Degradation and stability studies on perovskite

solar cells

A seminar report

Submitted in partial fulfilment of the requirements

of the degree of

Doctor of Philosophy

by

Abhishek Shubhrant
(Roll No. 164116005)

Supervisor:

Prof. Aswani Yella

Department of Metallurgical Engineering and Materials Science

INDIAN INSTITUTE OF TECHNOLOGY BOMBAY
(March 2017)

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 Contents
Pa g e
No.
Title page i

Contents ii

List of Tables iii

List of Figures iii

Chapter 1 Introduction
1.1 Introduction 1
Chapter 2 Degradation
2.1 Degradation 4
2.2 Oxygen induced degradation 5
2.3 Light induced degradation 7
2.4 Moisture induced degradation 8
2.5 Temperature induced degradation 9
2.6 Thermal & Electric field induced intrinsic degradation 11
Chapter 3 Stability
3.1 Moisture 12
3.2 Light 13
3.3 Temperature 15
Chapter 4 Conclusion
4 Conclusion 16
References 18

Acknowledgements 19

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 List of Tables

Table No. Description Page No.

Table 1 Device architecture and its stability for perovskite solar cells 10

List of Figures

Fig. No. Description Page No.

Figure 1.1 Crystal structure of an organic–inorganic metal halide perovskite 2

Figure 2.1 General electron-hole recombination process, moisture dissolution 5
process and photo-oxidation at the HTM-electrode interface
Figure 2.2 Oxygen induced formation of deep trap states and depletion area at 7
mesoporous TiO2 surface and interface
Figure 2.3 XRD patterns of films of TiO2/CH3NH3PbI3 before and after 9
degradation
Figure 3.1 Decomposition pathway of CH3NH3PbI3 in presence of the water 13
Figure 3.2 PCE (Normalised) degradation curves 14
Figure 4.1 Key directions for further studies on the stability 17

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 Chapter 1

Introduction

The day-by-day growing global energy demand coupled with depleting conventional non-
renewable fossil energy resources put a great threat to the environment, thus it challenges us
to explore on the alternative sources. Photovoltaics (PV) are one among the renewable
sources, the conversion of sunlight into electricity, which seems promising in this regard. The
current usage is dominated by Si-based solar cells. Although its cost has been reduced by
recent advancement but still it is constrained by high investments, one being requirement of
high temperature processing. In an alternative approach towards cheaper solar technology
could be achieved by substituting the crystalline Si with organic semiconductors. The use of
solution processing techniques in its fabrication significantly reduces the cost. In
approximately last 2 decades, the power conversion efficiency of upto 12% have been
achieved for such solar cells [1]. But still much advancement is desired in this area to make it
commercially viable.

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A new class of organic-inorganic metal halide perovskite semiconductors seems promising to
counter the issues and turn the dream into reality. The term "perovskites" refers to a group of
compounds represented by the general formula ABX3, which have the crystalline structure of
calcium titanium oxide (CaTiO3). Fig. 1 displays a structure of the ABX3 perovskite crystal
structure for a hybrid organic-inorganic metal halide perovskite.

Fig. 1.1 Crystal structure of an

organic–inorganic metal halide
perovskite

The A position contains an organic cation, B is a metal cation, and X is a halide anion. The
most usually investigated organic-inorganic metal halide perovskite, hereafter; perovskite is
CH3NH3PbI3 which acts as the absorber layer in the solar cell. The perovskite layer can be
prepared utilizing minimal-cost coating and printing methods.

Organometal-halide perovskite solar cells evolution has demonstration a commendable

growth rate in efficiency and stability. The conversion efficiency of perovskite solar cells has
come up in an exponential manner, with efficiencies over 20%. The main obstruction towards
its practical application is the unsatisfactory stability, but nowadays it is going in thousands of
hours. All these advancements have been brought by the use of different materials, interfaces
and optimization of device architecture, which propels us towards more robust, cheap and
easy manufacturing methods. Moreover, there are various other problems pertaining to such
degradations of different elements of the device and also device as a whole, which must be
countered to achieve repeatability and enhanced PCE as well as lifetime of these devices. This

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report discusses the main reasons behind failure, device degradation mechanisms and the
approach towards improvement in stability. However, instability is the major problem arises
with the perovskite layer when it comes in contact with moisture. Moreover it is also to be
explored about stability problems associated with the other elements of the device. [10, 11]

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 Chapter 2

Degradation

2.1 Degradation

Due to various problems, perovskite materials are yet to be utilized up to its potential. Like
unclear understanding device & active layer degradation mechanism which may help us to
understand and improve upon its life time and the stability of perovskite solar cell panels.
Hence, in general, it is really important to understand the degradation behavior to advance an
edge in the successful development of devices. Therefore, it is a pre-requisite to study the
degradation mechanisms for perovskite solar cell applications. These degradations may in
general be linked to extrinsically induced like oxygen-induced, light-induced, moisture-
induced and temperature-induced or intrinsically induced like thermal and electric field
induced degradations. The general recombination process is shown in Fig. 2, moisture

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dissolution of the perovskite and the photo-oxidation is observed at the HTM-electrode
interface.

In presence of TiO2, UV light speeds up the oxygen diffusion. This releases free radicals of
oxygen which reacts with the HTM or perovskite material. Also, the pinholes present in the
electrodes may allow the oxygen molecules/moisture to pass through them as shown in Fig. 2.
Perovskite materials like CH33NH3PbI3 and CH33NH3PbBr3 are susceptible to chemical
attack, hence they may degrade in the matter of hours when kept under 1 kW/m2 illumination
in the open atmosphere. The phenomena of extrinsic and intrinsic degradation and its
mechanisms in the perovskite materials and perovskite based devices are described in this
section. Moreover the various factors which influences the stability.

Fig. 2.1 General electron-hole

recombination process, moisture
dissolution process and photo-
oxidation at the HTM-electrode
interface. [2]

2.2 Oxygen induced degradation

An important operational requirement of any device is that it should be satisfactorily stable

without any encapsulant. The method of reasoning behind this is each gathering of materials
in a device that acknowledges surrounding soundness will deliver a contribution to future
change. Yang and colleagues thought about device put away in the dry air and in nitrogen

5
environment & demonstrated that degradation of the perovskite materials happened in
encompassing air – consequently, highlighting the requirement for protection. The diffusion
of atomic oxygen can be enacted by UV light in the presence of organic molecules, which
advance the formation of peroxide or superoxide compounds that target and degrade the active
layers.

In Perovskite Solar cell, the development of a Ti(III) (3d1) trap state is because of the
exchange of an electron with the Ti(IV) (3d0) of TiO2 from the perovskite. In this manner, the
electron effectively moves into Ti(IV) from Ti(III) as a result of the thinner band-gap amongst
Ti(III) & Ti(IV). Those under-coordinated Ti(III) produced because of vacancies for oxygen
dwell in sub-band gap states and act as profound trap destinations. Besides, they pull in the
oxygen molecule in atmospheric conditions, bringing about the development of α
(Ti(IV)+O2(adsorbed)). Similarly, electrons in sub-band gap states may form β
(Ti(IV)+O2(adsorbed)). These adjusted states don't meddle with the device's execution when
irradiated. The development of the depletion layer can be therefore because of the positive
potential at the TiO2 surface, brought on by the presence of O2.

The life of the device shortens when it is ceaselessly illuminated at high temperatures.
Conversion of the a super-oxide complex to a Ti(III) and freeing O2 may occur when photo
excitation of the mesoporous TiO2 brings about the arrangement of electron–hole sets,
through which openings in the VB are caught with O2 in the Ti(IV)+O2, as represented in Fig.
2.2(b). The generated free electron in the conduction band (CB) is then caught at the
recovering profound trap site and will at last recombine with an abundance gap in the spiro-
MeOTAD, as shown in Fig. 2.2(c). An adsorbed negative charge may bring about an
expansion in the depletion region, in this manner making an upward shift in the CB that
reduces interfacial charge transporter recombination. Moreover, O2 desorption upon light
decreases this upward band twisting and subsequently brings about the vanishing of the
Schottky boundary, a straightening of the CB-edge and a bringing down of the Fermi level, as
appeared in Fig. 2.2(d). Oxygen initiated defects in TiO2 are the significant reasons that
contributes to device’s degradation amid operation.

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Fig. 2.2 Oxygen induced formation of deep trap states and depletion area at mesoporous TiO2 surface
and interface: (a)–(c) the patterning of superoxide, alpha and beta(Ti(IV)+–O2) d) Desorption of
negatively charged superoxide molecules and their impact on the depth of the depletion zone

2.3 Light induced degradation

UV irradiation can decrease the output of perovskite solar cells on its exposure amid long haul
operation because of the numerous degradation processes. Electron recombination therefore
makes restricted trapping destinations and reduces the depletion layer and TiO2 band
excitation. This may oxidize the halogen atoms in the perovskite or HTM degradation,
because of UV light. Obviously, it ought to be perceived that there are different causes of
degradation other than UV light, e.g. oxidation-induced, heat and visible light. UV light is as a
rule the real reason for degradation and consequently is of major importance, which means it
is important to utilize robust and extensively retaining UV materials keeping in mind the end
goal to secure absorbing layer as well as the substrate by either starting a disintegration that
returns by other mechanism, for example, oxidation, or by straightforwardly absorbing UV
light.

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UV-invoked degradation mechanisms can be elaborated by considering the surface science of
TiO2. Mesoporous TiO2 consolidates imperfections (Ti3+) or trap sites working as productive
profound electron-discharging states; the electrons confined in these trapping states, tie with
O2 particles from the atmosphere, adsorbing the trapping sites, and creating a O2–Ti4+
complex. Thus, the adsorption procedure is the cause of the photocurrent degradation comes
up due to adsorbed oxygen on the surfaces TiO2. On bandgap excitation of TiO2, at the site of
adsorbed oxygen where recombination of hole from VB takes place. Therefore, this desorbs
the oxygen makes an electron–hole pair. The unbounded electrons are rebound due to
abundant holes present in the HTM. The trapped electrons recombine with the holes present in
spiro-MeOTAD. The oxygen’s’ partial pressure in the steady state inside profound trap
locales oversees the amount of unfilled oxygen vacant sites. These results from the slow and
reversible rates of oxygen’s desorption. In perovskite solar cells, the inorganic Pb2+–X makes
a very much ordered inorganic arrangement which effectively retains and re-emanates light. In
this way, UV illumination of the atmospheric condition of the Pb–X security could create free
radicals of halogen and disintegrate into dihalogens (I2, Br2, and Cl2) from the perovskite.
Consequently, oxidation induced halogen end might be one conceivable explanation behind
degradation of perovskite solar cell. In this manner, the exposure of MAPbI3 with light
prompts an irreversible breakdown into PbI2.

2.4 Moisture induced degradation

Moisure induced degrdation of perovskite layer might be associated with the change to the
MAI salt and metal halides from MAPbI3, and henceforth expulsion of halides of these metals
may likewise bring about perovskite cell degradation. Wang et al[3] announced that amid the
way toward assembling and testing, moist air can straightforwardly degrade these materials,
as demonstrated by the behaviour of films of TiO2/CH3NH3PbI3 via XRD pattern in Fig. 2.3.
The reversible deprotonation of the MA cation by water, formation of methylamine, hydrated
HI, and PbI2 has been suggested as the initial step in perovskite decomposition. In the event
that this speculation is right, one would expect that the volatile CH3NH2 would be quickly
taken out of the in situ job holder, implying that the procedure would be probably not going to
be reversible. The obvious reversibility in the thin films & bulk powder would likewise show

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a comparative reversible transformation to the hydrate stage. Moreover, the CH3NH3PbI3
when exposed to moisture leads to a hydrate formation as opposed to just PbI2.

Fig. 2.3 XRD patterns of films of TiO2/CH3NH3PbI3 before and after degradation

2.5 Temperature induced degradation

Raising the temperature of annealing, to 100 0C from 40 0C held for 30 min, enhanced the
output of a perovskite QD sensitized TiO2 film. But, a bit increment in toughening
temperature from 1000C to 160 0C reduced the efficiency from 4.73% to 3.71%, due
essentially to the rot in the density of photocurrent. External quantum effectiveness (EQE)
spectra demonstrated the diminished photocurrent density when treated at high temperature
(160 0C) is ascribed to a noteworthy decrease in EQE with larger wavelength (over 500 nm).
Hence, the temperatures of annealing as well as the temperature of storgae are critical
parameters that may bring about perovskite device degrdation, as can be seen from Table 2. In
spite of the fact that there is no writing report, plainly perovskite devices need to clear tests,
for example, thermal stress tests at 80 0C for 1000 h, for its useful application. Clearly the
working temperature will increment to considerably larger than 80 0C and heating the film

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amid operation because of nonstop illumination from a Solar simulator system (e.g., 0.1
W/cm2 sun-light). Moreover, moisture and oxygen induced degradation, these perovskite solar
cells face thermal degradation. This reality will, thusly, prompt extra essential issues over the
span of perovskite processes of degradation. This degradation may form PbI2 and organic salt
structures. The thermal stability of CH3NH3PbI3 was affirmed to be considerably higher than
300 0C. In any case, most recent literary works affirmed that the natural deterioration
temperatures could be brought down to 140 0C. The temperature induced disintegration of
methylammonium iodide may produce of HI and CH3NH2. CH3NH2 could remain inside the
system of the perovskite, and afterward alter the photovoltaic procedures. Besides, the
nearness of metal halides, for instance is also an issue, PbI2, as the product of perovskite
degradation. Because of its low optical conduct and low light absorption capacity and in
addition their higher bandgap, lead halides cause device decay. Furthermore, the mechanism
of compression & expansion in the dimensional differences of the perovskite structure at low
and high temperatures is not yet to be figured out. Besides, elevated temperatures can bring
about the interlayer diffusion, dispersion of the counter metal anode, degradation of ohmic
contact and device design degradation. Consequently, new perovskites which have improved
inherent resistance towards temperature are better possibility for future improvement in fields
of perovskite PV innovations. For example, FAPbI3 is more temperature safe than MAPbI3.

Table 1: Device architecture and its stability for perovskite solar cells

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2.6 Thermal and electric field induced intrinsic degradation

The interface is the primary cause of degradation in perovskite solar cells. The subject of how
the interface can induce degradation is identified with the intrinsic deprivation of perovskite
solar cells. The origination of this degradation is: (1) the temperature invoked stream of
components because of thermal evaporation amid deposition and light illumination amid
operations. This thermal incited movement of component materials at the interface brings
about between dispersion, phase segregation and partition, showing an intrinsic strain. (2)
Electric field invoked ion relocation which leads to electro-movement and hysteretic impacts.
The current carrying conductor may displace metal ions in the electro-movement process.
Electro-migration forces the anions towards the anode and develops a compressive stress. The
concentration of vacancies in the anode turns out to be not as much as the equilibrium
vacancy focus as indicated by the Nabarro Herring model of point-imperfection development
in a focused on solid.[4] In the hysteresis procedure, particle movement is very sensitive to
the mobile vacancy concentration contingent upon the mechanism. Hence, the measure of
crystalline regions, level of crystallinity and stoichiometry can influence the transient conduct
of perovskite devices.[5] This transient conduct is not quite the same as device to device. For
example, the bigger transient contrast amongst mesoporous and planar device is most
presumably because of varieties in the composition stoichiometry or morphology. Hence,
limiting migration of ions is fundamental in broadening the stability of devices.

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 Chapter 3

Stability

The responsible chemical processes of perovskite film degradation were astoundingly checked
on by Niu et al. [6]. They recognised few key variables bringing in the perovskite film
degradation: oxygen-induced and moisture-induced, UV light-induced & thermal effects.

3.1 Moisture

The probable process of CH3NH3PbI3 decomposition was shown schematically by Frost et al.
[7]. Refer Fig. 3.1. This demonstrates MA & HI are water soluble. The irreversible perovskite
layer degradation is an issue concerning the life of the PV cells; be that as it may, the issue is
intensified by the by-products. As showed in Fig. 2, a by-product of this reaction is PbI2, a

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water soluble product. The dissociation of PbI2 could bring about huge eco-toxicological
issues.

Fig. 3.1. CH3NH3PbI3 - decomposition flow process in presence of the water molecule.

Primarily it prescribes that PV output could be re-established utilizing dehydration techniques

[8]. Conversely, excess water interaction results in an irreversible change into PbI2. These
outcomes help illustrate the perovskite film’s central decomposition flow process, which
results into more robust materials as well as economically practical modules. It’s along these
lines, essential to make sense of the kinetic & thermodynamic benefits of the mechanisms of
degradation. Additionally, the science of moisture-induced degradation further requires point
by point computation and tests which confirms in request to support and elaborate over
degradation mechanisms which arises due to moist environment.

3.2 Light

With various other solar powered cell innovations, UV light illumination can make perovskite
solar cells degrade. Supporting earlier reported works of high proficiency devices was the

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arrangement of TiO2 transport layer of electron. Leijtens et al. demonstrated for perovskite
devices, the TiO2 layer is vulnerable to degradation by UV light. It was obtained by plotting
efficiency decay curve, for 5h under 1 sun for Air Mass 1.5 illuminated for encapsulated or
non-encapsulated cells and a filter for UV light. The outcomes demonstrated something
unnatural, the degradation of encapsulated device was quicker than the unencapsulated ones.
These PCE (normalised) estimations are shown in Fig. 3.2

Fig. 3.2 PCE (Normalised) degradation curves of TiO2 containing perovskite solar cells

The experiments by Ito et al. show the utilization of Sb2S3 as blocking layer to diminish Ultra-
Violet light initiated degradation. This procedure, already been implemented on inorganic
solar cells, included forming a Sb2S3 layer at the interface of TiO2/CH3NH3PbI3. This layers’
incorporation enhanced stability. For devices in air without encapsulation, the efficiency
decreased to very near to 0% within 12 h. Conversely, the device with the Sb2S3 layer
measured an efficiency of 65% of its underlying efficiency after being exposed to similar
conditions.

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3.3 Temperature

When exposed to a high temperature, perovskite degradation takes place. As the layer of
perovskite needs the annealing step, at last, during operation it encounters extremely high
temperature. Phillippe et al. explored the impact on both CH3NH3PbI3 and CH3NH3PbI3-xClx
films of high temperatures. The author, instead of XRD, utilized hard X-beam photoelectron
spectroscopy (PES, to explain film decomposition, as it considers for chemical content paying
little attention to the film’s crystallinity. During investigation, in an ultra-high vacuum
chamber heating of films was performed. Evacuating air & water is permitted in order to
explore independent impact of temperature on the film degradation.

While this basic investigation obviously shows that under high on mercury scale perovskite
materials are unstable, no air and water may impact the reaction’s rate. Heat treating the ZnO,
before perovskite deposition, enhanced the thermal robustness. The authors suggest that ZnO
film heat treatment expels surface hydroxyl groups who were responsible for quickened the
temperature assisted decomposition. In spite of the fact that this apparently enhances the
stability, a huge decrease in devices’ performance happened when heat treatment of ZnO film
was performed at higher temperatures.

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 Chapter 4

Conclusion

For perovskite cells to accomplish the long-lasting stability, upcoming research must
concentrate on enhancing the characteristic stability of the absorber layer of the perovskite
solar cells, cautious designing of the device, and searching long lasting encapsulants, which
can isolate the device in a moist environment.

Perovskite materials can possibly disturb the present Photovoltaics market. The steep rise in
the effectiveness of the device is empowering, as there are numerous roads for perovskite
solar cells via it could enhance the present innovations, regarding streamlining the
cost/execution. These solar cells are perfect with cost and effective processing outshined by
the OPV people group [9]; but anyhow the efficiencies are far better than polymer ones. On
the other hand, the absorber made of perovskite material could be combined with Si solar
cells, to frame high productivity couple cells. This promising material is along these lines

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intriguing to an extensive variety of present Photovoltaics groups. One key hindrance to
moving toward the commercialisation of these devices is the stability.

Fig. 4.1 Key directions for further studies on the stability

To summarize among the most critical issues related to the stability of perovskite solar cell is
introduced in Fig. 4.1. The assessment of the literature uncovers that the essential sympathy
toward Organometal-halide perovskites is the moisture induced intrinsic instability. The
prototypical, CH3NH3PbI3, quickly dissociates within the sight of moisture. Numerous
endeavours have been made to discover elective, highly stable forms of these materials by
altering components in the ABX3 structure.. Different stress variables, incorporating UV light
illumination and thermal dissociation, additionally assume a part; these components to a great
extent impact other layers of the cell.

Future advancement must consider two ways to deal with enhanced soundness i) appropriate
encapsulant and ii) enhanced characteristic perovskite film’s stability against moisture.
Encapsulation will take into account cells to achieve the longer life, explored under monitored
conditions of atmosphere, while enhanced perovskite stability will quicken the innovation to
the objective of commercialisation.

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 References
[1] 〈http://www.heliatek.com/〉
[2] Organometal halide perovskite solar cells: degradation and stability, Berhe et al, Energy Environ.
Sci., 2016,9, 323-356

[3] G. Niu, W. Li, F. Meng, L. Wang, H. Dong and Y. Qiu, J. Mater. Chem. A, 2014, 2, 705–710.
[4] C. Herring, J. Appl. Phys., 1950, 21, 437–445
[5] E. L. Unger, E. T. Hoke, C. D. Bailie, W. H. Nguyen, A. R. Bowring, T. Heumuller, M. G.
Christoforo and M. D. McGehee, Energy Environ. Sci., 2014, 7, 3690–3698.
[6] G. Niu, X. Guo, L. Wang, Review of recent progress in chemical stability of perovskite solar cells,
J. Mater. Chem. A 3 (2015) 8970–8980
[7] J.M. Frost, K.T. Butler, F. Brivio, C.H. Hendon, M. van Schilfgaarde, A. Walsh, Atomistic origins
of high-performance in hybrid halide perovskite solar cells, Nano Lett. 14 (2014) 2584–2590
[8] A. Mei, X. Li, L. Liu, Z. Ku, T. Liu, Y. Rong, M. Xu, M. Hu, J. Chen, Y. Yang, M. Grätzel, H.
Han, A hole-conductor–free, fully printable mesoscopic perovskite solar cell with high stability,
Science 345 (2014) 295–298.
[9] T.M. Schmidt, T.T. Larsen-Olsen, J.E. Carlé, D. Angmo, F.C. Krebs, Upscaling of Perovskite
Solar Cells: Fully Ambient Roll Processing of Flexible Perovskite Solar Cells with Printed Back
Electrodes, Adv. Energy Mater. 5 (2015) 1500569
[10] Stability of perovskite solar cells, Dian Wang et al., Solar Energy Materials & Solar Cells 147
(2016) 255–275
[11] Organometal Halide Perovskite Solar Cells: Degradation and Stability, Article in Energy &
Environmental Science · November 2015

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 Acknowledgements

I would like to express my sincere gratitude to Prof. Aswani Yella, Department of

Metallurgical Engineering and Materials Science, IIT Bombay, for introducing the
seminar topic and for her inspiring guidance, valuable suggestions and constructive criticism
throughout this seminar work.
I am very much thankful to Prof. Arup Bhattacharyya, Department of Metallurgical
Engineering and Materials Science, IIT Bombay, for his kind cooperation and constant
encouragement to execute this seminar course.

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