ARTICLES

PUBLISHED: 3 APRIL 2017 | VOLUME: 2 | ARTICLE NUMBER: 17052

Multiple exciton generation for

photoelectrochemical hydrogen evolution
reactions with quantum yields exceeding 100%
Yong Yan1,2*, Ryan W. Crisp1,3, Jing Gu1,4, Boris D. Chernomordik1, Gregory F. Pach1,5,
Ashley R. Marshall1,5, John A. Turner1 and Matthew C. Beard1*

Multiple exciton generation (MEG) in quantum dots (QDs) has the potential to greatly increase the power conversion efficiency
in solar cells and in solar-fuel production. During the MEG process, two electron–hole pairs (excitons) are created from the
absorption of one high-energy photon, bypassing hot-carrier cooling via phonon emission. Here we demonstrate that extra
carriers produced via MEG can be used to drive a chemical reaction with quantum efficiency above 100%. We developed a
lead sulfide (PbS) QD photoelectrochemical cell that is able to drive hydrogen evolution from aqueous Na2 S solution with a
peak external quantum efficiency exceeding 100%. QD photoelectrodes that were measured all demonstrated MEG when the
incident photon energy was larger than 2.7 times the bandgap energy. Our results demonstrate a new direction in exploring
high-efficiency approaches to solar fuels.

S
olar-to-chemical energy conversion for energy storage,
fuels and feedstocks, particularly to address greenhouse gas
emissions, is one of the primary goals for scientists in the field
of solar energy generation1,2 . High solar conversion efficiency is key
for a viable technology as that directly impacts the land area to be
covered and ultimately impacts the cost of the system. The main loss
limiting the conversion efficiency in solar conversion systems is that
photons with energies greater than the semiconductor bandgap (E g )
produce hot carriers that relax via electron–phonon scattering and
the subsequent phonon dissipation reduces the energy conversion
efficiency3 . Multiple exciton generation (MEG), within quantum-
confined semiconductor nanocrystals (also referred to as quantum
dots, QDs), describes a process where absorption of a high-energy
photon produces hot carriers that cool via the generation of
additional electron–hole pairs (excitons) rather than the generation
of heat and thus, overcome part of the losses associated with
hot-carrier cooling. The result is that the quantum efficiency (the
number of excitons produced as a fraction of the number of photons
absorbed) is greater than 100% for those wavelengths that can pro-
duce hot carriers with sufficient energy to drive the MEG process.
Quantum efficiencies exceeding 100% resulting from MEG have
been observed spectroscopically4 , as well as in the photocurrent of
appropriately designed QD solar cells. For example, a photovoltaic
system has been developed with an internal quantum efficiency
(IQE) close to 200% via chemically attaching a single layer of
PbS (E g = 0.96 eV) QDs on a single-crystal-anatase (001) TiO2
electrode5 . However, since only a single layer of QDs is employed
the amount of light absorbed was limited and the external quantum
efficiency (EQE) (defined as the number of electrons circulating
in the cell per second divided by the number of photons incident
on the photoelectrode per second) was lower than 1% (ref. 5).
Subsequently, enhanced photocurrents with EQEs greater than
100% due to MEG have been observed in PbSe QD solar cells6 , PbSe
nanorod-based solar cells7 and PbTe QD solar cells8 .
In addition to photovoltaic applications, quantum-confined
semiconductors are being explored for solar-fuel generation. In
that case, the photocarriers initiate chemical reactions at a
nanocrystal/liquid interface. For example, systems that exhibit
high EQE (60–90%) for photoelectrochemical (PEC) hydrogen
generation (EQEhy , defined as two times the number of H2
molecules divided by the number of incident photons) have been
developed that utilize CdSe9,10 , CdS11 and PbS12,13 QDs. The EQEhy
has approached 100% for photoelectrodes with 2 or 5 layers of
ZnS-coated CdSe in mesoporous TiO2 (ref. 14); however, an EQEhy
greater than unity for solar hydrogen generation has not been
experimentally demonstrated. An EQEhy > 100% not only has
practical significance towards highly efficient solar-fuel production,
but also represents a fundamental insight towards a new direction
for the capture and conversion of solar energy to fuels. Over 100%
EQEhy in the UV–visible range, which represents the major energy
portion of solar irradiation, is of particular significance.
In this study, we develop an approach that exhibits an
EQEhy exceeding 100% in the UV–visible range using PbS QD
photoelectrodes. The system consists of two separated electrodes
and is constructed so that hydrogen generation is accomplished
with no external voltage bias. One electrode consists of a conductive
PbS QD layer deposited on top of a FTO/TiO2 (fluorine-doped
tin oxide) dielectric stack, while the second electrode consists
of a platinum (Pt) mesh and is kept in the dark. Light is
absorbed at the photoanode within the QD layer producing free
electrons and holes. Photogenerated holes oxidize sulfide to sulfur
(nS2− + 2(n − 1)h+ →S2n− ) at the QD/solution interface (1M Na2 S
aqueous solution), while electrons make their way to the Pt electrode
where they can reduce H+ to H2 (g) (2H+ + 2e− →H2 ). Therefore,

1
Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, Colorado 80401, USA. 2 Department of Chemistry and Environmental
Science, New Jersey Institute of Technology, Newark, New Jersey 07102, USA. 3 Department of Physics, Colorado School of Mines, Golden, Colorado
80401, USA. 4 Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182, USA. 5 Department of Chemistry and
Biochemistry, University of Colorado, Boulder, Colorado 80309, USA. *e-mail: yong.yan@njit.edu; matt.beard@nrel.gov

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ARTICLES NATURE ENERGY

a b
e− e−
e−
TiO2 QD
Glass
e− e− FTO hν
TiO2 e−
H2O

Energy versus NHE (V)

PbS QDs e−
−0.42
H2
S2− Ef Eg −0.40

Salt bridge
H+/H2
pH = 7 + S2−/S2−
n
(phosphate buffer) h hν

hν h+
+
H
Sn2−
H2O H+
Pt H2O
Na+ 1 M Na2S

EQEhy = 2NH2 /Nhv > 100%

e hν

c d

PbS PbS H+/H2 MEG Eg

TiO2 TiO2
FTO S2−/S2−
n
FTO

500 nm

Figure 1 | MEG PEC cell illustration. a, Schematic of the PEC apparatus. The QD layers make up the active region of the photoanode. Photogenerated holes
oxidize sulfide in one compartment while electrons reduce hydrogen in the other compartment at the dark Pt cathode. A salt bridge connects the two
compartments and transports H+ and Na+ . b, The energy levels of the QD photoelectrode (Eg is the QD bandgap) with respect to normal hydrogen
electrode, NHE (V). Electrons leave the QD layer through TiO2 with enough chemical potential to reduce H+ to H2 while holes can oxidize sulfide.
c,d, Scanning electron micrographs of typical PbS QD photoelectrodes with QD layer thickness of 265 nm (c) and 370 nm (d). The scale bar is the same for
both images. e, For high-energy photons absorbed within individual QDs, MEG produces two or more electron–hole pairs that can participate in the
oxidation and reduction reactions. Using a chemical reaction at the QD surface can store the extra carriers directly in chemical bonds.

the overall reaction is to directly photosplit H2 S to H2 and S (which
further reacts to form S2n− ). Splitting of H2 S is thermodynamically
endoergic by 33 kJ mol−1 . Inexpensive and clean ways to remove
H2 S from both natural sources and chemical processes are being
sought15 . Photosplitting H2 S can be economical and has the added
benefit of the production of H2 gas, which can be used as either
a chemical precursor or energy source. We note that in our
experimental demonstration, developed here, the energy necessary
to split H2 S is provided by a combination of the chemical bias (via
a pH difference in each compartment) and the photovoltage of the
QD PbS photoelectrode.
Photoelectrochemical performance
We fabricated QD photoelectrodes with E g values of 0.85, 0.92
and 1.08 eV by depositing the QDs from solution using a layer-by-
layer approach on top of a patterned sol-gel TiO2 /FTO-coated glass
slide. In the layer-by-layer process we first employ PbI2 dissolved
in dimethylformamide to displace the oleate ligands and then
use 3-mercaptopropionic acid to deposit the final 3–4 QD layers
(refs 16,17 and see Methods). The resulting QD film can vary
between 250 and 500 nm depending on the number of layer-by-layer
cycles (see Supplementary Information for exact film thicknesses).
The PbI2 /dimethylformamide treatment produces films with very
little residual organic material, and results in I− -terminated QDs16 .
The finished QD photoelectrodes are immersed into an aqueous
1 M Na2 S solution and electrically connected to a Pt electrode
that is submersed in a phosphate buffer (pH = 7) in a separate
compartment. A salt bridge connects the two compartments to
complete the circuit (Fig. 1a). The gas-tight PEC cell is illumi-
nated with a xenon lamp employing 20 nm band-pass filters
at wavelengths ranging from 380 nm to 1,500 nm. The incident
power intensity is kept at ∼10 µW cm−2 using neutral density
filters and accurately determined by placing a calibrated silicon
photodiode or a germanium photodiode in the place of the QD
photoelectrode prior to adding solution. Light is directed onto
the PbS/Na2 S (aq) interface and following illumination hydrogen
evolves at the Pt electrode. The amount of hydrogen, collected
from the cathode, is determined by gas chromatography (Shimadzu
GC-2010 Plus, Tracera) with a Carbxen 1010 PLOT column and
a barrier discharge ionization detector. Since the electrodes are
shorted during the entire PEC reaction there is no external bias
applied to the system; therefore, only the photovoltage provides the
necessary driving force (which is reduced from the 33 kJ mol−1 by a
chemical bias).
To directly evaluate the efficiency of PEC hydrogen generation,
we measured EQEhy , at specific wavelengths. Since it takes two
electrons to produce one hydrogen molecule, the EQEhy is equal to
two times the number of H2 molecules divided by the number of
incident photons, or,
2nH2 NA hc
 
EQEhy (λ) = (1)
I0 At λ
where nH2 is the number of moles of hydrogen gas produced,
N A is Avogadro’s constant, I 0 is the incident light intensity, A is
the illumination area, t is the illumination time, λ is the incident
wavelength, h is Planck’s constant, and c is the speed of light.
The EQEhy under incident wavelengths from 380 nm to 500 nm is
shown in Fig. 2a. For each PbS QD bandgap we fabricated three
photoelectrodes and measured their response separately obtaining
less than a 5% difference indicating good reproducibility and
reliability of our system. In the wavelength range that MEG would
be expected for photoelectrodes with E g of 0.85 eV, at 450 nm

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NATURE ENERGY ARTICLES
a 120 120 c
0.85 eV
0.92 eV
100
110 1.08 eV 110 0.85 eV

Absorbance (a.u.)
80 0.92 eV
1.08 eV
EQEhy (%)

100 100

IPCE (%)
IPCE (%)
60
90 90
40

80 80 20

70 70 0
380 400 420 440 460 480 500 400 800 1,200 1,600
Wavelength (nm) Wavelength (nm)

b
λ = 400 nm
Io = 10 μW cm−2

5 μA cm−2
Current density

1.08 eV

0.92 eV

0.85 eV

0 100 200 300 400 500

Time (s)

Figure 2 | PEC performance characteristics. a, EQE (filled symbols) for hydrogen generation induced by PbS QD photoelectrodes with Eg of 0.85 eV (red
circles), 0.92 eV (green squares) and 1.08 eV (black triangles) in Na2 S aqueous electrolyte. IPCE (open symbols) at the range of 380–500 nm is also
illustrated for comparison. (Error bars generated from standard deviations of 5-times measurement, see Supplementary Note 1.) b, Typical steady-state
chopped-light current measurement of the PbS QD photoelectrodes (scale is 5 µA cm−2 ). c, The symbols show the IPCE of PbS QD photoelectrodes at Eg
of 0.85 eV (red circles), 0.92 eV (green squares) and 1.08 eV (black triangles). The dashed lines are the absorption spectra of the QDs in solution.

(3.24E g ), 420 nm (3.47E g ), 400 nm (3.65E g ) and 380 nm (3.83E g ),
or for photoelectrodes with E g of 0.92 eV, at 400 nm (3.37E g ) and
380 nm (3.55E g ), the EQEhy are all above 100% with the highest
value of 114 ± 1.3% for E g of 0.85 eV at incident light of 380 nm.
As far as we know, this is the first time that hydrogen has been
produced photoelectrochemically under visible light illumination
with a quantum yield greater than 100%.
In addition to the EQEhy , we also measure the incident photon-
to-current efficiency (IPCE), which is the number of electrons
delivered per second divided by the number of incident photons per
second and is determined from
J hc
 
IPCE = (2)
I0 e λ
where J is the photocurrent density (µW cm−2 ) and e is Coulombs
per electron. The Faradaic yield (FY) relates the EQEhy to the IPCE,
EQEhy = IPCE × FY, and is given by
2nH2
FY = F (3)
JAt
where F is Faraday’s constant (Coulombs per mole of electrons,
C mol−1 ). With our set-up under an applied external bias in the dark,
we find the FY for hydrogen generation is >97% (Supplementary
Figs 1 and 2). Therefore, the EQEhy is approximately equal to the
IPCE. We compare (Fig. 2a open and filled symbols) the IPCE to
the EQEhy at each wavelength and find good agreement confirming
that FY >95%. In the following we approximate the EQEhy by
the IPCE.
To determine the IPCE we measured the photocurrent using
mechanically chopped light and Fig. 2b displays the typical light
response profiles for 400 nm wavelength illumination used to
calculate the IPCE. In Fig. 2c the IPCE from 380 nm to 1,500 nm
is compared to the absorption spectra of the respective QD
photoelectrodes. A good match near the first exciton transition
energy demonstrates that the photocurrent is proportional to the
amount of light absorbed by the QDs. An IPCE >100% is observed
in the 450–380 nm range, reaching 118 ± 2.7% for QDs with
E g of 0.85 eV. For QD photoelectrodes with E g of 0.92 eV, the
IPCE reached 109 ± 2.6% at 380 nm (Fig. 2a,c). All of these
results demonstrate that we have developed a PbS QD system
that can photoelectrochemically produce hydrogen with an EQE
exceeding 100%. Note for these results we have quantified both
the photogenerated hydrogen gas and the photogenerated electrons
directly and show that both independently demonstrate MEG in a
PEC cell.
MEG comparison in PEC cells and solar cells
The enhanced IPCE or EQEhy , reported here is comparable to results
reported for QD solar cells with known MEG. For instance, we
previously reported a PbSe QD solar cell with an EQE reaching
114% at incident wavelength of 380 nm (ref. 6). EQEs of 122% using
narrow-bandgap PbSe nanorods7 , and exceeding 120% for PbTe QD
solar cells have also been reported8 .
Interestingly, the EQEhy of our PbS QDs PEC system is larger
than that of the photon-to-electron EQEPV of a PbS QD photovoltaic
cell. For example, the maximum EQEPV of the PbS QD solar cell
(E g = 1.3 eV) was reported at ∼80% for wavelengths between 430
and 500 nm (ref. 16). At shorter wavelengths, the EQEPV sharply
decreases towards zero. The difference is more obvious in the
blue wavelength range, less noticeable for redder wavelengths and
almost disappears for wavelengths longer than about 650 nm. The
differences between PV and PEC behaviour stem from the different
direction that light impinges on the devices. For PV operation
light enters through the glass/FTO/TiO2 interface while for the
PEC operation light is incident on the PbS QD/Na2 S interface.
To investigate, we illuminated a photoelectrode from the ‘back’

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ARTICLES NATURE ENERGY

a
120 Eg = 0.85 eV Front side

hν 100
110
hν
hν
100 80

APCE (%)
IPCE (%)

90 60

80
8 0 40
hν
hν
hν 0.85 eV
70
7 0 20
0.92 eV
Back side 1.08 eV
60
6 0 0

400 450 500 550 600 650 2.0 2.4 2.8 3.2

Wavelength (nm) Photo energy (eV)

Figure 3 | IPCE front and back illumination. Comparison of the IPCE

b
(QD Eg : 0.85 eV) for front (filled circles) and back (open circles)
illuminations and for two thicknesses of the QD layers (blue = 265 nm and 100
red = 370 nm). (Insets: demonstrations of light illumination pathway.)
80

(FTO side) similar to the illumination method that a QD solar
cell experiences. In that case we observe a decreasing IPCE in the
range of 420 to 380 nm (Fig. 3) similar to what is observed in PbS
QD solar cells. A maximum IPCE was obtained at 420 nm, but
the value at this wavelength is significantly lower than the IPCE at
420 nm when illuminated from the front, and is lower than 100%
(noted as 85%, Fig. 3a, red). Even though illumination through the
FTO/TiO2 is most common for QD solar cells, we find that such
‘back’ illumination is detrimental to achieving high IPCEs for PEC
cells where clearly ‘front’ illumination is advantageous.
There are at least three factors that can be responsible for the
different behaviours observed when photoexcited from the front or
back. First, the active wavelength range needed to observe MEG is
interfered with by the absorption of the TiO2 or FTO layers along
the path of the incident photons prior to reaching the QD layer,
since FTO and TiO2 begin to absorb light for wavelengths less
than 420 nm. This produces a drop in EQE values at wavelengths
shorter than 420 nm. When we illuminate from the PbS QD side any
photon losses arise from reflections from the cell window interfaces
and the sulfide solution rather than the FTO/TiO2 . Neither the
solvent nor the window absorb within the range from 350 to 600 nm
(Supplementary Fig. 3). As a result, in the wavelength range from
500 nm to 380 nm (Fig. 2a), we observe a continuously increasing
IPCE or EQEhy , rather than a sharp decrease for wavelengths
shorter than 420 nm. Such an observation also matches the expected
absorption spectra of the QDs (see Fig. 2c for comparison of the QD
solution absorption spectra (dashed lines) to IPCE).
A second reason that the different illumination pathways could
give different EQEs is due to the different reflection losses between
the glass/FTO and the PbS QD layer. The IPCE obtained from ‘back’
illumination is significantly lower than the ‘front’ illumination even
in the wavelength range where TiO2 and FTO are not expected to
interfere (no absorption of FTO/ TiO2 was observed from 420 nm
to 600 nm). The reflection losses at the QD/solution interface are
expected to be smaller than the sum of reflections incurred at the
glass/solution, glass/FTO, FTO/TiO2 and TiO2 /PbS interfaces.
Finally, the concentration of photogenerated carriers is highest
at the QD/TiO2 interface in the case of ‘back’ illumination and
at the QD/solution interface in the case of ‘front’ illumination.
This is due to the high extinction coefficient of the PbS QDs. At
the QD/solution interface, the holes undergo a quick irreversible
reaction of sulfide oxidation and are removed from the QD solid,
reducing recombination losses. In the case of ‘back’ illumination,
however, a higher fraction of the photogenerated carriers are lost
due to recombination at the back ohmic contact.
APCE (%)
60 hνth /Eg = 2.7
40
20
0
1.6 2.0 2.4 2.8 3.2 3.6
hν/Eg
Figure 4 | Absorbed photon-to-current efficiency measurements. a, APCE
as a function of illumination photon energy (eV). b, APCE as a function of
incident photo energy divided by QD bandgap energy, or multiples of the
bandgap (hν/Eg ). (Blue solid lines, linear fitting hν/Eg from 1.6 to 2.5 and
from 2.8 to 3.6.). The threshold photon energy (hν th /Eg ) is about 2.7.
For back illumination, holes that do not undergo interfacial
recombination must transport through the bulk of the PbS QD
film to oxidize sulfide within the solution and thereby complete
the circuit. Under front illumination electrons must transport
though the PbS QD film and reach the TiO2 to be collected. Bulk
recombination that occurs within the QD layer would increase
for thicker QD films. Therefore, we expect that the performance
difference between back and front illumination would depend on
the PbS QD thickness. We compare front and back illuminations for
PbS QD films that are 265 nm (Fig. 3, blue) and 370 nm thick (red).
The IPCE of front illumination remains indistinguishable; however,
the back illumination shows a significant difference: the 370 nm
thickness exhibits ∼10% lower efficiency than the 265-nm-thick
QD layer due to the longer hole-diffusion path length. The IPCE
differences are also prominent in the blue wavelength range while
less obvious in red. The differences corroborate our predication that
carriers (particularly holes) lost inside the PbS QD layer largely
depending on the carrier’s path length. Undoubtedly, our current
PEC system shows significant advantages over QDs solar cells in
terms of obtaining high EQE.
The internal quantum efficiency (IQEhy ) of our current system
can be determined by normalizing the EQEhy to the measured
absorbance of the QD photoelectrode and the sulfide solution,
IQEhy = EQEhy /A = EQEhy /(1 − R) ∼
= IPCE/(1 − R) = APCE (4)
where A includes absorbance from the solution and QDs, defined
as: A = APbS + ASolution . In the wavelength range of 380 nm–750 nm,

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NATURE ENERGY
no absorption of ASolution has been observed (Supplementary Fig. 3).
In addition, IQE may be easily characterized by APCE (absorbed
photon-to-current efficiency) due to the near-unity Faradaic
efficiency for hydrogen generation in our system. Here, we plot the
APCE versus the incident photon energy E = hv in Fig. 4a and versus
hv/E g in Fig. 4b (the photon energy normalized to the bandgap
of the QD). Interestingly, the APCE, not adjusted for solution ab-
sorbance or reflections from the cell window, remained nearly con-
stant for each QD sample at 78% ± 4% for excitation photon energy
at an absolute value at 1.6 eV up to 2.2 eV. This is in agreement with
the IQE observed in PbSe and PbS QD solar cells6 . Although the
QD photoelectrode at E g = 1.08 eV did not show IQE or APCE over
100%, a clear APCE increase was also observed at around 3.0 eV.
Surprisingly, it is very clear in Fig. 4b, that the hv/E g changes in
slope with the APCE are almost all observed at around 2.7. It is
indicative that in our PEC system, the MEG effect is observed for
photon energies that are larger than 2.7E g , this observation is very
similar to most of the reported value of isolated PbS QDs18 .
Conclusions
Theoretically, MEG is beneficial towards obtaining a higher limit
of solar-fuel generation efficiency19,20 . The overall solar-to-chemical
conversion efficiency, ηrxn = J tot V rxn /P in , where J tot is total current
density, V rxn is fixed at the voltage necessary to drive the chemical
reaction, and P in is the input power density from the solar irradiance.
The total current is Rdetermined by the EQE of the system and
the solar flux, Jtot = hvmin EQE(hv)0(hv)dhv, where 0(hv) is the
solar flux. Here hvmin is the minimum energy needed to initiate
the chemical reaction and includes any overpotential. Since V rxn is
fixed by the desired photochemical reaction to increase ηrxn one
needs to increase J tot . There are two ways to increase J tot : decrease
the overpotential such that hvmin is closer to the thermodynamic
limit; and utilize MEG to increase EQE. Finding an inexpensive
and efficient catalyst, which is a necessary and important research
direction, can decrease the overpotential. The results presented
herein show that, under the appropriate conditions, the EQE can
be over unity for a range of wavelengths and can thus increase J tot ,
demonstrating a parallel avenue for increasing the solar-to-chemical
conversion efficiency, ηrxn .
The generation of solar fuels is receiving significant interest1,2 .
However, the low efficiency of low-cost materials and the high cost
of the current set of high-efficiency materials for PEC hydrogen
generation are major concerns for the development of solar
fuels1,21–24 . In our results presented here, we show that it is possible
to capture multiple-exciton-generated electrons in a fuel-forming
reaction. It is encouraging for the future design and development
of PEC systems that MEG may be utilized to photosplit water to
generate hydrogen fuels with the goal of surpassing the Shockley–
Queisser limit. Effective water oxidation as a counter reaction is
undeniably another non-trivial step to investigate and was not
considered here. Two or more photoelectrodes connected in series
or in parallel with one able to take advantage of MEG is a potential
area of future research. Finally, to make the largest impact the MEG
onset should be as close to twice the bandgap as possible. Research
on new heterostructured QD systems that show onset for MEG
much closer to the 2E g limit is underway17,25 .
Methods
Materials for quantum-dot synthesis. PbCl2 (99.999%), oleylamine (OLA, tech.
grade, 70%), CdO (99.99%), oleic acid (OA, tech. grade, 90%), 1-octadecene
(ODE, tech. grade, 90%), sulfur powder (99.98%), ammonium sulfide (40–48 wt%
in H2 O), tetrachloroethylene (TCE, ≥99.9%), hexane (99.9%), octane (99.9%),
acetonitrile (ACN, grade ≥99.93%), N ,N -dimethylformamide (DMF,
TraceSELECT, for inorganic trace analysis, ≥99.99995% (trace metals analysis))
and ethanol (≥99.5%) were purchased from Sigma Aldrich. Lead oxide (PbO,
99.99%) was purchased from Alfa Aesar. All of the chemicals were used
as received.
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ARTICLES
Synthesis of PbS QDs from CdS QDs. PbS with different bandgap energies, E g
(given by the position of the first exciton peak), of 1.08 eV, 0.92 eV, and 0.85 eV
was synthesized by the cation exchange of CdS. CdS was also synthesized following
our previous procedure16,17,26 . Pb-precursor solution was synthesized by heating
OLA (5 ml) and PbCl2 (1.5 mmol) in a 50 ml three-neck flask to 140 ◦ C for 30 min
under nitrogen flow until a white, turbid solution was achieved. Then, the solution
was cooled or heated to a desired temperature for the injection of CdS QDs.
PbS-1.08 eV. The synthesis of PbS-1.08 eV was based on our previously reported
procedure17 . When the Pb-precursor reached 120 ◦ C, 1 ml of CdS QD
(∼58 mg ml−1 ) in ODE was swiftly injected. After 20 s, the reaction was
quenched by a water bath. Hexane (5 ml) and OA (4 ml) were added when the
reaction bath reached 70 and 40 ◦ C respectively. The washed QD solutions were
further isolated from the reactants by filtration with a 0.45 µm PTFE filter
followed by centrifuging at 7,500 r.p.m. The PbS QDs were washed 2–3 times
using hexane and ethanol, and then redispersed in octane. The CdS QDs were
synthesized by heating CdO (2.2 mmol, 0.28 g), 5.7 mmol OA (1.8 g) and 8 g of
ODE to 260 ◦ C for 20 min and allowed to cool to 30 ◦ C when a (NH4 )2 S:OLA
precursor solution was injected and stirred for 1 h without heating. The sulfur
precursor was prepared by stirring a solution of 80 µl (NH4 )2 S aqueous solution
with 10 ml of OLA for 20 min.
PbS-0.92 eV. The synthesis of PbS-0.92 eV was based on our previously reported
procedure17 . When the Pb-precursor reached 190 ◦ C, 1 ml of CdS QDs
(∼36 mg ml−1 ) in ODE was swiftly injected. All other conditions and treatments
were identical to those given for the PbS-1.08 eV synthesis. CdS QDs were
synthesized by heating CdO (1 mmol, 0.128 g), 3 mmol OA (0.942 g) and 15 g of
ODE to 260 ◦ C for 20 min, then the temperature was set to 250 ◦ C, 1 ml of the
sulfur precursor was injected and the solution was maintained at 240 ◦ C for
20 min. For these QDs, the sulfur precursor was prepared by dissolving S powder
at a concentration of 0.5 M in ODE at 130 ◦ C.
PbS-0.85 eV. The synthesis of PbS-0.85 eV was based on our previously reported
procedure17 . When the Pb-precursor reached 190 ◦ C, 1 ml of CdS QDs
(∼20 mg ml−1 ) in ODE was swiftly injected and the temperature was maintained
at 180 ◦ C. Twenty minutes later, the reaction was quenched by a water bath. The
remainder of the reaction conditions and treatments were identical the
PbS-0.92 eV synthesis. Larger CdS QDs were synthesized as in the PbS-0.92 eV
synthesis but the S-precursor was injected at 265 ◦ C and the solution was
maintained at 250 ◦ C; ∼13 min later, additional S-precursor was added drop-wise
until the desired size (∼5.5 nm diameter, 450 nm first exciton peak wavelength)
was achieved.
Photoelectrode fabrication. The final QD photoelectrode was a thick,
all-inorganic, air-stable conductive QD film formed on a patterned sol-gel
TiO2 /FTO-coated glass slide, which was fabricated on the basis of our previously
reported procedure16 . First, FTO/glass substrates were cleaned vigorously with
ethanol and UV–ozone-treated prior to depositing the TiO2 layer. Within 10 min
of UV–ozone treatment, 70 µl TiO2 sol-gel was deposited on the substrate and
spun at 1,400 r.p.m. for 30 s. The FTO contact pads were cleaned using ethanol
prior to drying at 115 ◦ C and annealing at 450 ◦ C for 30 min. The resulting films
were stored in air for at least 1 day. The TiO2 sol-gel was prepared by mixing in
air 5 ml anhydrous ethanol, 2 drops hydrochloric acid, and 125 µl deionized water
and stirred while adding drop-wise 375 µl titanium ethoxide. The resulting clear
liquid was stirred for 48 h in a nitrogen atmosphere and then stored in a freezer.
Second, the TiO2 -coated substrates were immersed in a 15 mg ml−1 solution of
the desired QDs in hexane. The substrate was removed and immersed in a
10 mM Pbl2/DMF solution for 30–60 s. The cycle was repeated to build up a thick
QD film. A post-ligand treatment with neat ACN was employed to help remove
residual DMF. A mixture of 20 vol.% DMF/ACN can also solvate PbI2 and a
photoelectrode made from this solution performed nearly as well as those with
PbI2 in DMF for the ligand treatment solvent. Typically, photoelectrodes used
10–40 layers of the PbI2 -treated QDs and then were followed by 3–4 layers of
QDs treated with 10% 3-mercaptopropionic acid in methanol, rinsing twice with
methanol and drying with nitrogen. All photoelectrodes presented here were
fabricated at room temperature (23.9–26.7 ◦ C) and relative humidity that
fluctuated between 16 and 20%. The resulting QD layer of the photoelectrode
varied between 250 and 500 nm depending on the number of
layer-by-layer cycles.
Photoelectrode assembly and active area determination. The top edge of the
PbS and TiO2 layer on the photoelectrode was removed by a blade. This exposed
FTO conductive area and the copper wire were glued together through
conductive silver epoxy (PELCO colloid silver). The edge of the above-mentioned
photoelectrode and the conductive connection area was then further completely
protected via an insulation epoxy (Loctite 9462 Hysol). Further, a resistance epoxy
(Loctite E-120 HP), cured at room temperature overnight, was then applied to
5
ARTICLES
prevent the epoxy layer from etching. The final active area of the photoelectrode
was accurately determined by a HP Scanjet 7650 in combination with ImageJ
software according to a previously reported method with slight modification27 . In
this method, the electrode surface was aligned parallel to the scanner glass and
was scanned to obtain an electrode surface image. The number of black pixels of
the measured active area can be extracted by the ImageJ software and such pixel
number was then converted to the actual area through a standard relationship
that was previously built (892,802 pixels per square centimetre).
Incident light and hydrogen gas calibrations. The incident light came from
white light passed through a monochromator, and a neutral density filter was also
applied to adjust the light intensity at ∼10 µW cm−2 , where typically a 75 W Xe
arc lamp was used as the source. The PEC system was placed in a dark room to
avoid interfering illumination. We used a silicon photodiode for the
380–1,060 nm range and a germanium photodiode for 1,060–1,500 nm. The
calibrated photodiodes all have NIST traceable calibration, and have a similar
area to the test photoelectrodes. We also applied a Newport UV-818-L detector
(NIST traced calibration) to compare the light intensity results at the 380–650 nm
range with the Si photodiode. The current measured from the Newport UV-818-L
detector and the Si photodiode has less than 0.2% difference in the range of
380 nm to 500 nm, while the difference was manifested to 0.5% at the range from
500 nm to 650 nm. The specific light intensity inside the PEC cell, at the specific
position where the photoelectrode will be placed, was accurately determined by
the current generated by the calibrated photodiode. Note that the light intensity
measurement might correspond to ∼3% systematic error under our
measurement conditions due to the refractive index difference between the
glass/air interface of the photodiode and the glass/solution interface of the
photoelectrode (note: light passes through the air/glass interface and then
through the glass/solution interface to reach the photodiode surface in solution).
Such difference can be illustrated according to the equation:
R = [n1 − n2 ]2 /[n1 + n2 ]2
in which R is reflectivity, n1 is the refractive index of glass and n2 is the refractive
index of solution in the photoelectrode case or air in the photodiode case. We can
approximate the reflective losses via n1 = 1.47 and n2 = 1.33 (for Na2 S solution,
approximated by water) or n2 = 1 (for air). We calculate Rsolu = 0.3% and
Rair = 3.4%. These two numbers indicated that (∼3%) more light might reach the
photoelectrode surface than the photodiode surface.
Hydrogen gas was measured with a Shimadzu GC-2010 Plus Gas
Chromatograph (Tracera) with a highly sensitive barrier discharge ionization
detector and the carrying gas was 99.9999% ultrapure helium gas to ensure a two
order higher detection limit on hydrogen than other common detectors in gas
chromatography. The standard hydrogen gas was generated with a sealed
two-compartment electrochemical cell filled with 1 M H2 SO4 and Pt as both
cathode and anode. The theoretical hydrogen concentration was plotted against
the detection area of GC, as shown in Supplementary Fig. 1 and Supplementary
Table 1. A highly correlated linear curve was obtained between the theoretical
hydrogen concentration and the detection area of GC, with a linear correlation
coefficiency of 0.999952. And this calibrated equation was applied for the future
accurate amount determination of hydrogen gas. To reduce any systematic
errors associated with different compartments we replaced only the anode with
our QD photoelectrode; the cathode compartment (where H2 evolves) remained
the same.
Scanning electron microscopy. Scanning electron microscopy (SEM)
measurement was conducted to obtain the thickness of the PbS films. The surface
morphology was analysed using a JEOL JSM 7600F field-emission scanning
electron microscope operated at 5 kV. First, the film on these photoelectrodes was
fabricated as follows: we used the methods (as described from photoelectrode
synthesis) to make PbS film from one batch of PbS solution at a specific bandgap
deposited onto a ∼3 cm × 3 cm as-prepared glass first. Then each photoelectrode
(in small size) was made from this large-area (3 cm × 3 cm) as-prepared
film-coated glass, which was carefully cut into the specific size (approximately
1 cm2 ) as noted in Supplementary Table 2. Note that the thickness results of the
film from the above table are listed below: for example PbS-0.85 eV, thicknesses
of electrodes 1, 2 and 3 (originated from the same large electrode), measured
using the SEM mentioned here, were very similar, noted as 265 nm; PbS-0.92 eV,
thicknesses of electrodes 4–6 are also almost the same, noted as 255 nm;
PbS-1.05 eV, thickness of electrodes 7–9 are also the same, noted as 270 nm.
A thicker electrode at bandgap 0.85 eV was also intentionally made to investigate
the IPCE difference from back and front illumination as shown in Fig. 3; SEM
(Fig. 1c,d) indicated a thickness of 370 nm for the film.
Data availability. The data that support the plots within this paper and other
findings of this study are available from the corresponding authors on request.
6 NATURE ENERGY 2, 17052 (2017) | DOI: 10.1038/nenergy.2017.52 | www.nature.com/natureenergy
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
NATURE ENERGY
Received 12 October 2016; accepted 3 March 2017;
published 3 April 2017
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Acknowledgements
We would like to thank B. To and C. Xiao from NREL for the scanning electron
micrographs. A. J. Nozik, J. Luther, D. Kroupa and Y. Yang are thanked for their helpful
discussions. Y.Y. would like to acknowledge the support from the startup fund at New
Jersey Institute of Technology. Y.Y., R.W.C., B.D.C., G.F.P., A.R.M. and M.C.B.
NATURE ENERGY
acknowledge support from the Center for Advanced Solar Photophysics, an Energy
Frontier Research Center funded by the Office of Basic Energy Sciences within the Office
of Science. J.G. and J.A.T. acknowledge the solar photochemistry programme within the
division of Chemical Sciences, Geosciences, and Biosciences of the Office of Basic Energy
Sciences within the Office of Science. All work is supported by the Department of Energy
under contract No. DE-AC36-08GO28308 to NREL.
Author contributions
Y.Y. and M.C.B. conceived the experiments and led the project; Y.Y. and J.G. carried out
the photoelectrode synthesis and characterization and photoelectrochemical
investigation; R.W.C., B.D.C., G.F.P. and A.R.M. carried out quantum-dot synthesis and
film preparation; Y.Y., J.A.T. and M.C.B. analysed the data; Y.Y. and M.C.B. wrote the
manuscript with input and discussion from all authors.
NATURE ENERGY 2, 17052 (2017) | DOI: 10.1038/nenergy.2017.52 | www.nature.com/natureenergy
© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.
ARTICLES
Additional information
Supplementary information is available for this paper.
Reprints and permissions information is available at www.nature.com/reprints.
Correspondence and requests for materials should be addressed to Y.Y. or M.C.B.
How to cite this article: Yan, Y. et al. Multiple exciton generation for
photoelectrochemical hydrogen evolution reactions with quantum yields exceeding
100%. Nat. Energy 2, 17052 (2017).
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Competing interests
The authors declare no competing financial interests.
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