coupled plasma

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reactive ion etching process first opens
10 µm wide trenches through the stack
(pitch = 100 µm) so that sidewalls of all the
n+-GaN layers can be exposed to the electro-
chemical etchant (trenches shown as grooves
in-plane view of Figure 2d). An example of
a final DBR multilayer stack structure is
shown in the cross-sectional SEM image of
Figure 2b cut cross the DBR xz-plane, where
the zoomed-in image shows the morphology
of NP-GaN with average pore size daverage ≈
10 nm. The distribution of pore sizes satis-
fies the criteria for minimal optical scat-
tering loss (a quantitative criterion requires
that a size parameter χ = πd/λ be much
smaller than unity, while d is diameter of
the pores—here χaverage ≈ 0.04).[39] Figure 2c
shows the measured reflectance spectrum
of the DBR where center of the stop band
was designed to locate at λ = 775 nm to fully
cover the anticipated optical gain region of
CH3NH3PbI3 (760–790 nm).[17] The a priori
design simulations of the reflectance spec-
trum match well with the measurement
(a finite discrepancy results from imprecision
in the values of refractive index of nanoporo-
sified NP-GaN layers).
Figure 2. GaN-based high-quality DBR mirrors. a) Schematic structure of GaN-based DBRs. We then proceeded to fabricate
After epitaxial growth of ten pairs λ/4 n+-GaN/GaN stack, trench grooves are dry etched to the CH3NH3PbI3 perovskite VCSELs.
expose the side walls of n+-GaN layers. The electrochemical etching process is then used to Figure 2e shows the cross-section image
convert n+-GaN into NP-GaN laterally. b) Cross-sectional SEM image of DBR xz-plane (Carte-
of DBR yz-plane after the first step of per-
sian coordinates). The inset is a zoomed-in image to show the optimized nanoporous mor-
phology of the NP-GaN layers. The measured thickness of NP-GaN and GaN layers are 117.5 ± ovskite thin film spin-cast deposition
6.5 and 81.8 ± 4.4 nm, respectively. c) Experimentally measured and simulated reflectance (d = 304.9 ± 11.3 nm) on one DBR. To enable
spectra for GaN-based DBRs. The wide wavelength range of DBR with high reflectance (>99%) possible multiple reuses of the DBRs in
fully covers the PL spectrum (black) of CH3NH3PbI3 thin film, that is, likely optical gain spec- repeat device fabrication, a layer of high-
trum. d) Top-surface SEM image of DBR xy-plane. The trenches are 10 µm wide and their pitch viscosity poly(methyl methacrylate) (PMMA)
is 100 µm. e) Cross-sectional SEM image of DBR yz-plane after CH3NH3PbI3 thin film deposi-
was first spin-cast onto the DBR. This step
tion. The thickness of the perovskite layer is 304.9 ± 11.3 nm.
also filled the trenches in the DBRs, and
prevented the perovskite precursor solution
is not (at least yet) available for the solution grown perovskites. from penetrating into the NP-GaN layers during spin-casting.
To meet the challenges of heterogeneous material integration To complete the monolithic VCSEL devices, a second DBR was
with the perovskite films we turned to monolithic solution by aligned and bonded atop of the perovskite film with wafer edges
designing DBR stacks using recently developed innovation for sealed with optical epoxy. For reducing the known sensitivity of
versatile thin film DBRs based on the wide-bandgap gallium CH3NH3PbI3 layers to chemical reaction with ambient oxygen
nitride.[19] As starting material, this new DBR process tech- and moisture, we deposited a very thin layer (≈10 nm) PMMA
nology uses epitaxially grown pairs of heavily n-doped and immediately atop the perovskite thin film before applying the
undoped GaN multilayers. By a controlled electrochemical top DBR bonding process. Time-resolved PL lifetime measure-
solution process, n+-GaN can be porosified on the nanoscale to ments (under same excitation level in Figure 1d) were con-
create the low-refractive-index layers (NP-GaN), while undoped ducted on the perovskite film with the PMMA layer, which
GaN maintains its original properties.[19,37,38] Lattice-matched yields slightly longer PL lifetimes to be 5.6 ± 0.6 ns. For sim-
NP-GaN/GaN multilayer stacks (electrically conducting) now plicity of the device analysis, we ignore the effect of PMMA
benefit from significant index contrast given nNP-GaN ≈ 1.6 and layer on the carrier dynamics, but rather treat it as a protec-
nGaN ≈ 2.4. Figure 2a shows the schematic structure of one tion layer for perovskite films. We oriented the second (i.e.,
NP-GaN/GaN DBR. A custom-designed pair of DBRs was used top) DBR so that its etch trenches were perpendicular to those
for our VCSELs with the perovskite gain medium sandwiched on bottom DBR thereby creating rather naturally by this wafer
between them (see the Supporting Information for device fab- level planar assembly a 2D square array of PeVCSEL devices
rication). For each DBR, ten pairs of λ/4 n+-GaN/GaN layers with individual device area of 100 µm × 100 µm (Figure S2,
were grown on top of a GaN buffer layer (2 µm), on sapphire Supporting Information).

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Figure 3. PeVCSEL laser characteristics under sub-ns pumping. a) Device output power with increasing pump fluences in log-log scale, showing the
threshold region as the “kink” between two linear regimes of spontaneous emission and lasing, and yielding threshold energy density of 7.6 ± 0.6 µJ cm−2.
The solid lines are rate equation fittings, the best fit to the experiment data gives estimated value of spontaneous emission factor β (≈0.001) and cavity
quality factor Q (≈1110). The fits to hypothetical β of 0.01 and 0.1 are also presented for comparison. The inset shows threshold knee behavior in the
L–L curve plotted on a linear scale. b) Spectrum (770–790 nm) evolution under different pump fluences. Spectral coherent single-mode lasing peak
at 778.4 nm with a FWHM of 0.24 nm is observed. Inset shows the spectrum on logarithmic plot demonstrating single mode operation (background
suppression ratio > 20 dB). c) Near-field images of a PeVCSEL device with pump energy densities below, near, and above the threshold. d) Far-field
pattern recorded from the PeVCSEL laser. Well-defined output beam is emitted perpendicular to the device plane, consistent with spatial coherence
and small divergence angle (<3°). e) Intensity polar plot of PeVCSEL lasing output through a rotational analyzer, showing linear polarization with DOP
to be 81%. f) High-speed time-resolved measurement of PeVCSEL lasing pulses (time referenced to pump pulses) at varying pump energy densities.
The gray background shows the temporal shape of pump pulses (532 nm, 0.34 ns, 1 kHz). The amplitudes of both pump pulses and PeVCSEL laser
output are normalized for ease of visual comparison.

Figure 3 provides a comprehensive summary of the meas-
ured temporal and spatial coherent output from PeVCSEL
devices at room temperature. In our first set of experiments, a
compact diode-pumped solid-state (DPSS) laser source provides
the optical excitation at λ = 532 nm, with τpulse = 0.34 ns and
repetition rate = 1 kHz. The excitation beam was focused to a
spot (r ≈ 30 µm) central within each device area, and the emis-
sion of PeVCSEL was collected through a long-pass filter to
block any residual pump laser light before entering other meas-
uring instruments (schematic setup configuration is shown
in Figure S3, Supporting Information). Figure 3a shows the
PeVCSEL lasing output as function of pumping fluence. The
light-input–light-output power relationship, or “L–L curve” is
presented as both log–log and linear (inset) plots (see discus-
sion below about determination of the spontaneous emission
factor β). The L–L curve suggests a sharp lasing threshold
of 7.6 ± 0.6 µJ cm−2 pulse−1 where the transition (slope
changes) from spontaneous emission to lasing is extracted
from the log–log plot, which corresponds to a carrier density
ρ = (4.17 ± 0.33) × 1017 cm−3 (excluding nonradiative recombi-
nation in this transient response regime). Beyond the threshold,
a single-mode peak at λ = 778.4 nm emerges and increases
sharply in intensity while narrowing to about Δλ = 0.24 nm
from the broad weak PL background (Figure 3b), approaching
the resolution limit of our spectrometer, ≥0.125 nm (further
comparison of the spectrum below and above the threshold
can be found in Figure S4, Supporting Information). The inset
emphasizes the single-mode operation by plotting out the spec-
trum on a logarithmic scale, yielding more than 20 dB back-
ground emission suppression ratio (from perovskite incoherent

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emission and that from external sources). Another classic
signature of lasing, highlighting the spatial coherence, was
observed in studying the spatial emission of the PeVCSEL
devices. Below the threshold, the device emits weak and dif-
fuse spontaneous emission whereas above threshold, a high-
brightness beam emerges perpendicular to device plane (near-
field images in Figure 3c). Figure 3d shows the far-field pattern
of the TEM00 lasing mode demonstrating its small angular
divergence (<3°) across the transverse plane (detailed Gaussian
fittings of intensity distribution can be found in Figure S5,
Supporting Information). The emission from the devices was
typically linearly polarized as shown in Figure 3e, with degree
of polarization DOP = (Imax − Imin)/(Imax + Imin), about 81% in
this example. We surmise that such robust linear polarization
originates from some unspecified built-in optical anisotropy
in our device structures (such as residual strain in the DBRs,
nanopore alignment,[40] or thickness variation across the per-
ovskite film). At present, the electronic origin of optical gain in
halide-perovskites is considerably less clear than conventional
semiconductor lasers. Experiments suggest that electron–hole
pairs may have only a few meV exciton binding energy in
CH3NH3PbI3 perovskite[31,32] so that free electron–hole Fermi-
plasma type of recombination is more likely at room tempera-
ture to account for the stimulated emission.[33,41]
Insight into the gain dynamics of our PeVCSELs was first
examined through their transient behavior acquired from
detailed time-resolved measurements of laser pulse shapes (see
the Experimental Section), summarized in Figure 3f. The sub-
nanosecond excitation pulse duration is used here in modeling
and quantifying the CH3NH3PbI3 optical gain. Figure 3f shows
variation in temporal pulse shapes emitted by the PeVCSEL
over a range of pump fluences (excitation pulse profile shown
as gray shaded area). Shorter delay times between onsets of
pump pulses and corresponding PeVCSEL lasing pulses are
observed at higher excitation levels where higher carrier densi-
ties are injected into perovskite layers to increase the net gain,
thus initiating laser oscillation at earlier stage. While for the
falling edge, the lasing pulses synchronize with the excitation
pulse as carriers supplied from the excitation pulse are insuf-
ficient to maintain laser oscillation condition. For microscopic
insight, we applied a classical rate equation analysis[42–44] to
model the coupled carrier and photon density dynamics upon
excitation. By constructing an analytical gain model[44] and
iteratively fitting the result of L–L curve data (both threshold
energy density and phase transition “kink” from spontaneous
emission to lasing) and the corresponding PeVCSEL temporal
pulse shapes under different pump fluences (see the Sup-
porting Information and Figure S6–S8, Supporting Informa-
tion, for detail), we obtain carrier density dependent gain coef-
ficient of perovskite film which converges to a gain coefficient
at threshold of gth ≈ 378 cm−1. Based on the value of threshold
gain (also indicates the total loss needs to be overcome to
achieve lasing condition), we calculate the cavity quality factor
Q ≈ 1.1 × 103, corresponding to a cold cavity mode linewidth
(Δλ = λ/Q) Δλ ≈ 0.71 nm. The observed laser mode linewidth
above (0.24 nm) includes the expected linewidth narrowing
from the stimulated emission process. As the free electron–
hole pair is the main carrier type in CH3NH3PbI3 film (i.e., in
contrast to well-defined excitons with high oscillator strength
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and strong exciton–photon coupling[45,46]), the coupling
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between cavity (VCSEL) mode and electronic transition in the
emitter (perovskite) is quite weak. Given also the large optical
mode volume (i.e., >>λ3), we do not expect an observable Pur-
cell effect from the high-Q cavity notwithstanding. We estimate
a spontaneous emission factor of β ≈ 10−3 (Figure 3a) which is
a measure for the fraction of spontaneous emission that is cou-
pled into the cavity mode for lasing. This value is comparable
to typical β values cited in single-crystal epitaxial III–V semi-
conductor VCSEL literature.[42,47] Smaller β values can result in
more drastic phase transition (Figure 3a where simulated L–L
curves for values of β = 10−3, 10−2, and 10−1 are presented for
comparison). At highest levels of excitation in our experiments
(though still modest), the net optical gain is sustained so that
the PeVCSEL temporal output nearly tracks that of the excita-
tion pulse profile (Figure 3f). We note the comparison with
gain-switching lasing behavior reported in III–V single crystal
laser devices[48–50] where injected carriers are consumed by
stimulated emission and lasing oscillations and self-terminated
in some cases on a very short time scale (from a few ps to a few
tens of ps).
Encouraged by the sub-ns pumping results, we optically
pumped the PeVCSEL devices by longer excitation pulses
(λ = 532 nm, τpulse = 5 ns, repetition rate = 10 Hz), anticipated
to reach a quasi-steady-state optical gain regime. We remark
here that using longer pulse excitation (labeled quasi-steady
state here) adds two additional factors of significance which
need to be addressed for a realistic device: (i the need to quan-
tify effects of Auger recombination adds to nonradiative loss,
and ii) the significant thermal load which the perovskite solid
film must endure and thus requires long-term thermal man-
agement challenges. In a cryogenic environment temperature
(to reduce the thermal stress), perovskite material was dem-
onstrated to lase by pumping using much longer pulses.[16] In
our case of room temperature, Figure 4 summarizes the prin-
cipal laser characteristics under ns pulse pumping of same
PeVCSEL devices described above. Now the excitation levels
required to reach laser threshold are 113.9 ± 15.0 µJ cm−2
pulse−1 (Figure 4a), which corresponds to estimated carrier
injection density ρ = (1.35 ± 0.18) × 1018 cm−3 from a rate
equation model for the carrier density which includes nonra-
diative Auger recombination in a quasi-steady-state limit. For
CH3NH3PbI3, there one finds variation of values for the Auger
recombination rates (three-particle inelastic scattering process)
spanning the range of (1.3–4) × 10−28 cm6 s−1.[33,51–53] From our
experiment results and self-consistent rate equation model, it
can be determined that the Auger recombination lifetime at
threshold carrier density level of our PeVCSELs is in the range
of 1.4–4.2 ns. Compared with CdSe-based colloidal quantum
dots where Auger process (τAuger ≈ 100 ps, two orders of magni-
tude faster than PL decay) severely hinders the dynamic build-
up of population inversion,[21] our PeVCSEL results reflect the
more moderate Auger process in dense CH3NH3PbI3 thin films
which benefit the laser from its high-Q, low-threshold micro-
cavity configuration. To improve the device performance, there
is room for further optimization by chemically designed strate-
gies whereby the Auger process might be further reduced by
tailoring the chemical and electronic structure of the perovs-
kites and/or operating at even lower optical loss conditions than
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Figure 4. PeVCSEL laser characteristics in quasi-steady-state regime (under nanosecond pumping). a) L–L curve for PeVCSEL device, with corre-
sponding pump energy density threshold of 113.9 ± 15.0 µJ cm−2. The threshold behavior is clearly seen in both linear and logarithmic plots. b) Single
mode lasing spectrum under different pump fluences at λ = 778.4 nm and FWHM Δλ = 0.24 nm. The inset shows the logarithmic plot to emphasize
the clean single mode operation with background suppression ratio >20 dB.
achieved here. We also note that in larger bandgap halide per-
ovskites the Auger cross sections could be significantly reduced
if the Br- and Cl-based perovskite materials scale similar to
inorganic single-crystal III–V and II–VI semiconductor lasers.
The higher excitation pulse energy content in quasi-steady-
state conditions leads to increase in both the electronic (elec-
tron–hole plasma[54]) and lattice temperatures of the perov­
skite active medium. The former includes a contribution from
the Auger process whereas the latter poses challenges to the
overall thermal stability of the CH3NH3PbI3 thin solid film in
the PeVCSEL devices (the temperature increase in the elec-
tronic and lattice degrees of freedom makes the full photon and
carrier density coupled rate equation modeling less instructive
than that in the transient case as multiple parameters are now
temperature-dependent in mostly unknown ways). Nonetheless,
our PeVCSEL devices operated robustly in single mode at λ =
778.4 nm with a sharp threshold as shown in Figure 4b. Here,
too, the background suppression ratio remained high (>20 dB)
under the nanosecond quasi-steady-state pumping condition.
Another critical issue is the photostability of CH3NH3PbI3
and the perovskite materials in general, which has recently
become a very important topic in the photovoltaic community.
Under our optical pumping regime, exposure to high levels
of optical and electronic excitation could perhaps be viewed
as “accelerated” lifetime test conditions for CH3NH3PbI3 thin
films. At this still early stage of the field, we speculate the per-
ovskite degradation is due to one or more of the three mecha-
nisms including those proposed in recent literature: i) a local
hot region within the excitation volume (heat diffusion is rela-
tively slow due to the low thermal conductivity of the film[55]).
Interaction with lattice excitations (phonons) in the release of
excess photoexcitation energy (in our case ≈0.74 eV per exci-
tation photon) or other carrier-phonon-related processes could
lead to a local temperatures sufficient for perovskite decompo-
sition (CH3NH3PbI3 perovskite material is reported to decom-
pose when temperature exceeds ≈150 °C[9]). ii) Chemical reac-
tion with oxygen and moisture (main) during the experiment
for perovskite films, further accelerated by the elevated tem-
peratures. iii) Photodegradation has also been speculated to
be a culprit (e.g., for perovskite solar cells), whether direct or
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indirect by mechanism (ii). Since the electronic and photonic
excitation levels are considerably higher in the PeVCSEL
devices when compared to perovskite solar cells, these factors
could accelerate degradation further. We then performed initial
characterization experiments measuring the PeVCSEL device
lifetime by continuous pumping with both sub-ns and ns pulses
at room temperature ambient environment as summarized in
Figure 5. In each case, pump pulse energy density was set at
1.5 times the threshold so as to compare our device lifetime
data with conditions similar to recent reports.[9,17,24] Under sub-
nanosecond pumping (Figure 5a), laser output of the PeVCSEL
device maintains its approximate original value for ≈4 h (total
laser shots > 107) by which its intensity has decreased down to
90% of original value (though lasing is still robust as evidenced,
for example, by the FWHM linewidth, shown as red triangles in
Figure 5a). Unsurprisingly, and given the reported low thermal
conductivity (0.5 W m−1 K−1) of CH3NH3PbI3 material,[55] heat
issues alone (perhaps compounded by accelerated photodegrad-
ation and chemical reaction with ambient oxygen and moisture)
are expected to be more severe under the quasi-steady-state
nanosecond pump conditions. Note how the laser output now
drops more rapidly (Figure 5b). Here, the lasing persists up to
nearly an hour, even if after 50 min continuous pulse pumping
the output power drops down to ≈10% of its original value. In
both cases, the reduction in the output laser power is irrevers-
ible, indicating material degradation is taking place during
these initial lifetime tests. Apart from the organic perovskite,
metal halide perovskites (CsPbX3, X = Cl, Br, I) nanocrystals
also exhibit promising results on the optically pumped ASE and
lasing,[24,56,57] however, clear evidence of much longer device
lifetime (beyond fs ultrashort pulse excitation) is still missing.
The surface organic ligands (e.g., oleylamine and oleic acid)
that are widely used[21,56,57] to passivate the surface states might
deteriorate the thermal properties and environmental stability
of the material. Based on our experiments in both the transient
and quasi-steady-state regimes with the corresponding experi-
mentally determined threshold carrier densities, we speculate
that the excitation power density needed for continuous wave
(CW) laser operation, with excitation at λ = 532 nm for pure
CH3NH3PbI3 devices would be ≈14 kW cm−2. At this writing,
Adv. Mater. 2017, 29, 1604781
www.advancedsciencenews.com www.advmat.de

6 management and hermetic protection of perovskite material

Communication
Laser shots (x 10 )
a) 0 2 4 6 8 10 12 will play a vital role for realizing competitive perovskite lasers
0.6 covering the visible and near-infrared spectrum. Finally, we
1.2 sub-ns pumping note that the nitride DBR of choice in these microcavities are
1.0 0.5 highly electrically conducting, so that electrical pumping (cur-
rent injection) might also become possible.
Intensity (a.u.)

FWHM (nm)
0.8 0.4
0.6 Experimental Section
0.3
0.4 Preparation of Perovskite Polycrystalline Films: Lead iodide (PbI2,
99.999%) and anhydrous dimethyl sulfoxide (DMSO) (99.9%) were
0.2
0.2 purchased from Sigma–Aldrich. Methylammonium iodide (MAI, >98%)
was purchased from Dyesol. PMMA (950 PMMA A4) was purchased
0.0 0.1 from MicroChem Corp. All the materials were used as received. In a
0 20 40 60 80 100 120 140 160 180 200 220 N2 filled 1 atm glovebox (with H2O < 0.1 ppm and O2 < 20 ppm), MAI
Time (mins) and PbI2 were mixed with 1.2:1 molar ratio into anhydrous DMSO for
a 40 wt% solution. Mixed solution (50 µL) was spread onto the quartz
b) 1.0 substrate or DBR surface and spin-cast at 3000 rpm for 63 s. During
ns pumping spin-casting, toluene (1 mL) was dripped vertically targeting the center
of substrate at 55 s after start of the spin-casting. Right after the spin-
0.8
casting and dripping process, the film was transferred onto a 100 °C hot
Intensity (a.u.)

0.6
t = 50 mins
t = 40 mins
0.4
t = 30 mins
t = 20 mins
0.2
t = 10 mins
t = 0 mins
0.0
720 740 760 780 800 820 840
Wavelength (nm)
Figure 5. PeVCSEL devices longevity lifetime test. a) PeVCSEL device life-
time measured under continuous sub-ns pulse pumping (0.34 ns, 1 kHz).
The incident pump energy density is 12.5 ± 0.7 µJ cm−2 (Ppump ≈ 1.5 Pth).
The blue dots record the output power evolution; the black dashed line
marks reduction to 90% of original intensity. The fluctuations originate
from the instability of the pumping source. The red triangles record the
FWHM linewidth during the experiment, underscoring the lasing opera-
tion. b) PeVCSEL device lasing under continuous nanosecond pulse
pumping (5 ns, 10 Hz), viewed through its amplitude and spectrum
recorded. The pump energy density is 175.3 ± 18.1 µJ cm−2 (Ppump ≈ 1.5 Pth).
The output laser power drops down to ≈10% of its original value after
50 min of continuous pumping, demonstrating significant perovskite
material degradation.
such a value is considerably higher than what we observed in
our perovskite films (on a DBR substrate) for damage threshold
when tested with a CW green laser pump at room tempera-
ture, while the GaN DBR thermal conductivity (and the very
high thermal conductivity of sapphire) may have helped in our
experiments. It is clear that further innovations in heat man-
agement strategies are needed, given the low intrinsic thermal
conductivity of solid films of CH3NH3PbI3.
In summary, the hybrid monolithic perovskite VCSEL struc-
ture is particularly promising for building practical perovskite
lasers. The high-Q, low-loss cavity enables PeVCSEL devices to
have low lasing threshold and achieve quasi-steady-state opera-
tion at room temperature. Further optimization on the chem-
ical composition and electronic structure of perovskite by using
other lead halide precursors or changing the organic cation
are expected to decrease the nonradiative loss and improve the
photostability of the perovskite solid thin films. Innovative heat
plate for 5 min annealing. Detail fabrication process can be found in the
Supporting Information.
Characterization of Perovskite Polycrystalline Films: Experiments were
conducted using fresh perovskite films at room temperature and under
ambient conditions (humidity ≈ 21%). Linear absorbance spectrum of
the films was measured by using supercontinuum laser (generated from
Coherent Reg A model 9000 Ti:sapphire pulsed laser; 800 nm, 100 fs,
100 kHz) as white light source and monochromator (Acton, SpectraPro)
to scan. Reflection signal from perovskite film surface was also measured
for more accurate absorbance values. The PL and lasing spectrum were
obtained by Princeton Instrument ACTON Inspectrum spectrometer
(resolution ≥ 0.125 nm). The effective refractive index of the perovskite
films was measured with variable angle spectroscopic ellipsometer (J. A.
Woollam M-2000DI). The PL lifetime was measured by time-correlated
single-photon counting (TCSPC) setup, using pump laser source (λ =
408 nm, τpulse ≈ 68 ps, 2.5 MHz repetition rate) from PicoQuant and
avalanche photon counting module from PerkinElmer. The surface and
cross-section morphology images were taken by LEO 1530 field-emitter
scanning electron microscope with 10 kV acceleration voltage. X-ray
diffraction (XRD) pattern was measured (perovskite thin film deposited
on quartz substrate) by Bruker D8 Discover X-ray Diffraction system.
PeVCSEL Laser Operation Characterization: DBR reflectance was
measured by using the same white light source and monochromator
as in absorbance measurement. The PeVCSEL devices were optically
pumped by sub-ns (Teem Photonics, Powerchip laser, frequency
doubled, 532 nm, 0.34 ns, 1 kHz) and ns (EKSPLA NT 342/1 Nd:YAG
laser, frequency doubled, 532 nm, 5 ns, 10 Hz) excitation pulses. All
experiments were conducted at room temperature. Near-field images
were measured by Thorlabs high-resolution monochromatic CMOS
camera. The transient pulse shapes were measured by an ultrahigh-
speed (40 GHz, 9 ps rise time), fiber-coupled photodetector module
from New Focus and an ultrahigh-speed digital sampling oscilloscope
(50 GHz) from Tektronix.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This research was supported by the Department of Energy (Basic Energy
Sciences) under Grant No. DE-FG02-07ER46387 and the Air Force
Office of Scientific Research (AFOSR), and Quantum Metaphotonics

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 www.advmat.de
and Metamaterials MURI (AFOSR Award No. FA9550-12-1-0488). This
Communication
research was also supported by the National Science Foundation (NSF)
under Award No. CMMI-1129964, and Yale University facilities used
were supported by YINQE and NSF MRSEC DMR 1119826. The authors
would also like to thank Prof. Humphrey Maris for sharing the Nd:YAG
ns laser for optical pumping experiments and Dr. Kwandong Roh for
useful guidance on the time-resolved pulse shape measurements.
Received: September 5, 2016
Revised: December 23, 2016
Published online: February 17, 2017
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