Supporting Information

Unassisted water splitting exceeding 9% solar-to-hydrogen

conversion efficiency by Cu(In,Ga)(S,Se) 2 photocathode
with modified surface band structure and halide perovskite
solar cell
Bonhyeong Koo,1 Daehan Kim,1 Passarut Boonmongkolras,1 Seong Ryul Pae,1 Segi Byun,2
Jekyung Kim,1 June Hyuk Lee,3 Dong Hoe Kim,4 Suncheul Kim,5 Byung Tae Ahn,1 Sung-
Wook Nam,6 Byungha Shin*,1

1Department of Materials Science and Engineering, Korea Advanced Institute of Science and
Technology, Daejeon 3414, Republic of Korea
2Center for Energy Efficiency and Materials, Korea Institute of Energy Research, Daejeon,

34129, Republic of Korea

3Neutron Science Division, Korea Atomic Energy Research Institute, Daejeon, 34057,

Republic of Korea
4Department of Nanotechnology & Advanced Materials Engineering, Sejong University, Seoul,

05006, Republic of Korea

5Memory Thin Film Technology, Memory Manufacturing Operation Center, Samsung

Electronics, Hwaseong, 18448, Republic of Korea

6School of Medicine, Kyungbook National University, Daegu, 41405, Republic of Korea

Corresponding author: byungha@kaist.ac.kr & nams@knu.ac.kr

Experimental section

Deposition of Cu(In,Ga)(S,Se) 2 absorber

CIGS thin films were fabricated on a Mo-coated soda lime glass substrate using co-sputtering

of Cu, In, and Ga precursors followed by selenization and sulfurization. The detailed procedure

of CIGS deposition can be found in our previous publication.1 The bandgap of CIGS was

extracted by an external quantum efficiency (EQE) measurement (QEX7 solar cell spectral

response/QE/IPCE measurement system, PV measurement) and was determined to be 1.17 eV,

which corresponds to the final composition of Cu 0.9 (In 0.7 Ga 0.3 )(S,Se) 2 . A calibration was done

by a silicon photodiode (THORLABS, LMR1/M) from 300 - 1200 nm.

Growth of ZnS and CdS buffer layers

As-deposited CIGS thin-films were immediately immersed into a home-made chemical bath to

deposit the ZnS buffer layer. The experimental details of ZnS formation on CIGS are described

in reference 2 and 3. The optimized CBD time of the ZnS was about 5 min, which resulted in

20 nm thick ZnS. After the deposition of ZnS, CIGS/ZnS layers were ultrasonicated in DI water

for 5 sec to remove surface residues followed by inert gas blowing. CdS buffer layers were

prepared by chemical bath deposition, the details of which can be found in reference 1.

Formation of reduced graphene oxide (binder)─Pt (electrocatalyst)

After the deposition of double buffer layers, reduced graphene oxide (rGO) was spray-coated

on the sample kept on a hot plate at 100 oC. The volume of the rGO solution optimized for the

size of our samples (0.5 cm2) was 0.25 mL. The full description of the fabrication process of
rGO is available in our previous work.4 After the spray-coating, the sample was immediately

loaded on an e-beam evaporator with a base pressure of low-10-6 Torr to deposit Pt

electrocatalysts. The deposition rate was kept at 0.05 Å/s to form Pt catalysts in the form of

nanoparticles. The thickness was monitored by Au coated quartz crystal and the final thickness

was estimated to be 1.5 nm.

Preparation of IrO X oxygen evolving electrocatalyst

Copper plate with a size of 2.5 x 2.5 cm2 was polished to remove the surface copper oxide and

to create a rough surface. A polished copper plate was ultrasonicated with acetone and

isopropyl alcohol to remove organic contaminants and small particles on the surface. After N 2

blowing and drying, the copper plate was immediately transferred to e-beam evaporator with

the base pressure of low-10-6 Torr. A 50 nm thick Ti was deposited as an adhesive layer

followed by the deposition of a 100 nm thick Ni layer. After that, 10 nm thick Ir was evaporated

with a fixed deposition rate of 0.5 Å/s. Prior to PEC measurement, the Ir anode was immersed

into a 1M KOH aqueous solution for 1 hr and then several dummy LSV measurements were

carried out to form iridium oxide and/or iridium hydroxide. OER is kinetically more sluggish

than HER, so a double-sided Cu/IrO X OER catalyst whose active area (6.25 cm 2) is much larger

than that of the CIGS photocathode (0.1 cm2) was adopted.

Device fabrication and characterization of perovskite solar cell

A triple cation hybrid organic-inorganic perovskite ((Cs 0.15 FA 0.65 MA 0.20 )Pb(I 0.8 Br 0.2 ) 3 ) solar

cell was fabricated via a one-step spin coating process. The perovskite solar cell used in this

study had a planar p-i-n structure with PTAA (Poly(triaryl-amine)) and C 60 as the hole transport
and the electron transport layer, respectively. The PTAA solution was prepared by dissolving

powder in toluene (5 mg/ml), and the PTAA solution was spin-coated onto a UVO-treated

indium-tin-oxide (ITO) substrate at 6000 rpm for 30 sec. After that, the spin-coated films were

annealed in 100 oC for 10 min. More details of the preparation of triple-cation perovskite layers

can be found in reference 5. A 20 nm thick C 60 layer was deposited using a thermal evaporator.

A buffer layer, the purpose of which is to minimize sputter damage during the subsequent ITO

deposition was applied. An ITO layer was deposited using sputtering, and finally the device

was completed with a thermally evaporated Ag grid. Light I-V curves of the perovskite solar

cell were performed under simulated 1 sun illumination using a solar simulator (McScience,

K3000). Prior to each measurement, the solar simulator was calibrated with a Si reference cell

(PVM-580-BK7).

PEC measurements

A three-electrode configuration was used to carry out PEC measurements of CIGS

photocathodes. Pt coil and Ag/AgCl (3M KCl) were used as a counter and reference electrode,

respectively. CIGS photocathode was used as a working electrode. A Mo back-contact was

connected to Sn-Cu wire using Ag paste and the active area was defined by an epoxy sealing

(Hysol 9460). The working electrolyte was a 0.5 M potassium phosphate buffer (KPi)

containing 0.5 M K 2 SO 4, 0.5 M KH 2 PO 4, and 0.5 M K 2 HPO 4 with the addition of 1 M KOH

to achieve pH 6.8. A 250 mL quartz cell with a flattened front window was used as the PEC

bath to supply a fresh aqueous solution to the electrodes. The optical response of all PEC

measurements was measured using a 300 W Xe arc lamp (Oriel Instruments 66902) with an

electronic safety shutter (Newport 71445) and an AM 1.5G optical filter (Newport 81904)

which was calibrated to simulate 1 sun illumination of 100 mW/cm2 using a Si reference cell
(PVM-580-BK7) prior to each measurement. A BiStat (Bio-Logic) was used to measure linear

sweep voltammetry, open-circuit potential, chronoamperometry, and Tafel plots. The scan rate

of the above measurements was fixed at 20 mV/sec. A light chopping during

chronoamperometry measurements was performed at every 30 sec. A SP-150 potentiostat (Bio-

Logic) was used to measure electrochemical impedance spectroscopy (EIS), Mott-Schottky

plot, and capacitance-potential measurements. EIS was performed under 1 sun illumination at

a fixed potential of 0.3 V RHE with a frequency from 100 kHz to 0.2 Hz. At 0 V RHE , bubble

formation on CIGS photocathodes interfered with exact measurements. The built-in software

(EC-lab) was used to fit the obtained Nyquist plots. Mott-Schottky plot and capacitance-

potential measurements were carried out under dark conditions. The quantification of hydrogen

and oxygen gases was performed by a home-built in-line gas measurement system shown in

Figure S5. The gas tight H-cell was used to build a bias-free water photolysis setup and to

measure hydrogen and oxygen gases separately. A bipolar membrane (FuelCellStore) was

utilized to compensate for pH incompatibility between HER (0.5 M phosphate buffer) and OER

(1M KOH) cells. During gas measurements, Ar (CIGS half-cell) and He (Pt or Ir half-cell) was

used to purge the ambient air remaining in the H-cell. After the confirmation of complete

removal of nitrogen and oxygen gases through GC measurements, a constant potential of 0

V RHE under simulated 1 sun illumination was applied to the CIGS photocathode and counter

electrode to evolve hydrogen and oxygen gases, respectively. The produced gases were

analyzed by in-line gas chromatography (INFICON, Micro GC Fusion with a thermal

conductivity detector) every 3 min.

Chemical and structural characterization

Cs-corrected scanning transmission electron microscopy (STEM, FEI Titan G2 ChemiSTEM

Cs Probe) and energy dispersive X-ray spectroscopy (EDS) with four Si drift detectors were

used to investigate cross-sectional morphology and atomic distributions of CIGS

photocathodes, respectively. To visualize morphology and layer distribution, samples were

extracted from the CIGS through a focused ion beam (FEI Versa3D LoVac) using Ga primary

ions. X-ray photoelectron spectroscopy (XPS) measurements (Thermo VG Scientific Sigma

Probe) were conducted under a base pressure of 1x10-9 Torr. A monochromatic Al Kα (1486.6

eV) was used as the X-ray source and the pass energy for high-resolution scans was set to 40

eV. For high-resolution scans, the step size was 50 meV and counts were integrated up to 10

scans. Spectra were calibrated using an adventitious C 1s at 284.5 eV. A time-of-flight

secondary ion mass spectrometry (TOF-SIMS, ION-TOF GmbH) was used to obtain depth

profiles of the CIGS photocathodes. Cs+ ions with 0.25 keV was used to yield a raster size of

300 x 300 μm 2. Positive ions from the CIGS were detected through Bi3+ primary ions with 30

keV. Steady-state photoluminescence (PL, Horiba Jobin Yvon) measurements were taken

using a continuous 514 nm He-Ne laser source at an input power of 10 mW. Before measuring

the steady-state PL, the temperature of the cryostat was cooled down to 10K using liquid

helium. Time resolved PL (TRPL) measurements were performed using a compact NIR PL

lifetime spectrometer (Hamamatsu C12132) at room temperature. A 532 nm SHG Nd:YAG

laser was adjusted as an excitation source with a pulse width of less than 1.3 ns and a frequency

of 15 kHz.
Definition of solar-to-hydrogen conversion efficiency

Solar-to-hydrogen (STH) conversion efficiency is the most benchmarking efficiency in the

photoelectrochemical (PEC) water splitting. During the STH measurement, the PEC cell was

exposed to the full spectrum of an incident light with an intensity of 1 sun illumination and

zero applied bias. This means that the power to drive STH conversion between the working

and counter electrodes is only generated by an incident light without an applied bias. With this

condition, the STH efficiency can be expressed as shown below:

�𝐽𝐽𝑂𝑂𝑂𝑂 (𝑚𝑚𝑚𝑚 ⁄ 𝑐𝑐𝑐𝑐2 )�×(1.23 𝑉𝑉 )×𝜂𝜂𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹

𝑆𝑆𝑆𝑆𝑆𝑆 [%] = � � (1)
𝑃𝑃𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 (𝑚𝑚𝑚𝑚 ⁄ 𝑐𝑐𝑐𝑐2 ) 𝐴𝐴𝐴𝐴1.5𝐺𝐺

where J op is the operating current density flowing over the PEC cell in two-terminal

configuration at zero applied bias under 1 sun illumination, voltage (1.23 V) is the

thermodynamic potential to drive water splitting, η Faradaic is the Faradaic efficiency which

describes the ratio of the experimentally measured amount of evolved hydrogen and oxygen

and the theoretical amount of identical gas species, and the P total indicates the total power

density of the incident light.

Figure S1. Linear sweep voltammetry of CIGS/ZnS/CdS/rGO-Pt photocathodes with various
deposition times of CdS during chemical bath deposition (CBD). The arrow indicates the sweep
direction (from a positive to a negative potential). A 0.5M KPi buffer of pH 6.8 was used as
the working solution.
Figure S2. XPS core level spectra of Zn 2p taken from (a) bare CIGS, CIGS/ZnS, and
CIGS/ZnS/CdS and (b) CIGS/ZnS with an increasing immersion time in NH 4 OH solution. The
peak position of Zn 2p 3/2 (vertical dotted line) is about 1022.05 eV.
Figure S3. Time of flight-secondary ion mass spectrometry measurements of CIGS/ZnS (top)
and CIGS/ZnS/CdS (bottom) electrodes. The vertical dotted line in CIGS/ZnS/CdS represents
the CIGS/CdS interface.
Figure S4. (a) Apparent open-circuit potential (OCP) of bare CIGS, CIGS/ZnS (ZnS),
CIGS/CdS (CdS), and CIGS/ZnS/CdS (ZnS/CdS) photocathodes decorated with rGO-Pt under
dark and 1 sun conditions. The dark OCP should be zero but the bare CIGS was about 0.25
V RHE . To obtain exact OCP values in an aqueous solution, the surface of the CIGS
photocathode had to be saturated with hydrogen bubbles. One of the possible ways to generate
hydrogen bubbles is an application of constant bias such as 0 V RHE to the CIGS photocathode
(working electrode) under 1 sun illumination for several tens of sec. However, the bare CIGS
is not able to evolve hydrogen sufficiently on its surface regardless of the high applied bias,
thus resulting in an erroneous potential in the light and dark illumination. (b) Average OCP, as
determined by the difference between apparent OCPs under dark and 1 sun conditions of the
corresponding photocathodes.
Table S1. (a) Equivalent circuit model for the fitting of the Nyquist plots (Figure 2c) and (b)
the corresponding fitting results. R S: contact resistance associated with all contacts, R 1:
resistance of bulk electrode, R 2: charge transfer resistance for HER, CPE: contact phase
element, and α: CPE exponent.
Figure S5. Schematic illustration of a home-built in-line gas measurement system.
Figure S6. (a) External quantum efficiency of CIGS solar cell consisting of
Mo/CIGS/ZnS/CdS/ZnO/Al:ZnO/Ni-Al and (b) extraction of bandgap of the CIGS.
Figure S7. Band diagram of CIGS/CdS (left) and CIGS/ZnS/CdS (right) photocathodes for
hydrogen evolution. Additional surface band bending of the CIGS:ZnS should lead to higher
open-circuit potential as well as more efficient charge separation. A spike-offset shown in the
CIGS/CdS interface was determined by fs-laser ultraviolet photoelectron spectroscopy
measurements performed in our previous work.1 The spike-like barrier height of approximately
0.2-0.3 eV has been shown to suppress the interface charge recombination and not to hinder
charge transport across the CIGS/CdS interface.6,7 Illustration is not to scale.
Figure S8. (a) Schematic illustration of the device structure for a perovskite solar cell. (b)
Current-voltage characteristic of the corresponding perovskite solar cell.
Calculation of STH efficiency of unassisted PEC cell for series- and parallel-illumination

<Series-illumination>

- Operating current, I expected : 0.7 mA

- Total device area, A projected : 0.1 cm2

- Operating current density, J expected : 7.0 mA/cm2

- STH expected : 8.61 % (assuming 100 % Faradaic efficiency)

<Parallel-illumination>

- Operating current, I expected : 1.55 mA

- Total device area, A projected : 0.2 cm2

- Operating current density, J expected : 7.75 mA/cm2

- STH expected : 9.53 % (assuming 100 % Faradaic efficiency)

Table S2. Reported STH efficiency of a bias-free water splitting PEC cell including a CIGS
photocathode for the hydrogen evolution. “(Tested)” means the total duration of measurements,
not necessarily the lifetime of the devices.
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