Bis(tri-n-alkylsilyl oxide) silicon phthalocyanines: A start to establishing a structure property relationship as both ternary additives and non-fullerene electron acceptors in bulk heterojunction organic photovoltaic devices

Article abstract of DOI:10.1039/c6ta10739g

Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)₂-SiPc) as a solid ternary electroactive additive in poly(3-hexylthiophene):phenyl-C₆₁-butyric acid methyl ester P3HT:PC₆₁BM bulk heterojunction organic photovoltaic (BHJ OPV) devices resulted in an increased performance. It has been hypothesized that the increase in efficiency is partially due to the unique and odd combination of high solubility and strong driving force of crystallization previously observed for (3HS)₂-SiPc. In this follow-up study, two chemical variants of (3HS)₂-SiPc, namely bis(tri-n-butylsilyl oxide) ((3BS)₂-SiPc) and bis(tri-n-isopropylsilyl oxide) ((3TS)₂-SiPc) were synthesized to determine how small changes in the chemical structure would affect the properties of the material and its performance within BHJ OPV devices. We observed that the use of either (3XS)₂-SiPc compound results in a further ～10% increase in J_SC compared to the use of (3HS)₂-SiPc. We also did a preliminary assessment of the use of three (3XS)₂-SiPcs as replacements for PC₆₁BM in straight binary P3HT-based BHJ OPV devices. Despite achieving only ～1% PCE efficiencies, observations including a ≈50% increase in V_OC over a P3HT:PC₆₁BM baseline and a decent fill factor indicate to us that (3XS)₂-SiPcs do have potential as non-fullerene acceptors and advantageous alternatives due to their low embedded energy and therefore their inherent sustainability. X-ray diffraction of ternary and binary BHJ devices demonstrates that both (3BS)₂-SiPc and (3TS)₂-SiPc experienced similar increase in crystallite density (d-spacing) relative to (3HS)₂-SiPc which we surmise plays a role in the improved device efficiency. Like (3HS)₂-SiPc, for these two new additives, we also observed a high tendency of crystallization. The results from this study suggest that solubility and driving force to crystallize are important factors in determining the extent to which an additive will migrate to the donor/acceptor interface and thus affect its performance as a ternary additive in BHJ OPV devices. Based on the three (3XS)₂-SiPcs used in this study, the smaller tri-n-alkylsilyl oxide molecular fragments seem to work better. Therefore, moving forward, we will continue to consider smaller molecular fragments that still enable solubility and processability of (3XS)₂-SiPcs.

Full text of DOI:10.1039/c6ta10739g

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
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Journal Materials Chemistry A
ARTICLE
Bis(tri-n-alkylsilyl oxide) silicon phthalocyanines: A Start to
Establishing a Structure Property Relationship as both Ternary
Additives and Non-Fullerene Electron Acceptors in Bulk
Heterojunction Organic Photovoltaic Devices.
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a,†
a,c†
b
b
a,c,
Minh-Trung Dang, Trevor M. Grant, Han Yan , Dwight S. Seferos , Benoît H. Lessard, * and
www.rsc.org/
,
a,b,d
Timothy P. Bender*
2
Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS) -SiPc) as a solid ternary
electroactive additive in poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester P3HT:PC61BM bulk heterojunction
organic photovoltaic (BHJ OPV) devices resulted in an increased performance. It has been hypothesized that the increase
in efficiency is partially due to the unique and odd combination of high solubility and strong driving force of crystallize
previously observed for (3HS)
(3BS) -SiPc) and bis(tri-n-isopropylsilyl oxide) ((3TS)
structure would affect the properties of the material and its performance within BHJ OPV devices. We observed that the
use of either (3XS) -SiPc compound results in a further ~10% increase in Jsc compared to the use of (3HS) -SiPc. We also
did a preliminary assessment of the use of the three (3XS) -SiPcs as replacements for PC61BM in straight binary P3HT-based
BHJ OPV devices. Despite achieving only ~1% PCE efficiencies, observations including a ≈ 50% increase in VOC over a
P3HT:PC61BM baseline and a decent fill factor indicate to us that (3XS) -SiPcs do have potential as non-fullerene acceptors
and advantageous alternatives due to their low embedded energy and therefore their inherent sustainability. X-ray
diffraction of ternary and binary BHJ devices demonstrate that both (3BS) -SiPc and (3TS) -SiPc experienced similar
increase in crystallite density (d-spacing) relative to (3HS) -SiPc which we surmise plays a role in the improved device
efficiency. Like (3HS) -SiPc, for these two new additives, we also observed a high tendency to crystallize. The results from
2
2
-SiPc. In this follow up study, two chemical variants of (3HS) -SiPc, bis(tri-n-butylsilyl oxide)
(
2
2
-SiPc) were synthesized to determine how small changes in chemical
2
2
2
2
2
2
2
2
this study suggest that solubility and driving force to crystalize are important factors in determining the extent to which an
additive will migrate to the donor/acceptor interface and thus affect its performance as a ternary additive in BHJ OPV
device. Based on the three (3XS)
work better. Therefore, moving forward, we will continue to consider smaller molecular fragments that still enable
solubility and processability of (3XS) -SiPcs.
2
-SiPcs used in this study, the smaller tri-n-alkylsilyl oxide molecular fragments seem to
2
inexpensive processing and short energy payback time compared to
1
silicon based devices. Bulk heterojunction (BHJ) OPV devices are
Introduction
among the most studied, where the active layer is most often
composed of a blend of an electron donating conjugated polymer
Increased interest in solar energy capture has seen a strong growth
in solar cell research over the past decade. There are also
continuing research efforts to provide an inexpensive source of
renewable energy capture with limited embedded energy within
1
and a fullerene based electron accepting small molecule. Poly(3-
hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester
(
PC BM) are by far the most studied donor / acceptor paired
61
1
the device. Among other solar collectors, organic photovoltaic
materials for use as an active layer within the BHJ OPV space, with
(
OPV) devices show great promise due to their potential for
2
baseline PCEs ranging from 2.5% to 5%. However the synthesis of
PC61BM, PC71BM and other emerging low band gap polymers are
potentially problematic due to their total energy requirements
emanating from numerous low yielding synthetic steps and
3,4
inefficient purification procedures. The need for active materials
with less demanding synthetic routes and therefore lower
embedded energy is required. For this technology to become a
commercial and environmental success it is important that we
apply the 12 principles of “green chemistry”/sustainable chemical
5
–7
processes. The development of more sustainable replacements
for PC BM should address several of the green chemistry
61
principles, for example, prevent waste, maximize atom economy,
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Journal Name
design
less
hazardous
synthesis,
the
reduction
of P3HT:PC BM BHJ OPV devices to determine if they would perform
61
32
derivatives/intermediates and the maximization of energy in a similar manner to (3HS)
efficiency resulting in minimized embedded energy.
2
-SiPc. Consistent with the results
from Honda et al., we observed an increase in device efficiency of
In addition to using starting materials that require less up to 20% for devices incorporating (3HS) -SiPc as an additive.
5
–7
2
energy intensive synthesis, how the devices themselves are built Furthermore, our study found that (3HS) -SiPc outperformed all
2
and processed can also aid in the overall devices performance. other additives, such as bis(tri-n-hexylsilyl oxide) germanium
Engineering parameters such as thermal annealing, choice of phthalocyanine ((3HS) -GePc) and tri-n-hexylsilyl oxide boron
2
solvent, weight ratios of donor to acceptor, and the use of an subphthalocyanine ((3HS)-BsubPc). While working with (3HS)
2
-SiPc,
electroactive solid additives have been reported to enhance the PCE we observed that the compound had an extreme tendency to
8
–17
for P3HT:PC61BM BHJ OPV devices.
So called ternary BHJs are crystallize while also being highly soluble – contradictory properties.
generically comprised of three photoactive and/or electroactive We hypothesized that the unique combination of high solubility and
components resulting in greater device efficiencies while a seemingly strong driving force to crystallize were in part
8
–10,14,15
maintaining comparable device fabrication ease.
For a ternary additive to be effective, they must produce Honda et al.
a cascade charge transfer effect between the P3HT and PC BM by Following up on these findings, we decided to synthesize a
acting as intermediate donor/acceptors. Additionally, a ternary series of chemical variants of (3HS) -SiPc to determine if the
responsible for the improved OPV device efficiency described by
2
9
6
1
8
2
additive should increase the light absorption of the OPV and crystallinity and solubility could be altered, and to determine if this
contribute to additional photocurrent production at wavelengths of would result in increased performance in BHJ OPV devices
light not absorbed by P3HT and PC61BM (e.g.: 450-650 nm).
therefore forming a structure property relationship. In this study,
-SiPc and determine
Metal/metalloid their potential roles in BHJ OPV devices as solid additives. Also
A solid ternary additive that has recently received renewed we explore two structural variants to (3HS)
interest is silicon phthalocyanine (SiPc).
2
1
8–20
containing phthalocyanines (MPcs) are molecules which classically based on their HOMO/LUMO energy levels and our previous
have been applied as industrial pigments and dyes, due to their experiences with SiPcs as electron acceptors, we for the first time
strong optical properties and general chemical stability. Compared have probed (3HS)
2
-SiPc and the structural variants as direct
to other active materials, such as PC61BM, MPcs require on average PC61BM replacements within BHJ OPVs and therefore start to
3
,4
2
-orders of magnitude less energy to synthesize and purify.
Recently, MPcs have found application as the photoactive layer in
expand their functional potential.
21–2324
planar heterojunction (PHJ) OPVs,
organic light emitting
2
5
26–28
diodes (OLEDs) and organic thin film transistors (OTFTs).
Unlike more common MPcs, such as copper and zinc, SiPc contains
a tetravalent metal that can form two axial bonds perpendicular to
Experimental
Materials
29–31
All ACS grade solvents were purchased from Caledon Laboratories
the phthalocyanine chromophore.
This enables a chemical
(
Caledon, Ontario, Canada) and used without further purification
handle for the tuning of both physical and electrical properties. We
have shown for example that the position and frequency of fluorine
atoms within fluoro phenoxy SiPcs influences such factors in PHJ
unless otherwise stated. 1,3-diaminoisoindoline (DI3) was
purchased from Xerox Corporation (Mississauga, ON) and used as
31
received. Silicon tetrachloride (SiCl
anhydrous, 99%), and cesium hydroxide (CsOH), were purchased
from Sigma Aldrich and used as received. Tri-n-hexylchlorosilane
3HS), tri-n-butylchlorosilane (3BS), and triisopropylchlorosilane
4
), 1,2-dichlorobenzene
OPVs.
(
The sum of favourable frontier orbitals, absorption in the
50-700 nm range and chemically addressable axial substituents
have been shown to make SiPcs promising candidates as ternary
6
(
3
2,33
(3TS) were purchased from Gelest (Morrisville, Pennsylvania, USA)
and used as received. Dihydroxysilicon phthalocyanine (SiPc-OH )
was synthesized according to the literature.
additives in BHJ OPVs.
of studies the use of bis(tri-n-hexylsilyl oxide) SiPc ((3HS)
Figure 1) as an electronically active ternary additive in BHJ OPV
Honda et al. first established in a number
2
2
-SiPc,
32
3
3–36
devices.
2
The addition of as little as 4 wt% (3HS) -SiPc to a
Methods
P3HT:PC61BM BHJ OPV was found to increase the device PCE by up
3
3
All reactions were performed under an atmosphere of nitrogen gas
using oven dried glassware. Ultraviolet-visible (UV-vis) absorption
spectra were acquired on a PerkinElmer Lambda 1050 UV / vis / NR
spectrometer using a PerkinElmer quartz cuvette with a 10 mm
path length. Electrochemical analysis was performed on a BASI C3
cell stand using an Ag / AgCl counter-electrode and a glassy carbon
working electrode and a scan rate of 100 mV / s. Samples were
dissolved in a 0.1 mol / mL tetrabutyl ammonium perchlorate
solution in DCM. The thermal stability of the SiPcs were
characterized by thermogravimetric analysis (TGA) using a TA
Instrument Q50 and differential scanning calorimetry (DSC) using a
2
to 20%. Honda et al. determined that (3HS) -SiPc was found
mostly at the P3HT:PC61BM interface and that the increased
efficiency from the additive arose not only from the increased
photo charge generation from the SiPc chromophore absorbance
(
at 700 nm), but also due to increased electron transfer from P3HT
3
6
to PC61BM due to the fore mentioned cascading effect. (3HS)
has also been chemically modified to comprise tert-butyl groups on
the SiPc aromatic periphery,
2
-SiPc
3
7,38
and has then been used in ternary
BHJ OPV devices or even used in combination with other additives
such as indene-C60 bisadduct (ICBA) in quaternary BHJ OPV
3
9
34
40–42
devices. Honda et al. as well as others
have also explored
d
TA Instrument Q1000. Thermal decomposition temperature (T )
the use of bis(tri-n-hexylsilyl oxide) functionalized silicon
naphthalocyanine (SiNc) based additives to take advantage of the
increased photo charge generation at 750-850 nm corresponding to
the dyes respective absorbance.
Our group recently completed a follow up study to that of
Honda et al., where we explored the use of various phthalocyanine
and subphthalocyanine compounds as solid additives in
was obtained by TGA using a heating rate of 10 °C / min and was
defined as the temperature at which 5% weight loss of the
compounds is observed under nitrogen. DSC was performed on the
SiPc derivatives using the following profile: first heat to 275 °C
(
(
bellow T ) at a rate of +5 °C / min followed by a first cooling to 0 °C
-5 °C / min), a second heat to 275 °C (+5 °C / min), a flash cooling to
d
0
°C (-100 °C / min), a third heat to 275 °C (+5 °C / min) and a final
2
| J. Name., 2012, 00, 1-3
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ARTICLE
cooling to 0 °C (-5 °C / min). The melting temperature (T ) and required for each device and were stirred again at 50 °C for 3 hours
m
enthalpy of melting (∆H
as the onset and the area of the peak in the heat flow versus casted onto the PEDOT:PSS at 600 rpm for 1 minute. The resulting
temperature plots, respectively. The crystallization temperature (T layers were placed in a glass Petri dish with a partially uncovered lid
m
) were identified in the second heating run to ensure complete mixing. The photoactive solutions were spin-
c
)
and enthalpy of crystallization (∆H ) were calculated from the first for 20 h. It should be noted that no any thermal treatment was
c
cooling run as the onset and the area of the peak in the Heat flow performed in this study. LiF (1 nm) and Al (80 nm) were deposited
-7
versus temperature plots, respectively. The flash crystallization under high vacuum (~ 1 x 10 Torr). The resulting ternary solar cell
temperature (Tcf ) and associated enthalpy of crystallization (∆Hcf have the following structure: Glass / ITO / PEDOT:PSS / P3HT:(3XS)
were identified from the fourth run (second cooling) and quantified SiPc:PC BM / LiF / Al.
)
2
-
6
1
c c
similarly to T and ∆H .
Preparation of devices containing binary blend P3HT:(3XS) -SiPc.
2
Chemical Synthesis
Bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS) -SiPc).
P3HT is first solubilized in 1,2-dichlorobenzene (ODCB) to form a
solution with concentration of 20 mg/ml. The solution was heated
at 45 °C for 2 hours.. The concentration of (3HS) -SiPc, (3BS) -SiPc
2 2
2
3
2,43
(
3HS)
2
-SiPc was synthesized according to the literature.
For
example, the synthesis of (3HS) -SiPc was accomplished by
and (3TS) -SiPc were 11.8 mg/mL, 11.3 mg/mL and 11 mg/mL,
2
2
introducing SiPc-OH
2
(1.82 g, 3.17 mmol), tri-n-hexylchlorosilane
respectively. The resulting solutions were heated at 45 °C
overnight. The active layer was created by spin-coating the mixture
onto the PEDOT:PSS at 1000 rpm for 1 minute. It should be note
that the solution was kept at 45 °C during spin-coating process.
Spin-casting the active layer at lower speed of 500 rpm led to the
film with the visible crystals at the surface (Fig S2-4, Supporting
Information). Also, spin-casting solution at room temperature led to
(10.1 g, 31.7 mmol) and pyridine (182 mL) in a 250 mL three neck
round bottom flask with a reflux condenser and nitrogen inlet. The
mixture was stirred and heated at 115 °C under nitrogen for 5
hours, allowed to cool to room temperature and gravity filtered
resulting in a purple powder residue. The filtrate was concentrated
and precipitated in methanol prior to filtration, yielding a dark blue
powder. (Yield = 41%) Analytics were identical to previously
2
the formation of crystals. Using higher concentration of (3XS) -SiPc
of 16 mg/mL also led to the formation of film with defaults. (See
Figure 4S, Supporting information). A thin layer of bathocuproine
5
reported. Prior to device integration, (3HS)
2
-SiPc was further
purified by vacuum distillation to achieve electronic grade purity.
(
BCP) was deposited on the top of the active layer as buffer layer (7
Bis(tri-n-butylsilyl oxide) silicon phthalocyanine ((3BS)
3BS) -SiPc was synthesized and purified using the same method as
3HS) -SiPc, except reacting SiPc-OH (1.22 g, 2.12 mmol) with tri-n-
2
-SiPc).
nm). The cells were completed by evaporating 80 nm of Ag as top
electrode. The resulting photocells have the following architecture:
(
(
2
2
2
Glass / ITO / PEDOT:PSS / P3HT:(3XS)
2
-SiPc / BCP / Ag. The vacuum
-8
butylchlorosilane (5.0 g, 21.2 mmol) in pyridine (112mL), yielding a
dark blue powder. (Yield = 43%) HRMS (EI) [M] calcd for 971.46,
chamber had a base pressure of ~ 8 x 10 Torr, and a working
-
7
pressure ~ 1 x 10 Torr during deposition of BCP and Ag.
Deposition rate was monitored by quartz crystal microbalance
(QCM, Inficon) calibrated against films deposited on glass with
thicknesses measured by step edge contact profilometry.
1
found 971.5. H NMR: δ = 9.63 to 9.65 ppm (8H, m), 8.30 to 8.33
ppm (8H, m), 0.10 to 0.01 ppm (30H, m), -1.26 to -1.30 ppm (12H,
m) and -2.41 to -2.44 ppm (12H, m).
Bis(tri-n-isopropylsilyl oxide) silicon phthalocyanine ((3TS)
2
-SiPc).
-SiPc was synthesized and purified using the same method as
-SiPc, except reacting SiPc-OH (1.49 g, 2.59 mmol) with tri-n-
Photovoltaic Characterization of Devices.
Voltage characteristics and external quantum efficiencies (EQE)
were obtained under nitrogen atmosphere using simulated solar
(
(
3TS)
3HS)
2
2
2
isopropylchlorosilane (5.0 g, 25.9 mmol) in pyridine (149 mL) for
0h, yielding a dark blue powder. (Yield = 52%) HRMS (EI) [M] calcd
for 887.30, found 887.4. H NMR: δ = 9.62 to 9.65 ppm (8H, m), 8.30 Monochromator with a Keithley 2401 Low Voltage SourceMeter.
light supplied by a 300W Xenon Arc lamp with an Air Mass 1.5
TM
2
Global filter, fed through
a
Cornerstone
260 1 / 4 m
1
to 8.33 ppm (8H, m) and -1.13 to -1.18 ppm (36H, m) and -2.03 to -
.09 ppm (6H, m).
Wavelength scans of the devices were performed and
corresponding currents measured using a Newport Optical Power
Meter 2936-R controlled by TracQ Basic software and the light
2
Fabrication and characterization of photo voltaic devices
intensity was calibrated with reference to
a
UV-silicon
Preparation of substrates. Indium tin oxide (ITO) coated glass photodetector. Each device contained five pixels and the error bars
substrates (Colorado Concept Coatings LLC) were rubbed with found in all device plots and tables correspond to an average of
2
aqueous detergent followed by ultra-sonication in aqueous these pixels. The surface of the active layer is 20 mm .
detergent, deionized water, acetone, and methanol for 5 minutes
each, followed by air plasma treatment for 10 minutes. A thin layer
of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) Results and discussion
TM
(
PEDOT:PSS, Clevios AI 4083) was then spin-coated onto the ITO
glass at subsequent speeds of 500 rpm for 10 seconds and 4000rpm
for 30 seconds, then dried in air at 115 °C on a hot plate for 15 Chemical, Optical and Electrochemical Characterization of (3XS)
2
-
minutes. All the subsequent steps were performed in the controlled SiPc derivatives
atmosphere in the glove box.
Wheeler et al. first synthesized (3HS)
phthalocyanine dichloride ((Cl) -SiPc) into silicon phthalocyanine
dihydroxide ((OH) -SiPc) which was then coupled using chloro tri-n-
2
-SiPc by converting silicon
2
Preparation of photocells containing ternary blend P3HT:(3XS)
2
-
2
SiPc:PC61BM. P3HT, PC61BM and the (3XS)
dissolved in 1,2-dichlorobenzene (ODCB, 40 mg / mL solutions) and 1). The formation of (OH)
-SiPc derivatives were hexylsilane through simply refluxing in pyridine for 5 h (Scheme
2
43
2
-SiPc can be performed with negligible
were stirred at 50 ˚C overnight to ensure complete dissolution of losses in yield however the coupling with tri-n-hexylsilane itself
the solids. The individual solutions were then combined in ratios as gave a total yield of roughly 53%. Since then Gessner et al.
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3
2,33
successfully synthesized (3HS) -SiPc by directly reacting (Cl) -SiPc reported results,
we were able to achieve a device PCE of
2
2
with chloro tri-n-hexylsilane under reflux in chlorobenzene for a few ~3.3%.
hours using Aliquat® HTA-l (trioctyl methyl ammonium chloride), a
Following this set of devices, we then explored the use of
-SiPc and (3TS) -SiPc in place of (3HS) -SiPc. It was observed
yield of as much as 93%. In this study we chose to avoid the use of that the use of both (3BS) -SiPc and (3TS) -SiPc as a ternary additive
phase transfer catalyst. This procedure resulted in an improved (3BS)
2
2
2
44
2
2
Aliquat® HTA-l due to its inevitable presence in the final product resulted in a further but modest increase in JSC of roughly ~10%
and the difficulty associated to its necessary removal prior to when compared to (3HS) -SiPc, while maintaining the increase in
2
3
3–
integration into sensitive organic electronic devices. Honda et al.
V
OC and subsequently
a higher efficiency (Figure 3A). The
3
5
45
and Flora et al.
used (3HS) -SiPc which was purchased from pronounced secondary peak in the EQE at 700 nm confirms that
2
Aldrich, and based on publication date we surmise it was these compounds are also contributing to photogeneration (Figure
synthesized using the method described in the Wheeler et al. study. 3B). Additionally, the increase in the EQE spectrum in the primary
We have previously described our synthetic protocol for range (300-600 nm) indicates that (3BS)
3HS) -SiPc (Figure 1) which follows the Wheeler method.
2
-SiPc and (3TS)
The enabling a further increase in efficiency via the cascade electron
procedure was replicated to synthesize the two chemical variants transfer from P3HT to PC61BM as when using (3HS) -SiPc. This
bis(tri-n-butylsilyl oxide) SiPc ((3BS) -SiPc, Figure 1) and bis(tri-n- increase in EQE over the entire spectra as well as the simultaneous
2
-SiPc are
3
2,43
(
2
2
2
2
isopropylsilyl oxide) SiPc ((3TS) -SiPc, Figure 1). See the increase in JSC and VOC suggests that the SiPc derivatives are in fact
experimental section for details on the synthesis and analysis. This at the interface. When the additive is miscible in the P3HT or the
1
.
2,13
relatively high yielding synthesis requires no formation of PC61BM phase we would expect a drop in VOC and increase in JSC
derivatives/intermediates, contains no hazardous reagents, Corresponding metrics are tabulated in Table 2.
produces little waste and is only 3-steps: characteristics that are in
line with the 12 principles of “green chemistry”/sustainable microscopy (AFM, surface area: 5 × 5 µm ) on films of P3HT:PC61BM
chemical processes. blends incorporating various (3XS) -SiPc (Figure 4). The image of the
Once purified, the compounds were characterized by UV- P3HT:PC61BM blends cast from ODCB in the absence of (3XS) -SiPc
We performed 2D and 3D tapping-mode atomic force
2
2
2
vis absorbance spectroscopy in toluene and the resulting (Figure 4A) reveals coarse chain-like features, which is typical for
characteristic spectra can be found in Figure 2A. The energy gap the mixture of P3HT:PC61BM. The root-means square (RMS)
(E
GAP,Opt) associated to each SiPc derivative was calculated using, roughness of P3HT:PC61BM was found to be 8.45 nm. The blend
GAP,Opt = c*h/ λonset, where c = the speed of light, h = Plank’s films incorporating (3XS) -SiPc (3.7% in weight) showed a rougher
constant and λonset is taken as the onset of the absorption spectra surface relative to that of P3HT:PC61BM. A RMS roughness of 13.1
for each compound. The maximum absorbance (λmax) and EGAP,Opt nm and 12.9 nm was measured for (3HS) -SiPc and (3TS) -SiPc
are outlined in Table 1. As expected, it was found that all three respectively. The highest RMS was found for the mixtures
compounds absorb in the same wavelength range at 600-700 nm incorporating (3BS) -SiPc of 17.7 nm. Rougher actives surface layers
and have nearly identical EGAP,Opt all consistent with previous studies can provide a rougher metal–polymer interface, which can be
E
2
2
2
2
3
1,32
43,46,47
by our group
Electrochemical analysis was performed on both (3BS)
3TS) -SiPc and compared to previously obtained values for (3HS)
and others
.
desirable for efficient charge collection through a larger surface
5
2
2
-SiPc and area. The morphology of the three ternary systems (topography
and phase) shows the similarity, the presence of (3XS) -SiPc as solid
(
2
2
-
2
3
2
SiPc (Figure 2). From the measured half wave potentials, the additives alter the morphology of the blend, which is showed in
highest occupied molecular orbital (HOMO) and lowest unoccupied AFM images in phase (Figure 5). This demonstrates that the three
molecular orbital (LUMO) energy levels can be estimated using (3XS)
2
-SiPcs induce a change in nanomorpholoy of the resulting
48–51
empirical correlations.
Again, as expected, the three SiPc blend in the same way. These results further suggest that an
derivatives have similar electrochemical properties (Table 1). No additional phase is not formed and that the morphology of the
significant changes in photo- or electro-physical properties were P3HT:PC61BM binary mixture is preserved.
therefore observed due to the variation of functional groups from
n-hexyl to n-butyl to isopropyl.
2
P3HT:(3XS) -SiPc binary BHJ OPV devices
As previously mentioned above, we have demonstrated
Baseline P3HT:PC61BM BHJ OPV Devices
the application of SiPcs as electron accepting layers in PHJ OPVs
A series of baseline BHJ OPV devices, where the active layer was a when paired with electron donor materials such as α-
2
2,53–56
1.0:0.8 mixture of P3HT:PC61BM, were repeatedly fabricated sexithiophene.
To the best of our knowledge, the use of SiPcs
throughout the study and used as a point of comparison. The as a sole electron accepting material in place of PC61BM in BHJ OPV
2
devices were found to have an average JSC = 8.8 mA/cm , VOC = 0.55 devices has not yet been reported. As we have found in our
V, FF = 0.60, and PCE = 2.90% (averaged over 6 sets of device runs, previous studied and outlined herein, (3HS)
2
-SiPc and its analogs
each run had a total of 3-4 cells). These results are consistent with have an odd mix of high solubility and the high tendency to
2
,25
efficiencies reported by our group and others.
crystallize. We therefore explored the hypothesis that they may be
able to substitute PC61BM in a solution processed BHJ OPV device.
In an attempt to compare directly against our baseline
P3HT:PC61BM:(3XS) -SiPc ternary BHJ OPV Devices
2
As mentioned in the introduction, Honda et al. previously P3HT:PC61BM, the ratio of P3HT:(3XS)
established that the addition of small amount of (3HS) -SiPc (3.7% concentration of P3HT of 20 mg/mL was used initially. However, the
in weight) to a P3HT:PC61BM BHJ OPV resulted in significant resulting films where highly defective with crystals formed large
2
-SiPc of 1:0.8 and the
2
33
increases in JSC
.
In our previous study, we explored the use of enough to see visually (Figure S5, Supporting Information).
different MPcs as ternary additives and found that none were as Therefore, we decreased the concentration to 11 mg/mL and the
3
2
effective as (3HS) -SiPc. We again replicated our devices with 3.7 resulting films were suitable to make functional devices.
2
wt% (3HS)
2
-SiPc as a ternary additive and similar to the previously
The photovoltaic performance of devices containing P3HT
as donor and (3XS) -SiPc as acceptor are tabulated in Table 3.
2
4
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Compared to the P3HT:PC BM baseline device, the P3HT:(3XS) - (3HS) -SiPc. Each compound has similar π-π stacking arrangements
6
1
2
2
SiPc devices gave a higher VOC, while even though a substantially with only a slight change in overall density of 1.204 g/mol and 1.251
reduced Jsc limited their overall efficiency. The best performances g/mol for (3HS) -SiPc and (3BS) -SiPc respectively. The single crystal
2
2
have been obtained for devices prepared with (3TS)
2
-SiPc as diffraction of (3TS)
2
-SiPc proved to be less straightforward. Very
acceptor, resulting from higher VOC and JSC.
large (apparent) crystals, often in the mm range, were grown from
Figure 6B shows the external quantum efficiency (EQE) of binary various techniques, such as evaporation from pyridine, vapour
devices. Compared to the P3HT:PC BM devices, an EQE peak at diffusion of heptane into THF and others (pictures of some of the
61
700 nm was observed, which corresponds to the absorbance of SiPc specimens can be found in the supporting information, Figure S6).
(
Figure 6C), suggesting indicating that the (3XS) -SiPc does in fact In all cases, these exceptionally large (apparent) crystals would
2
contribute to photogeneration. These results illustrate that SiPc can crumble rather than split into pieces and no characteristic X-ray
act as electron acceptor molecules in fullerene-free BHJ OPV diffractions could be obtained from any of the fractions. In addition
devices. The devices composed of P3HT and (3TS)
highest EQE, resulting to the highest current density. The UV-Vis that these molecules may not pack periodically. Therefore, the solid
absorption of the P3HT:(3XS) -SiPc films show similar features. The state arrangements could not be characterized for (3TS) -SiPc.
absorption of film containing P3HT:(3TS) -SiPc exhibits a slight These results represent the beginning of a structure property
2
-SiPc showed the to frustrating the X-ray crystallographer, these observations suggest
2
2
2
redshift as compared to those of P3HT:(3HS)
2
-SiPc and P3HT:(3BS)
2
-
relationship and as our groups develop additional families of SiPc
SiPc which is comparable to the EQE spectrum, but the reason is not derivatives we will be able to more clearly correlate the crystal
clear. AFM was used to identify a possible reason for the improved diffraction patterns to OPV performance.
performance of P3HT:(3TS)
P3HT:(3HS) -SiPc. Figure 7A elucidates the topology and the phase
images of P3HT:(3HS)
-SiPc films. Significant phase separation took X-ray diffraction (XRD) of the thin solid films
place as evidence by the relatively large domains which were X-ray diffraction (XRD) was performed on spun cast thin solid films
formed on the microscale size (1 µm × 0.500 µm). We determined of both P3HT:(3XS) -SiPc binary mixtures and P3HT:PC61BM:(3XS)
the RMS roughness = 21.2 nm. When using (3BS)
-SiPc we observed SiPc ternary mixtures (Figure 9A). The concentrations, compositions
smaller square domains on the order of 150 nm (Figure 7B), and and spin rates used were identical to those used to make the
when using (3TS)
-SiPc no significant crystal were identified (Figure respective BHJ OPV devices found in Table 3. All films experienced a
C). Thin films prepared using (3BS) -SiPc and (3TS)
-SiPc exhibit primary diffraction peak at 2θ = 5.46° which corresponds to the d-
smoothers surfaces compared to (3HS)
-SiPc with RMS = 12.9 nm spacing of P3HT at (d = 1.62 nm).
and 9.43 nm, respectively. These results suggest that smaller only the primary peak for P3HT was observed with no significant
domain sizes afforded by the use of (3BS) -SiPc and (3TS)
-SiPc peaks associated to PC61BM. This has been well reported and
2 2
-SiPc and P3HT:(3BS) -SiPc over
2
2
2
2
-
2
2
7
2
2
5
9,60
For the P3HT:PC61BM films
2
2
2
3
7
could be the reason for their improved performance over (3HS)
SiPc.
2
-
understood as neat films of PC61BM are known to be amorphous.
However, under the same conditions, when substituting the
-SiPcs, a secondary sharp crystalline diffraction
While these device efficiencies are not record-breaking it is PC61BM for a (3XS)
2
important to note that they show tremendous promise. This is the is observed in the XRD patterns. In all films (Figure 9A) the P3HT
first report of their use in OPVs which suggest a great deal of diffraction is roughly the same intensity while the intensity of SiPc
improvement in device performance can be expected through changes with chemical structure. For example, (3HS)
future molecular design and device optimization. Secondly, it is well diffraction, with a larger d = 1.32 nm compared to (3BS)
known that the synthesis of PC61BM and other low band gap where d = 0.99 nm and (3TS) -SiPc, d = 1.03 nm (Figure 9B). The
polymers are extremely energy intensive due to the numerous fwhm (full width half max) of (3HS) -SiPc (0.21°) and (3BS) -SiPc the
(0.19°) are very small and much smaller than P3HT (1.04°),
Phthalocyanines, however, require a fraction of the energy to indicating strong (3XS) -SiPc crystalline domains even when mixed
synthesize and purify due to the limited required synthetic steps with P3HT. These results are consistent with the idea that (3HS)
2
-SiPc exhibits a
2
-SiPc,
2
2
2
3
,4
complex synthetic steps and low yielding purifications.
2
2
-
3
2
and straight forward purification procedures. For example, Anctil et SiPc has a strong driving force for crystallization. These results are
al. have shown zinc phthalocyanine and copper phthalocyanine interesting when compared to the OPV device performance: (3BS)
require 70-120 times less energy to produce than PC61BM and 105- SiPc and (3TS) -SiPc were characterized by having higher density
73 times less energy to produce than PC71BM. These findings crystallites (smaller d-spacing) compared to (3HS) -SiPc and both
2
-
2
3,4
1
2
suggest that while SiPc derivatives are not yet outperforming resulted in increased device efficiency as a ternary additive or as a
PC61BM, they do merit further investigation. This leads to the PCBM substitute. We surmise that the tendency to form larger
question of direction in molecular design and engineering of (3XS)
SiPcs.
2
-
crystallites may be the reason (3HS)
compared to the new derivatives. That being said, Figure 9B
illustrates the XRD patterns of P3HT:P61BM:(3XS) -SiPc ternary films.
None of the ternary mixtures exhibited the sharp crystalline peaks
For reference, during our previous study, large single crystals of observed in the binary mixture. While it is likely that at this loading
3HS)
-SiPc were grown by slow evaporation from pyridine and (3.7 wt%) the signal is too weak to observe, Oku et al. have
diffracted by X-ray crystallography,
state arrangements to other soluble SiPc derivatives. While SiPc molecules are at the P3HT:PC61BM interfaces. In all cases the
synthesizing and purifying (3BS)
-SiPc we found that, similar to P3HT diffraction is similar and no peaks corresponding to the SiPc
3HS)
-SiPc, the compound had a strong tendency to crystalize. was observed, suggesting that the overall P3HT:PC61BM crystallinity
Crystals of (3BS)
-SiPc (CCDC#: 1522758) were also grown by the is preserved regardless of the (3XS) -SiPc additive.
same method, and displayed a similar crystal packing motif and
2
-SiPc is underperforming
2
2
X-ray diffraction (XRD) of (3XS) -SiPc single crystals.
(
2
3
2
and had comparable solid hypothesized that the absence of peak is in fact indication that the
57
37
2
(
2
2
2
32,51,58
crystal densities to (3HS)
2
-SiPc.
Figure 8 illustrates the Thermal characterization
characteristic solid state arrangements of both (3BS) -SiPc and
2
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ARTICLE
Journal Name
Using thermogravimetric analysis (TGA), the thermal decomposition
Secondly, binary P3HT:(3XS) -SiPc BHJ OPV devices using
2
temperature (T
S1). In all cases, similar degradation profiles were obtained, 0.25% and 0.78% and 1.07% respectively. An increase in VOC over
resulting in T = 318 °C, 342 °C and 375 °C for (3BS) -SiPc, (3HS) the P3HT:PC61BM baseline devices was observed, and despite the
d 2 2 2
) was obtained for all three SiPc derivatives (Figure (3HS) -SiPc, (3BS) -SiPc, and (3TS) -SiPc achieving efficiencies of
d
2
2
-
SiPc and (3TS) -SiPc respectively (Figure 10). In attempts to gain a relatively low overall efficiencies this result exemplifies the
2
better insight into the melting and crystallization characteristics of potential for SiPc as an electron acceptor in solution processed BHJ
these SiPc molecules differential scanning calorimetry (DSC) was OPV devices. It is also important to note that (3BS) -SiPc and (3TS) -
2
2
used to characterize all three SiPc derivatives resulting in the SiPc outperforms (3HS)
2
-SiPc as acceptors and as an additive. It is
identification of the melting temperature (T ), enthalpy of melting also important to note that phthalocyanine, such as these SiPc
m
(∆H
m
), crystallization temperature (T
c
)
and enthalpy of derivatives, require 2-orders of magnitude less energy to synthesize
crystallization (∆H ) were calculated from the heat flow versus compared to PC BM due to the limited required synthetic steps
c
61
temperature plots represented in Figure 10 and can be found in and the straight forward purification procedures. These findings
Table 4.
For (3HS)
suggest that while SiPc derivatives are not yet outperforming
-SiPc a single transition was observed between 0 °C PC61BM, their use merits further investigation as a greener
2
and 275 °C, where T < T and ∆H ≈ ∆H , which is consistent with a sustainable alternative overall to PC BM.
c
m
c
m
61
common undercooling effect. (3BS)
2
-SiPc appears to have two
XRD of the resulting devices exhibited a consistent and
similar and distinct transitions consistent with two melt / crystalize characteristic signal corresponding to P3HT in all the binary and
transitions (Figure 10, Table 4). The first transition (≈ 60 °C) ternary devices. In the binary devices, we see a second sharp and
experienced a smaller ∆H
transition (≈ 220-230 °C) has a greater ∆H
contrast, (3TS) -SiPc had no discernable transitions between 0 °C P3HT. Maybe even more interesting the d-spacing suggests that
and 275 °C, which is perhaps consistent with the fact that it is not (3BS) -SiPc and (3TS) -SiPc have higher density crystallites (smaller
diffractable material as outlined above. It is important to note that d-spacing) compared to (3HS) -SiPc. Therefore, we surmise that the
even when flash cooling the samples (-100 °C / min) the same tendency to form smaller crystallites may be the reason (3BS) -SiPc
transitions were observed, albeit at slightly lower temperatures, and (3TS) -SiPc are superior additives to (3HS) -SiPc.
which is expected with the increase in cooling rate (Table 4). The Thermogravimetric analysis confirmed that both (3BS) -SiPc and
DSC results confirm that both (3BS) -SiPc and (3HS) -SiPc have a (3HS) -SiPc have a thermodynamic tendency to crystalize at both
thermodynamic tendency to crystalize at both slow and fast cooling slow and fast cooling rates.
rates, while the kinetics of nucleation growth is will admittedly The results from this study suggest that solubility and
dependent on the system. This confirms our original hypothesis for driving force to crystalize are important factors in determining the
3HS) -SiPc. It also perhaps begins to form some design rules extent to which an additive will migrate to the donor/acceptor
c
≈ ∆H
m
2
≈ 26 J / g while the second intense peak corresponding to (3XS) -SiPc. The peaks indicate that
c
≈ ∆H ≈ 31-36 J / g. In (3XS) -SiPc has a tendency to crystalize even when blended with
m
2
2
2
2
2
2
2
2
2
2
2
2
(
2
around the molecular design for these types of SiPcs for the interface and thus increase device performance. However, it is
applications outlined herein. Further analysis into nucleation rates currently unclear as to exactly how the crystallization affects the
and processing conditions would be required to fully quantify the migration of the additive to the interface. Future work will be
tendency to crystalize from a solution of organic solvent, P3HT and conducted to build a larger library of SiPc derivatives in attempt to
PC61BM. As mentioned above, these results represent the beginning better understand what structural fragments and chemical
of
a structure property relationship and with the further properties are responsible for improving the performance of a
2
development of SiPc derivatives we likely will be able to correlate certain (3XS) -SiPc for BHJ OPV application(s).
thermal characterization with XRD and OPV performance.
Acknowledgements
Conclusions
This work was supported by a Natural Sciences and Engineer
In this study we have confirmed our previous result that the use of Research Council (NSERC) Banting Post-Doctoral fellowship to BHL
3HS) -SiPc as a ternary additive in P3HT:PC BM BHJ OPV device and a Discovery Grant to TPB.
(
2
61
can achieve efficiencies of up to 3.3%. We then synthesized two
chemical variants of (3HS) -SiPc (trihexyl), namely (3BS) -SiPc
2
2
(
tributyl) and (3TS)
2
-SiPc (triisopropyl), and explored their chemical Notes and references
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electron acceptors in fullerene-free BHJs and as solid ternary
additives in P3HT:PC BM:(3XS) -SiPc BHJ OPV devices. No
significant change in their respective UV-Vis absorption spectrum or
electrochemical analysis was observed between (3TS) -SiPc, (3BS) -
‡
Pictures of (3TS)
thermo gravimetric analysis (TGA) obtained from powders of
3XS) -SiPc and photographs of the thin film composed of
P3HTand (3XS) -SiPc can be found in the ESI.
2
-SiPc crystals grown by various techniques,
6
1
2
(
2
2
2
2
SiPc and (3HS)
2
-SiPc.
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ARTICLE
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1
Figure 1. Energy level diagram and chemical structure of poly(3-hexylthiophene) (P3HT), bis(tri-n-hexylsilyl oxide) silicon phthalocyanine
(3HS) -SiPc), bis(tri-n-butylsilyl oxide) silicon phthalocyanine ((3BS) -SiPc), bis(tri-n-isopropylsilyl oxide) silicon phthalocyanine ((3TS) -SiPc),
(
2
2
2
and phenyl-C61-butyric acid methyl ester (PC61BM). The energy levels of the HOMOs and LUMOs were either taken from the literature or
derived from electrochemistry (Table 1).
Scheme 1. Chemical synthesis scheme for (3HS) -SiPc, (3BS) -SiPc or (3TS) -SiPc, where (i) SiCl (1.5 x molar excess), quinoline, 219 ºC, 30
2
2
2
4
min; (ii) CsOH (50% in water), DMF, 120 °C for 4 h and (iii) chlorosilane derivative (R
3
-Si-Cl, 5x molar excess), pyridine, 130 °C for 5 h.
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Figure 2. A) Normalized UV-vis absorbance and B) Electrochemical spectra for (3BS) -SiPc and (3TS) -SiPc. The inset in Figure A is a close up
2
2
2
of the scaled absorption peaks between 650 nm and 690 nm. As a comparison, the absorption of (3HS) -SiPc was added to Figure A.
Table 1. Electrochemical and UV-vis Characterization of (3HS)
2
-SiPc, (3BS)
2
2
-SiPc, and (3TS) -SiPc.
a
b
c
d
SiPc derivatives
ERED,1 / 2
V)
EOX,1 / 2
EHOMO
ELUMO
λmax
Egap,Opt
(
(V)
(eV)
(eV)
(nm)
(eV)
e
(
(
(
3HS)
3BS)
3TS)
2
-SiPc
-0.85
-0.84
1.04
1.04
1.11
-5.31
-3.42 / -3.49
-3.43 / -3.49
-3.51 / -3.56
669
669
671
1.82
1.82
1.82
2
-SiPc
-5.31
-5.38
2
-SiPc
-13.4, -0.76
a
b
c
48–51
E
HOMO = -(4.27 + EOX, 1 / 2) eV (scaled to an internal standard of decamethylferrocene)
E
LUMO,Electro
LUMO,Opt Gap,Opt HOMO
/ ELUMO,Opt where ELUMO,Electro = -(4.27 + ERed, 1 / 2) and E = E - E
Maximum absorbance, λmax
,
of respective compounds dissolved in toluene.
d
e
EGap,Opt determined from the onset of the solution absorbance spectra
32
The values associated with (3HS)
2
-SiPc were taken from the literature as a comparison.
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Figure 3. A) Characteristic of current density versus voltage (JV) and B) External quantum efficiency (EQE) versus wavelength for device
containing P3HT:PC61BM:(3XS) -SiPc (weight ratio: 1.0:0.8:0.07). The error bars in A are the 95% confidence interval of 5-10 devices.
2
Table 2. The photovoltaic performance of P3HT:PC61BM devices incorporating (3XS)
2
-SiPc as additives.
a)
b)
P3HT:PC61BM:X
Additives
JSC
VOC
(V)
FF
PCE
%)
2
(
(
mA / cm )
7.8 ± 0.1
9.2 ± 0.3
1
:0.8:0
-
0.56 ± 0.01
0.56 ± 0.01
0.60 ± 0.01
0.63 ± 0.02
2.61 ± 0.04
3.29 ± 0.07
1
1
1
:0.8:0.07
:0.8:0.07
:0.8:0.07
(3HS) -SiPc
2
(3BS) -SiPc
10.0 ± 0.3
10.1 ± 0.4
0.56 ± 0.01
0.57 ± 0.01
0.59 ± 0.01
0.60 ± 0.02
3.30 ± 0.10
3.40 ± 0.10
2
(3TS) -SiPc
2
a) Mass ratio used to fabricate the active layer of the bulk heterojunction organic photovoltaic (BHJ-OPV) devices, where P3HT represents
poly(3-hexylthiophene), PC61BM represents phenyl-C61-butyric acid methyl ester and X represents (3XS) -SiPc = bis(tri- -hexylsilyl oxide)
silicon phthalocyanine ((3HS) -SiPc), bis(tri- -butylsilyl oxide) silicon phthalocyanine ((3BS) -SiPc) or bis(tri- -isopropylsilyl oxide) silicon
2
n
n
n
2
2
2 2
phthalocyanine ((3TS) -SiPc). 1:0.8:0.07 corresponds to a 3.7 wt% loading of (3XS) -SiPc.
b) identifies which (3XS)
2
-SiPc was used in the fabrication of the BHJ OPV device.
In all cases experiments the values were averaged with a minimum of 4-5 devices in the case of the P3HT:PC BM baseline, the values were
6
1
averaged over a minimum of 46 devices fabricated over the span of 12-16 weeks in the same apparatus. The values were obtained under
-2
AM1.5G irradiation at 100 mWcm .
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Figure 4. Two and three dimensional of topographic AFM images of the surfaces of photoactive layers : A) P3HT:PCBM (RRMS = 8.45 nm), B)
P3HT:PCBM:(3HS) -SiPc (RRMS = 13.1 nm), and C) P3HT:PCBM:(3BS) -SiPc (RRMS = 17.7 nm), and D) P3HT:PCBM:(3TS) -SiPc (RRMS = 12.9 nm)
2
2
2
1
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2 2
Figure 5. AFM phase images of the surfaces of photoactive layers : A) P3HT:PCBM, B) P3HT:PCBM:(3HS) -SiPc, C) P3HT:PCBM:(3BS) -SiPc,
and D) P3HT:PCBM:(3TS) -SiPc
2
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2
Table 3 The photovoltaic performance of devices containing binary blend P3HT:(3XS) -SiPc
Donor:Acceptor
V
OC
J
SC
FF
PCE
2
(
V)
(mA / cm )
0.99 ± 0.17
2.61 ± 0.26
3.00 ± 0.18
(%)
P3HT:(3HS)
2
-SiPc
0.70 ± 0.06
0.75 ± 0.03
0.84 ± 0.01
0.37 ± 0.02
0.40 ± 0.03
0.43 ± 0.01
0.25 ± 0.05
0.78 ± 0.07
1.07 ± 0.05
P3HT:(3BS) -SiPc
2
2
P3HT:(3TS) -SiPc
a) Bulk heterojunction organic photovoltaic (BHJ-OPV) devices, where P3HT represents Poly(3-hexylthiophene) and (3XS) -SiPc =
2
bis(tri-
bis(tri-
n
-hexylsilyl oxide) silicon phthalocyanine ((3HS)
2 2
-SiPc), bis(tri-n-butylsilyl oxide) silicon phthalocyanine ((3BS) -SiPc) or
n-isopropylsilyl oxide) silicon phthalocyanine ((3TS) -SiPc). In all cases experiments the values were averaged with a
2
-2
minimum of 4-5 devices obtained under AM1.5G irradiation at 100 mWcm .
Figure 6. (A) Characteristic current density versus voltage (JV); ( B) external quantum efficiency (EQE) versus wavelength, and (C) UV-Vis
2
absorption spectrum of P3HT:(3XS) -SiPc thin films .
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Figure 7. Height (left) and phase (right) AFM images of the surfaces of photoactive layers: A) P3HT:(3HS)
P3HT:(3TS) -SiPc.
2 2
-SiPc, B) P3HT:(3BS) -SiPc, and C)
2
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3
2,51,58
Figure 8. Solid state arrangements for (3HS) -SiPc (A, B)
, and for (3BS) -SiPc (C, D) obtained from X-ray diffraction (CCDC#: 1522758).
2
2
1
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Figure 9. Powder X-ray diffraction (XRD) patterns of spun cast thin films of A) P3HT:(3XS) -SiPc binary mixtures and B) P3HT:PC BM:(3XS) -
2
61
2
SiPc ternary mixtures. The mixture compositions are the same as those used in the BHJ OPV devices represented in Table 2,3.
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Figure 10. Differential scanning calorimetry (DSC) obtained from powders of (3HS)
DSC was performed using the following profile: first heat to 275 °C at a rate of +5 C / min followed by A) a first cooling to 0
B) a second heat to 275 C (+5 C / min), C) a flash cooling to 0 C (-100 C / min), a third heat to 275 C (not shown, +5 C / min) and a final
cooling to 0 ºC (not shown, -5 C / min).
2
-SiPc (green), (3BS)
2
-SiPc (red) and (3TS)
2
-SiPc (blue).
°
°
C (-5
°
C / min),
°
°
°
°
°
°
°
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Table 4. Thermodynamic Characterization of (3HS)
2
-SiPc, (3BS)
2
2
-SiPc, and (3TS) -SiPc
a
b
b
b
b
SiPc derivatives
Td
Tm
∆Hm
Tc
∆Hc
Tcf
∆Hcf
(
ºC)
(ºC)
173
(J / g)
(ºC)
(J / g)
23.5
(ºC)
(J / g)
(
(
(
3HS)
3BS)
3TS)
2
-SiPc
342
318
375
26.9
110
103
200 / 54
-
19.9
2
-SiPc
231 / 61
-
36.1 / 25.7
-
219 / 63
30.7 / 26.5
-
30.6 / 27.7
-
2
-SiPc
-
a
b
Degradation temperature ( d
T
) was determined at 5% weight loss using thermo-gravimetric analysis (TGA).
and crystallization temperature (Tc) and and enthalpy of crystallization (∆Hc)
Melting temperature ( m) and enthalpy of melting (∆Hm
T
)
,
were obtained from the second heat and second cool, respectively, using differential scanning calorimetry (DSC). Both the heat and cooling
runs were performed at 5 C / min. Tm and Tc are calculated as the onset of melting and of crystallization, respectively. A final run was
performed at -100 °C / min and the flash crystallization temperature (Tcf) and associated enthalpy of crystallization (∆Hcf) were identified.
°
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2
28x96mm (150 x 150 DPI)