Small band-gap nanostructured perovskite

materials for photovoltaic and photocatalytic

hydrogen generation applications
IZERZ0_142176: from 1.1.2013 until 30.4.2016

Thomas Lippert
Paul Scherrer Institut, Materials Group, Switzerland

Maria Dinescu
National Institute for Lasers, Plasma and Radiation Physics, Photonic
Processing of Advanced Materials Group, Romania

PROIECT CO-FINANȚAT PRINTR-UN GRANT DIN PARTEA ELVEȚIEI PRIN INTERMEDIUL CONTRIBUȚIEI ELVEȚIENE
PENTRU UNIUNEA EUROPEANĂ EXTINSĂ

www.institution.ro
 The Teams

Markus Pichler, Daniele Pergolesi, XX

the PhD student who The direct supervisor
did most of the work of Markus

Ruxandra Birjega, Marius Dumitru, Nicu Doinel Maria Dinescu,

researcher PhD student Scarisoreanu, Romanian team
researcher leader

www.institution.ro 2
 The Project-Aim
The aim of this project was to explore the potential of
combined photovoltaic and photocatalytic properties of
perovskite-based materials which exhibit a small band
gap. For these 2 different properties 2 different
material classes have been selected:

Photocatalytic oxynitrides, such Ferroelectric materials, such as

as LaTiO2N, that can be used for BiFeO3 (BFO), which exhibit a
water splitting using visible light. photovoltaic effect.
The ferroelectric materials are also
exhibiting a photocatalytic properties.

www.institution.ro 3
 The Project-Approach
Each group will prepare one of the material classes in
the form of thin films using the same deposition
technique, i.e. pulsed laser deposition. The thin films
are then characterized by standard methods, such as
XRD, in each group, while techniques, which are only
available in one group will be used also for the
samples of the other group.
Deposition of oxynitrides, characterization by Rutherford
backscattering (RBS) and ERDA (elastic recoil detection analysis).
Building a setup for photocatalytic or photoelectrocatalytic
characterization. Samples from both groups.

Deposition of ferroelectric materials, based on BiFeO3 and cation

doped BiFeO3, photovoltaic characterization and characterization by
spectroscopic ellipsometry and AFM. Additionally, new oxynitride
materials, such as YGeO2N, which have been predicted to show
photovoltaic and photocatalytic properties.
www.institution.ro 4
 Cooperation between the teams: the schematics
Emerging idea: new
materials or new material’s
functionalities for sustainable
energy harvesting
INFLPR, PPAM Group expertise: PSI, Materials Group expertise:
- laser and plasma processing of materials. - Pulsed Reactive Crossed-Beam Laser Ablation
- Radiofrequency assisted Pulsed Laser (PRCLA) for oxynitrides and nitrides
Deposition of thin films - Pulsed Laser Deposition of thin films for
- properties characterization of thin films: optical, electrochemistry applications.
electrical, structural, stoichiometry. - photoelectrochemical characterization of thin
films water-splitting efficiency

New project: Small band-gap nanostructured perovskite materials

for photovoltaic and photocatalytic hydrogen generation applications

- LaTiO3-xNx samples delivery for optical

characterization made at INFLPR
INFLPR, PPAM Group tasks in the project: PSI, Materials Group tasks in the project:
- LaTiO3-xNx samples delivery for
- Cation doped BiFeO3, oxynitride YGeON - LaTiO3-xNx deposited with various N-
- dielectric measurements performed at
thin films for enhanced functional content and test of photocatalytic
INFLPR
properties (photovoltaic and photocatalytic). photovoltaic activity.
- Tailoring the BFO thin films properties - Evaluation of the photoelectrochemical
and integration in heterostructures for (water splitting) properties of the thin
- BiFeO3, YSiON samples delivery for films
photovoltaic and photocatalytic evaluation.
ERDA measurements performed at PSI
- Y-doped BiFeO3 samples delivery for
PEC measurements performed at PSI

- Previous scientific collaborations between PSI, Materials Group and INFLPR, PPAM Group: NATO SfP and EC FP7.

www.institution.ro 5
 Oxynitrides for Photo(electro)catalysis
For solar driven water splitting:
• Photocatalysis: particulate samples-with co-catalysator.
• Photoelectrochemical (PEC), with electrodes (and co-catalysator).
• Photovoltaic (PV), solar cell + electrocatalyst.

O2 evolution is the rate determining step during water

splitting since it needs more charge carriers and has
slower kinectic compared to H2 evolution ➜ Photoanode:
n-semiconductor: minority holes to the surface.

www.institution.ro 6
 Oxynitrides for Photo(electro)catalysis
• Most common photocatalyst-TiO2: a band gap of 3.2 eV,
only excited by UV light (3% of solar light), while visible light
accounts for 44% ➜ visible-light responsive catalysts are
needed.
• Requirements for photoelectrodes:
1. Bandgap in the visible light range.
2. Band edges straddling O2 and H2 evolution potentials.
3. Reasonable chemical and structural stability.
4. Appropriate surface reaction kinetics.
5. High charge separation and mobility to avoid recombination.

• Oxynitride materials:
• Tunable band gap in visible range due to N substitution
of O.
• Several unknown or very few studied promising
candidates.

www.institution.ro 7
 Oxynitrides Thin Films for
Photo(electro)catalysis
• Goals:
1. High quality crystals as model systems,
2. With well defined surfaces and low defect number.
3. Control over the crystallographic orientation.
4. Compare to modeling.
• Why the thin film approach
• “In any case, there are certainly some problems in the photocatalytic
matrix. We are at the cusp not only of finding nitridation or post-
treatment conditions which fulfill all the requirements (i.e., to reduce
the defect density, enhance the crystallinity, and inhibit
decomposition, at the same time), but also to target more
aggressively a direct preparation method to obtain high-quality
crystals of (oxy)nitrides”
Y. Moriya, T. Takata, K. Domen, Coordination Chemistry Reviews 257, 19557 (2013)

www.institution.ro 8
 Main Results: Oxynitrides

Shift of band gap: visible Photocurrent is observed:

light will be absorbed active for photoelectrocatalysis

www.institution.ro 9
 Main Results: Oxynitrides-Influence of
Crystallographic Orientation

www.institution.ro 10
 Cation doped BiFeO3 thin films with enhanced functional
properties (photovoltaic and photocatalytic).

BiFeO3 – brief presentation

-rhombohedrally distorted ferroelectric perovskite, R3c
-antiferromagnetic Néel temperature of TN=643° K
-ferroelectric Curie temperature of TC=1103° K.
- the R3c symmetry permits the development of spontaneous polarization
(Ps) along the pseudocubic [111] direction.
-high remnant polarization in thin films form: 90 μ C/cm2

P-E hysteresis loops obtained from BiFeO3 /SrRuO3/SrTiO3

thin films
-bulk BFO crystal structure High photoinduced voltage- over 5-times the band gap of BFO
after: J. B. Neaton et al., Physical Review B Vol. 71, 014113
(2005). after: Axel Lubk, S. Gemming, and after S.Y.Yang et al, Nature Nanotechnology, 5, 2010
N. A. Spaldin, Phys. Rev. B Vol. 80,
104110 (2009).

www.institution.ro 11
 Cation doped BiFeO3 thin films with enhanced functional
properties (photovoltaic and photocatalytic).

- The goal of cation (Y or La) doping of BFO is to obtain enhanced photovoltaic and photocatalytic (water splitting) behavior by
decreasing the BFO band gap and to study the effect of the induced structural and chemical strain on these functional properties.
- The Y and La-doped BFO thin films have been deposited by PLD.

Samples Structural parameters

a (nm) D (nm) ε (x10-3)

BFO(1456) 0.40577 65 89

BYFO(1443) 0.40456 28 261

BLFO(1450) 0.40221 86 280

3.8 0.8

3.6 0.7 1454 BFO /ST O ;

1454 BF O/ST O ;
1444 BYFO //ST O ;
3.4 1444 BYFO //ST O ;
0.6 1450 BLFO /ST O ;
1450 BL FO /ST O ;
XRD patterns of BFO, BYFO and BLFO thin films

E xctin ction co e fficie n t

3.2
0.5
refractive inde x

* 1454 Eg~ 2.35 eV

3.0
0.4 * 1444 Eg~ 2.05 eV
2.8 * 1450 Eg~ 1.91 eV
0.3 1/2
T auc plot ( E) = f(E)
2.6
0.2
2.4

- The dopant structural effects are significant, especially at the 2.2

0.1

induced ε micro-strain levels.

0.0
2.0
-0.1
- The ellipsometry measurements evidenced that the band 400 500 600 700

(nm )
800 900 1000 400 500 600 700

 (nm )
800 900 1000

gap values for the cation doped BFO/STO thin films is

smaller than for the BFO/STO sample The optical behavior of cation doped
and pure BFO thin films and the calculated band gap values

www.institution.ro 12
 Main results: Y doped BiFeO3 thin films with enhanced
functional properties- dielectric.

- Y doped BiFeO3 thin films have been obtained by PLD, different level of doping being used.
- We have studied the joined role of chemical pressure (Y-doping) and epitaxial strain (induced by the substrate) on the Y-BFO
thin films structural, electrical and photoelectrochemical properties

a) Comparison between -2 diffraction patterns of the Y-BFO and BFO films;
b) Comparison between Φ-scans for the same samples;
c) Full width at half maximum (FWHM) values of the rocking curve of the (002) diffraction
peaks for Y-BFO and BFO films.

-the appearance of nanoscale stripe structure into Y-BFO thin

films has been observed- HR-TEM figure a, b.
- this peculiar nanoscale structure creates conditions for easy
reorientation of polarization and high dielectric response. Comparative HRTEM, FFT and stress/strain GPA maps and line profiles of
the Y-BFO ((a), (c), (e)) and BFO ((b), (d), (f)) films far from the interface.

www.institution.ro 13
 Main results: Y doped BiFeO3 thin films with enhanced
functional properties- dielectric.

- Huge improvements on the dielectric response (losses and dielectric constant values) has been obtained for Y-BFO thin
films
- The switching behavior has been evaluated by Piezoelectric Force Microscopy (PFM) technique.

www.institution.ro 14
 Main results: Y doped BiFeO3 thin films with enhanced
functional properties- photoelectrochemical
(hydrogen generation by water splitting)

- Huge improvement of the Incident Photon-to-Current Eciency (IPCE) for the Y-doped samples.

Potentiodynamic PEC measurement of undoped BFO sample (left) and Y-doped BFO sample (right)

www.institution.ro 15
 The Cooperation-Examples
Planned cooperation:
• Photoelectrochemical (PEC) measurements of the BiFeO3
(BFO) and doped BFO films produced in Romania. An
example of the results is shown on the next slide (VERY
PROMISING).
Not planned:
• During the project the following question came up for our
oxynitride films: do they have a direct or indirect bandgap?
Approach: spectroscopic ellipsometry in Romania-strong
indication for indirect bandgap. For final confirmation
experiments at the synchrotron are planned (SE was
instrumental to get beam time).
Planned cooperation:
• Deposition of various BFO and doped BFO films on
conducting substrates (required for PEC).
• Deposition of new materials
Not planned:
• Spectroscopic ellipsometry measurements on
LaTiOxNy films.
www.institution.ro 16
 The Cooperation-Examples
Photoelectrochemical measurements performed at PSI on the BFO and Y-BFO samples provided by INFLPR

Potentiodynamic PEC measurement of undoped BFO sample (left) and Y-doped BFO sample (right)

www.institution.ro 17
 Visits and Exchange of Knowledge

VISITS:
- Maria Dinescu at PSI- 27.02.2013- 01.03.2013
- Maria Dinescu at PSI - 23.10.2014- 26.10.2014
- Maria Dinescu at PSI- 26.01.2014- 29.01.2014

- Thomas Lippert at INFLPR- 25.09.2013- 28.09.2013

- Thomas Lippert at INFLPR- 25.03.2014- 29.03.2014
- Thomas Lippert at INFLPR- 18.02.2015- 21.02.2015

What can we list for exchange of knowledge? SE, long discussion about film
deposition….to meet challenges…

VISITS special: one scientist from the Romanian group works now on a CTI project in
Switzerland

Another scientist form the Romanian group was as SCIEX fellow in CH group

VERY SUCCESSFUL projects and exchange beyond the project.

www.institution.ro 18
 Visits and Exchange of Knowledge

www.institution.ro 19
 Challenges Met

- One of the major challenge was to integrate the used materials as thin films into a functional,
measurable heterostructure for evaluating the photocatalytic or photovoltaic properties. In this point of
view, the following problems have been issued and solved:

• the problem of the bottom electrode for photoelectrochemical (PEC) characterization:

- must be an electronic conducting buffer layer to collect the photo-induced charge carriers.
- must have the required lattice matching and thermal expansion coefficient to promote an
ordered growth of the oxynitride or oxide layer.
- must be chemically stable at high temperature in strongly reducing environment (the
oxynitride films are deposited at about 800°C in N and ammonia containing atmosphere)

• the problem of the top electrode for photovoltaic and dielectric evaluation:
- must be an transparent and electronic conducting buffer layer to collect the photo-induced
charge carriers.
- the deposition temperature of the top electrode must be as low as possible not to damage
the structure of the active thin layer.

www.institution.ro 20
 Challenges Met
- Used bottom electrodes for BFO and Y-BFO thin films deposition: comparison between SrRuO3/SrTiO3, Nb:SrTiO3

- similar highly (00l) oriented BFO layers can be noticed

in both cases with no trace of other misoriented
peaks.
- due to the smaller lattice mismatch between the film
and substrate for the BFO/SRO/STO as compared
with BFO/Nb:STO (or STO), the micro-strain values
are higher for the latest.

However…
XRD patterns of BFO/STO and BFO/SRO/STO thin films

Y-BFO/ Nb:STO- Successful PEC measurement

and high photocurrent value.

Y-BFO/ SRO/STO- NOT so successful result!

www.institution.ro 21
 Lessons Learnt
- The recommended use of certain bottom electrodes for PEC measurements:
Nb:STO in the case of Y-BFO thin films which are able to sustain the PEC set-up
enviroment

What could we write here?

www.institution.ro 22
 Follow up?

- The work on the oxynitrides and oxides with perovskitic structure will go on in the frame of
future calls.
- Strain engineering and doping of different perovskites would be the trend to follow in the
case of oxides.
- The promising PEC results for doped BFO thin films led to the conclusion that the work on
tuning the functional properties of this material is an attractive perspective.

Something along the lines, that the cooperation is now established

and that the corresponding setup have been built a first very
promising data, e.g. for doped BFO in PEC have been obtained….

more

measurements are needed

So a clear YES
We will try to continue in one or another form.

www.institution.ro 23