Proceedings of the Nature Research Society

doi: 10.11605/j.pnrs.201802004
Review View Online

A Review on Tailoring PEDOT:PSS Layer for

Improved Performance of Perovskite Solar Cells
Khan Mamun Reza, Sally Mabrouk, Qiquan Qiao*
Department of Electrical Engineering, Center for Advanced Photovoltaics, South Dakota State University, Brookings, South Dakota 57007, United States
*Corresponding Author. Email: Qiquan.Qiao@sdstate.edu
Received: 15 March 2018, Accepted: 29 March 2018, Published Online: 30 March 2018
Citation Information: Khan Mamun Reza, Sally Mabrouk, Qiquan Qiao, Proceedings of the Nature Research Society, 2, 02004 (2018). doi: 10.11605/
j.pnrs.201802004

Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is the most com-

monly used hole transport layer (HTL) in inverted (p-i-n) structured perovskite solar cells
(PSCs) due to remarkable transparency and conductivity. Despite high transparency and
conductivity, PEDOT:PSS has some concealed problems such as acidity, hygroscopic  nature,
lower work function than the ionization potential of perovskite, and poor electron blocking
capability. All these properties hinder the efficient charge extraction and transport from
perovskite absorber to ITO. In addition, acidic and hygroscopic nature of PEDOT:PSS can
corrode the ITO electrode and degrade the moisture sensitive PSK layer, respectively. These
can degrade the long-term stability and lower the performance of PSCs. Therefore, tailoring
PEDOT:PSS HTL is essential for achieving highly efficient PSCs to mitigate these drawbacks.
This review article gives an overview of approaches tailoring PEDOT:PSS that can minimize
the limitations as HTL to improve the performance of PSCs. These include solvent treat-
ment, composite structure, doping, and bi-layer structure PEDOT:PSS. In addition, the roles
of tailored PEDOT:PSS HTL was understood in perovskite solar cells.

M
etal halide based perovskite (PSK) materials pos-
sess excellent structural, optical and electrical
properties including low exciton binding energy
[1], broad absorption spectrum in visible range [2], large
electron and hole diffusion lengths [1, 3], ambipolar charge
transport capabilities with high electron hole mobility [4].
Because of these excellent properties, PSCs exhibit enor-
mous advantages in power conversion efficiency (PCE) as
it increased from 3.8% in 2009 to 22.7% in 2017 and still
have potential of reaching even higher efficiency [5, 6].
Perovskite materials do not require interfaces for exciton
separation due to weak exciton binding energy. However,
the PCE without HTL (also act as electron blocking layer)
is lower than that of PSCs with HTL due to the probability
of higher charge recombination [7-9]. Therefore, effective
HTLs are still an important issue to achieve higher efficien-
cy of PSCs.
In inverted (p-i-n) structured PSCs, the HTL requires
high transparency in addition to conductivity. Among sev-
eral conductive polymers used as charge transport layers,
PEDOT:PSS is the most commonly used HTL [10]. Jeng et
al. in 2013 first reported on PEDOT:PSS in inverted planar
PSCs with a device structure of ITO/PEDOT:PSS/CH3N-
H3PbI3/C60/BCP/Al [11]. In addition to high transparency
and conductivity, PEDOT:PSS HTL is solution-processable
at low temperature, making it compatible for mechanically
flexible devices [12, 13]. Nevertheless, PEDOT:PSS is not
considered as the most efficient and appropriate HTL.
Electrical conductivity of PEDOT:PSS is significantly
lower than that of commonly used metal cathode due
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to the presence of insulating PSS, which causes energy
loss during charge transport, reducing the photocurrent
desnity. Moreover, conductivity of PEDOT:PSS is lower
compared to that of widely used electron transport layers
(ETLs) such as [6,6]- phenyl-C61-butyric acid methyl ester
(PC61BM). Unbalanced charge transport from the conduc-
tivity difference of ETL and HTL can create charge carrier
accumulation, which reduces shut resistance, resulting
in large leakage current and low fill factor (FF) [14, 15].
Furthermore, mismatched energy level alignment between
the work function (WF) of PEDOT:PSS and the valence
band maximum (VBM) of PSK causes inferior open circuit
voltage (Voc) due to large potential energy loss at the inter-
face [16-18]. In addition, acidic and hygroscopic nature of
PEDOT:PSS can corrode the ITO electrode and degrade the
moisture sensitive PSK layer, respectively; these can de-
grade the long-term stability and lower the performance of
PSCs [19]. Inferior crystallization of PSK on PEDOT:PSS is
also one of the major reasons behind the poor performance
of PSCs [20]. In these circumstances, tailoring PEDOT:PSS
can improve the performance of PSCs.
In this review, we focus on various approaches applied
to modify the properties of PEDOT:PSS HTL of inverted
(p-i-n) structured PSCs. Properties change of HTL due to
tailored PEDOT:PSS and the impact on crystallization of
PSK layer are also provided. Finally, the factors that im-
prove the performance of PSCs after modification of PE-
DOT:PSS HTL are also discussed.
2 APPROACHES TAILORING THE PEDOT:PSS
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doi: 10.11605/j.pnrs.201802004
HTL IN PEROVSKITE SOLAR CELLS
2.1 Solvent treated PEDOT:PSS HTL
Conductivity of PEDOT:PSS depends on the arrangement
and the amount of PEDOT and PSS. Most reports suggested
that solvent additive methods help to rearrange PEDOT and
PSS. In addition, solvent post treatment partially removes
the insulating PSS from the film resulting in an increased
ratio of PEDOT to PSS [21, 22]. Both the procedures help
PEDOT to orient themselves leading to high crystallinity
and efficient charge transport [23].
In 2017, Huang et al. [24] added different volume ratios
of dimethylsulfoxide (DMSO) into the aqueous solution
of PEDOT:PSS, which considerably enhanced charge ex-
traction and photocurrent production of PSCs. The PCE
of untreated PEDOT:PSS based devices was 11.8%, which
significantly increased to 15.8% with a champion cell at
16.7%. The higher shunt resistance (Rsh) induced by the
DMSO treated PEDOT:PSS indicated a lower leakage cur-
rent while more efficient PL quenching confirmed that the
charge transfer between the perovskite and DMSO-treated
PEDOS:PSS is more favorable [25, 26]. PEDOT:PSS treat-
ment also affected the morphology and crystallization of
the perovskite layer. DMSO added PEDOT:PSS surface
Table 1. Summary of the crystallite sizes, stacking distances, and the PEDOT ratios in PEDOT:PSS films treated by organic solvents [29].
PEDOT:PSS PSS PEDOT
treatment distance (Å) distance (Å)
Pristine 4.99 3.53
MeOH 4.92 3.45
DMF 4.97 3.43
EG 4.81 3.39
Figure 1. Atomic force microscopy (AFM) topography images of: (a) pristine, (b) DMF-treated, (c) MeOH-treated, and
(d) EG-treated PEDOT:PSS. The RMS roughness values are 1.98, 0.76, 1.32 and 2.53 nm, respectively. Reproduced with
permission from Ref. [29]
Proceedings of the Nature Research Society, 2, 02004 (2018)
showed the enhancement of aggregated PEDOT-rich par-
ticles. These aggregated particles acted as the growing sites
for crystal nucleus of PSK films during annealing, which
resulted in more compact, highly crystalline and larger
grain size. Improved morphology of PSK accounted for
more efficient pathways of charge carrier transport to the
electrodes [27, 28].
Enhanced PCEs of perovskite solar cells were achieved by
Chen et al. [29] when PEDOT:PSS was rinsed by Methanol
(MeOH) and N,N-dimethylformamide (DMF) in compari-
son to the reference devices with pristine one. Regardless of
higher conductivity, the ethylene glycol (EG) treated devic-
es showed lower efficiency. A small fraction of PSS is actu-
ally removed when the film is treated with solvents, leading
to increased PEDOT ratio in PEDOT:PSS film. Besides the
volume fraction of PEDOT, distance and crystallite size
of PEDOT also affects the conductivity. Table 1 shows the
summary of the crystallite sizes, stacking distances, and
the PEDOT ratios in PEDOT:PSS films treated by different
solvents. Solvent-treated devices had higher PCEs than the
reference one (PCE = 16.69%). DMF is found to be more
appropriate as the highest PCE of 18.02% is found for PE-
DOT:PSS treated by it. However, reduced open-circuit volt-
ages (VOC) and (FF) were observed for EG-treated devices
regardless of the highest conductivity among all the treated
samples. This may results from the higher surface rough-
PSS PEDOT PEDOT/
Crystal size (Å) Crystal size (Å) Total ratio
16.81 12.96 0.41
17.08 17.99 0.42
21.48 24.41 0.45
16.30 18.90 0.40
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 doi: 10.11605/j.pnrs.201802004
ness of ~2.53 nm after EG treatment compared to ~1.98 nm to the addition of glucose in the GO (GGO) suspension
of pristine PEDOT:PSS films (Figure 1). The rough surface facilitating the GO reduction process [49, 50] while the en-
of PEDOT:PSS could create sharp traps, which facilitates hanced wettability is due to the presence of hydroxyl group
surface charge-carrier recombination resulting in lower terminations [51]. The improved morphology of the PSK
VOC and FF [27]. The RMS roughness of the DMF-treated film on the nanocomposite results in photovoltaic (PV) de-
sample decreased to ≈0.76 nm (Figure 1b). The smoother vice performances of 12.8%, higher than the reference cells
surface of PEDOT:PSS obtained from the DMF treatment based on unmodified PEDOT:PSS (9.4% PCE) with a very
could facilitate the interfacial contact between the HTL and high , reaching values over 1.05 V. This suggests minimal
the PSK layer, resulting in a high VOC and FF [30]. recombination losses.
Figure 2 shows the XRD patterns of GO, compared to
2.2 Composite structure of PEDOT:PSS HTL that of GO-PEDOT:PSS and GGO-PEDOT:PSS composites
before annealing. Peak at is the characteristic peak of GO.
Despite high transparency and conductivity, PEDOT:PSS This peak disappears after adding GO to PEDOT:PSS indi-
has some concealed problems such as acidity, hygroscop- cating that GO sheets do not stack when dispersed (Figure
ic nature, lower work function than the ionization poten- 2a). Some stacked GO sheets are seen from the SEM images
tial of perovskite, and poor electron blocking ability [31- (Figure 2c), whereas addition of glucose results in homo-
33]. Several groups have developed promising alternatives geneous film with evenly dispersed GO sheets (Figure 2d).
to PEDOT:PSS [31, 34-36]. Recently, graphene based deriv- Steric bonding between carbon glucose and carbon of GO
atives show potential toward high performance PSCs [19]. assist to disperse GO, facilitating the formation of homoge-
Wu et al. [37] employed graphene oxide (GO) as HTL in neous GGO-PEDOT:PSS film.
planar PSC and achieved efficiency more than 12%. How- The wettability of PEDOT:PSS films with the addition
ever, the performance is highly sensitive to the thickness of glucose and GO was measured using contact angle
of HTL due to the insulating property of GO. The homoge- measurements (Figure 3a). GGO reduces the CE from to
neous dispersion and high uniformity with full coverage of . Importantly, CE of perovskite precursor solution on the
ITO is difficult to get. This can result in poor hole transport GGO-PEDOT:PSS has the minimum value of (Figure
and collection due to the direct contact of PSK layer with 3b). This suggests superior wettability and compatibility
the ITO. Furthermore, ununiformed GO deposited on ITO of GGO-PEDOT:PSS substrates with perovskite precursor
will lead to poor repeatability and reliability of device per- solution. Figure 3c shows perovskite grown on GGO-PE-
formance owing to the insulating property of GO. To over-
come this, HTLs were prepared by successive spin-coating
of GO and PEDOT:PSS (GO/PEDOT:PSS) [38]. The syner-
gistic effects of GO and PEDOT:PSS help to develop effi-
cient HTL for improved performance of PSCs with high re-
peatability. Meanwhile, GO/PEDOT:PSS composite results
in a smoother surface indicating that sequential deposition
of PEDOT:PSS and GO can planarize the rough GO films.
GO is an insulator due to the presence of oxygen contain-
ing functional groups on the carbon basal plane. Graphene
can improve the conductivity of PEDOT:PSS [39]. More-
over, improved charge extraction occurs at the interface of
perovskite/graphene-PEDOT:PSS. Despite high electrical
conductivity and mobility, graphene can shift the work
function towards vacuum level and increase the roughness
of PEDOT:PSS HTL, which is not favorable for the deposi-
tion of PSK layer. As an alternative GO can be used by im-
proving the conductivity using several reduction methods
based on thermal [40, 41], photo reduction [42], chemical
[43, 44], or electrochemical approaches [45].
Giuri et al. [46] developed PEDOT:PSS+graphene nano-
composite HTL by reducing GO through a green, simple
and cost effective way by using UV radiation. UV treatment
improves the wettability of the HTL, which influences the
morphology of PSK film and, hence, the devices perfor-
mances. Huang et al. [47] also used environmental friendly
thermal reduction method to reduce GO. Both the HTLs
reduced by thermal and UV reduction method give rise to Figure 2. a) Diffraction XRD patterns of GO, GO -
increased open circuit voltage, which suggests that energy PEDOT, and GGO-PEDOT, b) nanocomposite precursors;
level of rGO/PEDOT:PSS HTLs is in good alignment with SEM images of c) GO PEDOT and d) GGO -PEDOT
the VBM of PSK. nanocomposite films and corresponding AFM micrographs
Synergistic effect of glucose and GO enhances the wetta- of e) GO-PEDOT (scan area 20 × 20 μm2, Z-range 25 nm)
bility of PEDOT:PSS while improving the conductivity of and f) GGO-PEDOT (scan area 50 μm × 50 μm, Z-range 25
the composite [48]. Improved conductivity is mainly due nm). Reproduced with permission from Ref. [48]
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doi: 10.11605/j.pnrs.201802004
DOT:PSS has more compact and closer grains with fewer
defects compared to that grown on pristine PEDOT:PSS.
Higher performance is mainly due to higher and antici-
pated from improved conductivity of HTL, and minimal
recombination loss and very efficient charge extraction due
to high quality perovskite film [52-54].
Without reduction technique, conductivity of GO can
also be improved by chemically doping with silver trifluoro-
methanesulfonate (AgOTf) inorganic dopant [55]. Both the
optical and electrical properties of GO can be controlled by
the doping concentration. Thickness and roughness of the
GO film increase with the doping concentration while the
sheet resistance gradually decreases (Figure 4). Optimized
doped GO incorporated with PEDOT:PSS improves the per-
formance of PSCs.
PEDOT:PSS-GeO2 composite HTLs are developed by in-
corporating GeO2 NPs [56] and GeO2 aqueous solution [57]
into the PEDOT:PSS aqueous dispersion. GeO2 particles
affect the morphology of the PSK layer. Island-like particles
are perceived on the composite film (Figure 5b). These
particles act as growing sites of crystal nucleus of the per-
ovskites. PSK films on pristine PEDOT:PSS contain inter-
connected nanoscale domains with lot of pin-holes (Figure
5c). These obstructs charge transport and induces carrier
recombination, which results in lower performance. Supe-
rior quality of PSK film with large-scale domains (Figure
5d) and high crystallinity (Figure 5f) was obtained by the
seed-mediation of GeO2 particles. Further improvement of
PSK film and enhancement of the performance might be
achievable if the voids (Figure 5d) could be eliminated.
2.3 Doped PEDOT:PSS HTL
Additives were introduced to improve the conductivity of
PEDOT:PSS HTL [58]. As additives reside in the layer, they

Figure 3. a) Contact angle of pristine PEDOT:PSS, GO-PEDOT, G-PEDOT, and GGO-PEDOT on ITO, b) contact angle of
perovskite precursor drops on nanocomposite substrates, and c) SEM of PSK layer deposited on different nanocomposite
substrates. Reproduced with permission from Ref. [48]

Figure 4. Roughness, thickness and sheet resistance of AgOTf-doped GO layers as a function of doping concentration.
Reproduced with permission from Ref. [55]

Proceedings of the Nature Research Society, 2, 02004 (2018) Published by Nature Research Society http://nrs.org | 4

also affect the morphology of PEDOT:PSS and PSK layer. It
also has influence on the work function of PEDOT:PSS lay-
er.
Huang et al. [59] employed highly conductive polyeth-
ylene oxide (PEO) doped PEDOT:PSS as HTL to improve
the performance of PSCs. Enhanced conductivity of PEO-
doped PEDOT:PSS facilitates the hole extraction and trans-
port to the ITO anode from the active layer. Improved con-
ductivity originates from the tuned film morphology of the
doped HTL and increased ratios of PEDOT in the bipolaron
states. Morphology of PEDOT:PSS with different doping
concentrations of PEO are shown in the AFM topography
images (Figure 6a-e). RMS roughness values calculated
from the height images are ≈1.38, ≈1.25, ≈0.88, ≈1.43 and
≈1.73 nm for the PEO doping concentration of 0, 0.3, 0.5,
0.8 and 1.2 vol%, respectively.
Rough surfaces of pristine PEDOT:PSS or PEO-doped PE-
DOT:PSS at higher doping concentration create trap states
at the interface of PSK and HTL [60]. Fiber-like PEDOT
domains at higher doping concentration (over 0.8 vol%)
introduce extra pin-holes, resulting in trap-assisted charge
Figure 5. SEM images of (a) PEDOT:PSS film, (b) PEDOT:PSS-GeO2 (4:1) film, crystalline PSK films deposited on
(c) PEDOT:PSS, and (d) PEDOT:PSS-GeO2, XRD patters of crystalline PSK films deposited on (e) PEDOT:PSS and (f)
PEDOT:PSS-GeO2. Reproduced with permission from Ref. [57]
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doi: 10.11605/j.pnrs.201802004
carrier recombination [61]. The highest PCE was observed
at 0.5 vol% doping concentration despite higher conduc-
tivity at higher doping concentrations (Figure 7a). PEO-
doped PEDOT:PSS with optimized doping concentration
(0.5 vol%) was used to adjust the thickness of the HTL and
50 nm (similar to pristine PEDOT:PSS) offered the highest
efficiency of 16.52% compared to 11.43% from pristine PE-
DOT:PSS HTL (Figure 7b).
Qian et al. [62] prepared Ag-NPs doped PEDOT:PSS HTL
and observed that the performance of PSCs is influenced by
the doping concentration of Ag-NPs. Ag-NPs improves the
conductivity of PEDOT:PSS and the crystalline properties
of PSK films. Besides these, it has minimal influence on
the energy level alignment and absorption due to Plasmon
resonance effect. Liu et al. [63] improved the morphology
of PSK films (Figure 8) deposited on core/shell NPs doped
PEDOT:PSS and perceive the only reason for improved per-
formance of PSCs.
Proper energy level alignment of HTL with PSK is report-
ed by several research groups by doping PEDOT:PSS. Dop-
ing PEDOT:PSS film with 2,3,5,6-tetrafluoro-7,7,8,8-tetra-
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Figure 6. AFM topography images of PEDOT:PSS films doped at different concentrations of PEO. Reproduced with
permission from Ref. [59]

Figure 7. (a) Electrical conductivities of the PEO-doped PEDOT:PSS layer and PCEs of PSCs versus doping concentrations of PEO in
the layer; (b) J-V characteristics of PSCs incorporated with the pristine and PEO-doped PEDOT:PSS HTL at different thickness. Repro-
duced with permission from Ref. [59]

cyanoquinodimethane (F4-TCNQ) [64] increases the work
function of the HTL from 5.08 eV to 5.18 eV (Figure 9a),
whereas Huang et al. [65] achieved similar outcome using
dopamine (DA) (Figure 9b). The work function of PE-
DOT:PSS was tuned by Lim et al. [32] using self-organized
HEL (SOHEL), which was composed of PEDOT:PSS and
tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-oc-
tene-sulfonic acid copolymer (Figure 9c).
2.4 Bi-layer structure of PEDOT:PSS HTL
Appropriate energy level tailoring can improve device
performance by increasing. This also facilitates efficient
charge extraction and transfer which contribute to increas-
ing Jsc and FF [66]. Suitable interfacial layer can modify the
WF of ITO/PEDOT:PSS HTL to reduce the potential energy
loss at the junction formed by PSK and PEDOT:PSS.
Malinkiewicz et al. [52] and Lin et al. [67] reduced the
energy gap between WF of HTLs and VBM of PSK em-
ploying PEDOT:PSS/poly-TPD and PEDOT:PSS/conjugat-
ed polymers (DPP-DTT, PCDTBT, P3HT and PCPDTBT)
double layers, respectively. Due to poor wetting of DMF or
DMSO on the hydrophobic polymer surface, these struc-
tures are only compatible for vacuum-deposited PSCs.
Xue et al. [16] solved the above problem introducing two
new alcohol-soluble conjugated copolymers PTPAFSONa
(HSL1) and PTPADCF3FSONa (HSL2) (Figure 10a) with
Proceedings of the Nature Research Society, 2, 02004 (2018)
tailored energy levels (Figure 10b) and hydrophilic prop-
erty (Figure 10c-f). Deeper HOMO levels of HSLs provide
efficient hole transfer and the high LUMO energy levels
block the electron preventing charge recombination at the
anode interface. They achieved remarkable improvements
in PCEs (16.6%) and (1.07 V) of PSCs by using HSL2 com-
pared to 14.2% and 0.98 V of pristine PEDOT:PSS based de-
vices. Similarly, cross-linked electron blocking interlayers
made from QUPD and OTPD can improve the performance
of PSCs by reducing the electron-hole recombination
[68].
GO and PEDOT:PSS hybrid bi-layer HTLs can remark-
ably suppress leakage current and electron-hole recom-
bination. Li et al. introduced GO layer in between ITO
and PEDOT:PSS [69]. In contrast, Feng et al. [70] added
GO on top of the PEDOT:PSS layer. The work function of
PEDOT:PSS-GO film is found to be 5.19 eV, which is high-
er than that of pristine PEDOT:PSS (5.10 eV). The work
function is further improved to 5.37 eV by introducing
ammonia modified GO layer (PEDOT:PSS-GO:NH3). The
performance of PSCs depends on the doping concentration
of ammonia into GO and the highest efficiency of 16.11%
was achieved for the doping ratio of 1:03 (GO:NH3). Per-
formance improvements were caused by increased quality
of PSK films (Figure 11a-c) and enhanced optical absorp-
tion (Figure 11d). PSK films deposited on PEDOT:PSS-GO
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 doi: 10.11605/j.pnrs.201802004

Figure 8. SEM images of PSK films deposited on (a) pristine and (b) 20% NPs doped PEDOT:PSS layers, and (c, d) their
corresponding AFM images. Reproduced with permission from Ref. [63]

Figure 9. Energy level diagram of the cell with (a) F4-TCNQ doped, (b) DA, and (c) SOHEL doped PEDOT:PSS HTLs.
Reproduced with permission from Ref. [64, 65, 32]

have more regular and larger grain size with some pores
compared to that atop pristine PEDOT:PSS. Higher ordered
structure of PSK with complete coverage was achievable by
depositing on PEDOT:PSS-GO:NH3 film. This was caused
by the surface and electronic property changes due to the
GO:NH3 film.
Analogous consequence was also observed when
perylene was deposited atop PEDOT:PSS [71]. Depend-
ing on varied concentrations of perylene, the morphology
of perylene layer and corresponding PSK layers changes
(Figure 12a-h). In comparison with the reference devices
(only PEDOT:PSS HTL), PSCs having perylene layer with a
concentration of 4 mg/mL shows the best performance and
improved PCE from 12.67% to 17.06%, from 0.91 V to 0.98
V, from 19.61 mA/cm2 to 22.61 mA/cm2, and from 71%
to 77%. The maximum PCE is mainly ascribed to the en-
hanced and in comparison with the other perylene-based
devices. The fabric feature of the PSK film (Figure 12g)
deposited on branch-shaped perylene under layer (Figure
12c) was found to be the most favorable morphology.
3 ROLES OF TAILORED PEDOT:PSS HTL IN
PEROVSKITE SOLAR CELLS
As a HTL, PEDOT:PSS has some limitations. To improve
the performance of PSCs, these drawbacks should be prop-
erly addressed. Tailoring PEDOT:PSS can improve the
morphology of HTL and perovskite layer deposited atop it.
Among several roles of tailored PEDOT:PSS, we will dis-
cuss on the contributions to electrical conductivity, energy
level alignment, trap passivation and long-term stability.
3.1 Electrical conductivity of tailored PEDOT:PSS HTLs
Charge accumulation at the interface occurs due to the
difference in electrical conductivity between the PSK and
the charge transport layer. This can cause the formation of
space charges that can inhibit efficient charge transport.
Therefore, high electrical conductivity of charge transport
layers is important to ensure efficient charge transport to
desired electrode.

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doi: 10.11605/j.pnrs.201802004
Figure 10. (a) Molecular structure of HSL1 and HSL2,
(b) energy level diagrams of PSCs using HSL1 and HSL2
as HTLs, isopropanol contact angle measurements of
(c) PEDOT:PSS, (d) HSL1, (e) HSL2, and (f ) PSK film.
Reproduced with permission from Ref. [16] Loss in built-in potential due to the energy level differ-
Conductivity of PEDOT:PSS can easily be modulated
by the removal of PSSH chains [72-74]. Removal of PSSH
chains results in conductive PEDOT rich film. Further-
more, the removal of PSSH chains can induce the confor-
mational change of PEDOT chains from a coil structure to
an extended coil structure [75].
Conductivity variation of PEDOT:PSS affects the per-
formance of PSCs. Sin et al. [76] varied the concentration
of PSS and added small amount of DMSO before spin
casting PEDOT:PSS, which improved the conductivity of
PEDOT:PSS HTL from to without significant variations
in their energy levels. With conductivity, grain size of PE-
DOT:PSS also increased with fibril structures. In contrast,
no significant morphological differences were observed be-
tween the PSK films deposited on different conductive PE-
DOT:PSS films, confirming that the performance of PSCs
are affected solely by the properties of PEDOT:PSS films.
Incident light power (ILP) dependent photocurrent of PSCs
with low and high conductive PEDOT:PSS (PEDOT-L and
Figure 11. SEM images of PSK films on (a) PEDOT:PSS, (b) PEDOT:PSS-GO, (c) PEDOT:PSS-GO:NH3 and (d) UV-vis
absorption spectra of PSK films on three different substrates. Reproduced with permission from Ref. [70]
Proceedings of the Nature Research Society, 2, 02004 (2018)
PEDOT-H, respectively) was measured to investigate charge
collection balance or charge accumulation (Figure 13a,b).
At effective applied voltage far from open circuit condition
(3 V) with minimum charge carrier recombination, the S
parameter (approaches a unity for ideally fabricated device)
for the PEDOT-H-based PSCs is 0.969. Whereas, for the PE-
DOT-L-based PSCs, S parameter is 0.904, which represents
that highly conductive PEDOT:PSS HTL reduces hole ac-
cumulation. S parameter at low effective applied voltage
(0.4 V) also shows much higher value (0.953 compared to
0.893) for PEDOT-H based device, which means reduced
nongeminate recombination with increased conductivity.
Higher conductivity of HTL reduces charge accumulation
and recombination loss, which result in enhanced short cir-
cuit current density (Jsc) and. Facilitation of hole transport
through the highly conductive PEDOT:PSS HTL finally
leads to 25% higher PCE in PSCs.
3.2. Energy level tailoring
ence between PSK and HTL can lead to decrease in perfor-
mance of PSCs. Energy level tailoring helps to reduce the
charge accumulation at the interface decreasing charge
recombination probability which results in enhanced and
. Moreover, proper alignment between the energy level of
HTL with the VBM of PSK materials increases the due to
the increase in quasi-fermi level difference between the
ETL and HTL.
Xue et al. [16] calculated charge recombination lifetime
from TPV measurement of PSCs for CH3NH3PbIxCl3-x (I)
and CH3NH3Pb(I0.3Br0.7)xCl3-x (Br) using PEDOT:PSS/PT-
PAFSONa (HSL1) and PEDOT:PSS/PTPADCF3FSONa
(HSL2) double layers as HTLs (Figure 14a). Charge recom-
bination lifetime increases for all the cells using HSL1 and
HSL2 (HSL1-I: 6.2 µs, HSL2-I: 6.3 µs, HSL2-Br: 4.9 µs) com-
pared to the cells with pristine PEDOT:PSS (None-I: 1.8 µs,
None-Br: 1.5 µs), indicating lower charge recombination
rate. These suggest that proper energy level alignment ef-
fectively suppresses charge recombination.
Lin et al. [67] introduced different polymeric organic
Published by Nature Research Society http://nrs.org | 8

Figure 12. SEM images of perylene films deposited on PEDOT:PSS from varied concentrations of (a) 2 mg/mL, (b) 3 mg/
mL, (c) 4 mg/ mL, and (d) 5 mg/mL in chloroform; (e-h) SEM images of PSK films deposited on the perylene under layers
corresponding to (a-d). Reproduced with permission from Ref. [71]
semiconductors to ITO/PEDOT:PSS HTLs and observed
higher (Figure 14b) with the devices having polymers of
higher ionization energy (IEs), Figure 14c. Devices with
PCDTBT interlayer show the highest average of 1.03 V,
which is higher than those with P3HT (0.7 V).
3.3. Passivation of traps
Increased conductivity of the PEDOT:PSS films does not
assure higher performance of PSCs all the time. Quality
films of PSK and PEDOT:PSS after treatment also play
significant role. Surface properties of PSK films depends
on the surface morphology of PEDOT:PSS . Unfavorable
surface morphology of PEDOT:PSS induces defects on the
PSK layer, which can increase leakage current with low-
ering shunt resistance. Defects such as grain boundaries
or atomic vacancies act as trap sites where charge carriers
recombine [77, 78]. However, these problems are rarely
addressed, where people found lower performance of PSCs
after the treatment of PEDOT:PSS [79-81]. It is obvious that
surface roughness, wettability, additives and composite
materials of tailored PEDOT:PSS can impact the growth of
PSK layer. A majority of groups reported superior quality
of PSK films deposited on treated PEDOT:PSS with fewer
traps, leading to improved performance of PSCs [16, 38, 48,
59, 71].
Adam et al. [82] developed pinhole free thin film PSK
Figure 13. Incident light power dependent photocurrent of the
perovskite solar cells with (a) PEDOT-L and (b) PEDOT-H at two
different effective applied voltages. Reproduced with permission
from Ref. [76]
Published by Nature Research Society http://nrs.org
doi: 10.11605/j.pnrs.201802004
layers on highly conductive PEDOT:PSS (Clevios PH1000)
using DMSO and Zonyl as additives. They found that PE-
DOT:PSS after treatment with optimum additives helps to
grow better quality of PSK layer, which is the key reason
for enhanced performance with good operational stability
and moderate hysteresis (Figure 15). Additives reduce the
number and size of defects in the PSK films (Figure 15c-f)
compared to that deposited on ITO (Figure 15a) or pristine
PEDOT:PSS (Figure 15b). Optimized concentration of ad-
ditives (0.7% v/v Zonyl and 5% v/v DMSO) produces PSK
film with no visible gaps and defects (Figure 15f). Devices
fabricated from this PSK film show low leakage currents.
Traps in PSK absorbers has been considered as the major
cause of photocurrent hysteresis of PSCs, which hinders
the measurement of truthful performance and stability of
devices [83-87]. It may also originate from interface and
surface-trap defects [67, 88]. Tailored PEDOT:PSS based
devices can minimize hysteresis by reducing trap states and
charge accumulation [38, 58, 59, 64, 65, 89, 90].
3.4 Enhancement in stability
The acidic and hygroscopic properties of PEDOT:PSS
HTL lead to poor stabilities of the PSCs owing to the acid
corrosion of ITO by PEDOT:PSS and conductivity degrada-
tion of PEDOT:PSS films by absorbing water, respectively
[67]. PSS− is a strong acid that can react with In2O3 dissoci-
ating indium ions which can easily diffuse into active layer,
deteriorating the stability of the devices [91]. A common
way to neutralize acidic properties of PEDOT:PSS is to add
strong bases such as NaOH [92], KOH [93] and guanidine
[94]. However, the neutralization using strong base badly
affects the conductivity of PEDOT:PSS, which results in
low device performance [92].
Wang et al. used [95] mild base imidazole to improve the
long-term stability of PSCs. Easily miscible imidazole into
PEDOT:PSS can neutralize acidity with minimal effect of
conductivity. Acidic PEDOT:PSS (pristine) keeps 38% of its
PCE after two weeks, whereas basic-PEDOT:PSS (imidazole
doped) maintains 75% of that. PCEs of all the devices show
Proceedings of the Nature Research Society, 2, 02004 (2018) | 9
doi: 10.11605/j.pnrs.201802004

Figure 14. TPV measurements for PSCs using PEDOT:PSS (pristine), HSL1 and HSL2 HTLs; (b) J-V curve of PSCs using
different polymer interlayers; (c) schematic illustration of the energy levels of CH3NH3PbI3 perovskite, PC60BM ‘electron
affinity’ and ionization potential of different polymer interlayers. Reproduced with permission from Ref. [16, 67]

Figure 15. SEM images of perovskite films coated on top of (a) Glass/ITO; (b) PEDOT:PSS; PEDOT:PSS processed with
(c) 5% v/v DMSO, (d) 0.7% v/v Zonyl FS-300, (e) 0.7% v/v Zonyl, FS-300 and 2.5% v/v DMSO, (f) 0.7% v/v Zonyl and 5% v/v
DMSO. Reproduced with permission from Ref. [82]

faster decrease of with time. Basic-PEDOT:PSS apparently of thin films [39].

inhibits the indium contamination, leading to excellent
ambient stability. Similarly, dopamine doped PEDOT:PSS
improves the stability by reducing the acidity, which in
turn inhibits the impurity diffusion from ITO. In parallel,
it makes the PEDOT:PSS layer less hygroscopic, which re-
duces the decomposition of PSK layers [65]. Erosion of ITO
by the acidic PEDOT:PSS can be effectively prevented by
incorporating MoO3 layer between ITO and PEDOT:PSS.
After 10 days, PCE of the devices having MoO3 degraded
only 7%, whereas without MoO3 failed completely [96].
Device stability also depends on the crystallinity of
perovskite structure. Highly ordered perovskite structure
deposited on the GO:NH3 layer shows improved device sta-
bility of PSCs compared to that with lower quality of PSK
film deposited on pristine PEDOT:PSS [70]. In addition,
graphene has a great potential for bridging between the PE-
DOT:PSS polymer segments, favoring stability and integrity
4 CONCLUSIONS AND OUTLOOK
In this review paper, we discussed the progresses of
PEDOT:PSS HTLs in PSCs. Tailored PEDOT:PSS HTLs
have crucial roles in improving PCE and stability of PSCs.
Higher conductivity can improve charge transport prop-
erties; whereas the proper alignment between the WF of
PEDOT:PSS HTL and VBM of PSK reduces the energy off-
set, and thereby facilitates charge extraction. Surface mod-
ification of tailored PEDOT:PSS can passivate traps in PSK
films and at the interface, which can eliminate hysteresis
and lessen the leakage current. Acidity and hydrophilicity
of PEDOT:PSS HTL can also be controlled to reduce the
corrosion and degradation of moisture sensitive PSK active
layer. On the basis of above optimizations of PEDOT:PSS
HTLs, further improvement in PCE and long-term stability

Proceedings of the Nature Research Society, 2, 02004 (2018) Published by Nature Research Society http://nrs.org | 10

of PSCs can be achieved.
Inverted (p-i-n) structured PSCs are more promising
due to low cost and possibility of further simplification of
the structure. Higher processing temperature of TiO2 ETL
and the hysteresis problem originated from FTO and TiO2
compact layer can be minimized by inverted structure. PE-
DOT:PSS, a most widely used HTL in inverted structure, is
solution processable and flexible. This makes it applicable
to low cost solution processed flexible devices. It is also
possible to achieve high conductivity, improved morpholo-
gy and a wide range of WF from tailored PEDOT:PSS. WF
of PEDOT:PSS can be varied to make it compatible with
PSK absorber of different bandgap and VBM. Specially, in
case of tandem structure, WF of PEDOT:PSS can be adjust-
able with the high and low band gap absorber. PEDOT:PSS
with enhanced conductivity can replace expensive and brit-
tle metal oxide electrodes. However, the major limitation
of PEDOT:PSS is the stability, which can also be partially
solved by reducing the acidity and hygroscopicity.
The attempts on exploring the mechanisms of tailoring
PEDOT:PSS may help and guide future researchers to find
more efficient way to improve the optical, electrical and
structural properties of PEDOT:PSS. This can improve the
performance of PSCs and will be applicable to more feasi-
ble applications in the future.
Notes
The authors declare no competing financial interest.
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