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Impact of molecular quadrupole moments

on the energy levels at organic heterojunctions
Martin Schwarze 1, Karl Sebastian Schellhammer2,3, Katrin Ortstein 1, Johannes Benduhn 1,
Christopher Gaul 3, Alexander Hinderhofer4, Lorena Perdigón Toro 5, Reinhard Scholz1, Jonas Kublitski 1,
Steffen Roland5, Matthias Lau1, Carl Poelking6, Denis Andrienko 6, Gianaurelio Cuniberti 2, Frank Schreiber4,
Dieter Neher 5, Koen Vandewal 1,7, Frank Ortmann 3 & Karl Leo 1
1234567890():,;

The functionality of organic semiconductor devices crucially depends on molecular energies,

namely the ionisation energy and the electron affinity. Ionisation energy and electron affinity
values of thin films are, however, sensitive to film morphology and composition, making
their prediction challenging. In a combined experimental and simulation study on zinc-
phthalocyanine and its fluorinated derivatives, we show that changes in ionisation energy as a
function of molecular orientation in neat films or mixing ratio in blends are proportional to the
molecular quadrupole component along the π-π-stacking direction. We apply these findings
to organic solar cells and demonstrate how the electrostatic interactions can be tuned to
optimise the energy of the charge-transfer state at the donor−acceptor interface and the
dissociation barrier for free charge carrier generation. The confirmation of the correlation
between interfacial energies and quadrupole moments for other materials indicates its
relevance for small molecules and polymers.

1 Dresden Integrated Center for Applied Physics and Photonic Materials (IAPP), Technische Universität Dresden, 01069 Dresden, Germany. 2 Institute for

Materials Science, Max-Bergmann Center of Biomaterials and Dresden Center for Computational Materials Science, Technische Universität Dresden, 01069
Dresden, Germany. 3 Center for Advancing Electronics Dresden, Technische Universität Dresden, 01069 Dresden, Germany. 4 Institute of Applied Physics,
University of Tübingen, Auf der Morgenstelle 10, 72076 Tübingen, Germany. 5 Institute of Physics and Astronomy, University of Potsdam, Karl-Liebknecht-
Str. 24–25, 14476 Potsdam, Germany. 6 Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany. 7Present address: Instituut
voor Materiaalonderzoek (IMO), Hasselt University, Wetenschapspark 1, 3590 Diepenbeek, Belgium. Correspondence and requests for materials should be
addressed to M.S. (email: [email protected]) or to F.O. (email: [email protected]) or to K.L. (email: [email protected])

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O
rganic semiconductors gained much attention because of excess charges with static charge distributions and shifts IE and
their attractive application in low-cost, large area, and EA equally17–20. We concentrate on the permanent contribution
flexible electronic devices1–4. While organic light- in this study, which is often dominated by the charge−quadru-
emitting diodes (OLEDs) already entered the market in thin pole term in the multipole expansion because molecules with
film displays, several other promising applications such as solar dipole moments often stack with alternating molecular orienta-
cells, transistors, photodetectors, or lasers still require improve- tions in ordered organic solids16,18. In this case, the permanent
ments in performance. In contrast to their inorganic counter- contribution can be approximated by a sum over the interaction
parts, organic semiconductors typically consist of weakly bound energies of a charged molecule, described by its atomic excess
molecules, where charge carriers occupy rather localised states. charges qj at positions rj, with the quadrupole tensors Qi of all
Associated to these states are the ionisation energy (IE) and surrounding molecules at sites ri 27:
electron affinity (EA) of organic molecules, which are related to    
the transport energies of holes and electrons and, consequently, X qj r i  rj  Q i  ri  rj
determine the functionality of electronic devices5,6. EQ ¼   5 ; ð1Þ
8πϵ0 ϵr  
In organic solar cells (OSCs), fundamental processes deter- i;j  ri  rj 
mining the device performance are the dissociation of charge-
transfer (CT) states at the donor−acceptor interface into free where we use the dielectric permittivity εr as a macroscopic
charges and their non-geminate recombination via CT states back constant. We describe the charged molecule by its actual dis-
to the ground state7–9. Therefore, the CT state energy (ECT) tribution of atomic charges to have an appropriate description at
determines the open-circuit voltage (Voc) of OSCs10, while its distances in the range or below the spatial extent of molecules.
difference to the energy of separated charges (ECS) influences the Due to the strong dependence of EQ on distance, EQ changes
generation efficiency of free charge carriers and, thus, crucially with the chemical and crystal structure of the compound. Like
affects both the short-circuit current density (jsc) and the fill- many other planar molecules, FnZnPc typically arranges in a π
factor (FF)11,12. Both ECT and ECS are linked to IE of the donor −π-stacking geometry28,29, where the intermolecular distance
and EA of the acceptor. along the stacking direction (approximately 3.8 Å 28) is signifi-
IE and EA of molecules in organic films significantly depend cantly smaller than along the other two directions (13−14.5 Å 30).
on molecular orientation and mixing ratio in blends13–15. In Therefore, we first investigate if the quadrupole component
particular, charge−quadrupole interaction can induce large perpendicular to the molecular plane (Qπ) dominates EQ (see
electrostatic shifts of the electronic levels in crystalline films16–19, Fig. 1 for Qπ values) by analysing for FnZnPc layers (20 nm) the
which, for example, allows in blends with molecular intermixing, difference in IE between face-on and edge-on orientation of the
a continuous tuning of IE and EA by adjusting the ratio of two molecules (Fig. 2a, see Supplementary Figs. 1–3 and Supplemen-
different molecular species20,21. Furthermore, simulations indi- tary Note 1 for X-ray scattering results). The representative UPS
cated that these interactions can assist the dissociation of CT spectra in Fig. 2b show that IE of a ZnPc film in edge-on
states at planar donor−acceptor interfaces22,23. However, it orientation is 0.22 eV smaller as compared to the film in face-on
remains an open question to which extent such findings for these orientation, in agreement with previous results13. In contrast,
model systems are general and, particularly, how they are F8ZnPc exhibits an IE value in edge-on orientation that is 0.37 eV
applicable to donor:acceptor blends without long-range order larger than the IE value in face-on orientation. To connect this
which are usually employed in efficient OSCs. behaviour to molecular properties, we calculate Qπ by density
In this study, we demonstrate the tunability of the solid-state IE functional theory (DFT) for ZnPc and its fluorinated derivatives
by charge−quadrupole interactions and their relevance in sys- (results in Supplementary Table 1). As displayed in Fig. 2c, the
tems with long-range and short-range order, being, thus, relevant difference in IE between edge-on and face-on orientation
for most organic devices. As a model system, we choose zinc- increases with Qπ from ZnPc to F16ZnPc.
phthalocyanine (ZnPc) because of the possibility to gradually To prove that Qπ dominates in EQ (see Eq. 1), we calculate EQ
change its quadrupole moment (QPM) by stepwise fluorination for a single charged molecule at the film surface for both
(FnZnPc)20. In order to establish the role of the quadrupole orientations (see Methods and Supplementary Fig. 4). The
component perpendicular to the molecular plane (Qπ), we mea- difference in EQ between both orientations exhibits the same
sure for FnZnPc the change in IE with molecular orientation, film correlation with Qπ as observed for the IE difference in
thickness, and mixing ratio in blends. The ultraviolet photoelec- experiment (Fig. 2c). Interestingly, the simulations reveal that
tron spectroscopy (UPS) analysis reveals a linear change of IE the relevant range of charge−quadrupole interactions is different
with Qπ in all cases. Moreover, when applying these findings to between both molecular orientations (Supplementary Fig. 5). For
OSCs, we demonstrate how QPMs influence ECT at planar and edge-on orientation, EQ is dominated by interactions between the
bulk heterojunctions between donor and acceptor. Time-delayed next few neighbours along the π−π-stacking geometry. For face-
collection field (TDCF) measurements further show that elec- on orientation, EQ is also dominated by interactions with Qπ
trostatic gradients induced by QPMs can assist free charge carrier components at small integration limits, which however is
generation in these solar cells. Finally, we extend the study to compensated by the interaction with other components when
other material systems, indicating the relevance of the findings for the integration limit in the lateral direction becomes larger
a large variety of organic semiconductors. than 100 nm. Previous investigations indicate that the interaction
with other components than Qπ can be even more dominant in
face-on orientation for molecules with a different symmetry than
Results FnZnPc such as pentacene, having two molecular short axes19,31.
Dependence of thin flm energies on the component Qπ. IE and In the absence of long-range order, such as in donor:acceptor
EA of molecules in thin films deviate from their gas-phase values, blends with crystal sizes much smaller than 100 nm, the
IE0 and EA0, due to polarisation effects24–26. In weakly bound interaction of charges with Qπ components should dominate32–34.
solids with localised states, the electrostatic corrections (Δ+ and To further verify the dominance of charge−quadrupole
Δ−) to the gas-phase values consist of an induced and a perma- interactions along the π−π-stacking direction for edge-on
nent contribution. While the first term decreases the distance orientation, we measure IE of FnZnPc for coverages below the
between IE and EA, the latter originates from the interaction of monolayer thickness and evaporate the material stepwise onto

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F F 3
4
2
F F F F F
1 F
3
F
2
N N F F F F
N
1 4 N N
N N F N N
N N F F
N Zn N N N N N N N
N Zn N Zn
N N Zn N N Zn N
N N N N N
F N
4 1 N N N
F F
N N N
3 2 N N
1 4 F F F F
F 2 3 F
F
ZnPc (–57.6 ea 02) F
F4*ZnPc (–41.6 ea0 2) F4ZnPc (–2.5 ea02) F F F
F
F
F F F8ZnPc (49.0 ea02) F16ZnPc (72.0 ea02)
F F F F
F F F F
N
N
F F F F
N N
N N N N
N Cu N
N Cu N N N
N N
F F N N
N N
N F N N F
N F F F N N F
C60 (0 ea 02)
F F
F F F N N F
F F
CuPc (–59.8 ea02) F16CuPc (72.0 ea02) HATNA-F6 (21.8 ea02)
F F F F
HATNA-F12 (45.2 ea02)
S S S
C6H13 C6H13
S S S
+
DH6T (–94.9 ea02) S S S
N
B
- N

DIP (–55.5 ea 02) S S S F F

PEN (–40.8 ea 02) alpha-6T (–66.5 ea02) bDIP (–32.5 ea 02)

Fig. 1 Chemical structures and quadrupole components of small molecules: Values in brackets are the quadrupole components perpendicular to the
molecular plane (Qπ), as calculated with density functional theory (DFT). Supplementary Table 1 summarises the in-plane quadrupole components. F4ZnPc
is a mixture of different isomers, where the fluorine atom is bonded to one of the two outer carbon positions (2 or 3)20

p-doped BPAPF, leading to an edge-on orientation in thin films acceptor molecules interact electrostatically with the other
(Supplementary Figure 6). IE at very small coverages, denoted as species despite the phase separation in these blends. The larger
IEs, deviates strongly from the value of thick layers (see dotted IE change of F8ZnPc at higher C60 contents indicates that F8ZnPc
lines in Fig. 2d). Notably, for all ZnPc derivatives, IEs is reduced by molecules which are closer to C60 molecules experience a larger
0.6 eV compared to their respective gas-phase ionisation energies electrostatic shift.
IE0, indicating minor influence of charge−quadrupole interactions To validate that the electrostatic changes originate from charge
on IE at low coverages. With increasing layer thickness, IE −quadrupole interactions, we compare the behaviour of F8ZnPc:
strongly changes and approaches the value of a thick edge-on C60 blends to previously reported ZnPc:C60 blends13, as ZnPc and
oriented film when the monolayer thickness (13−14.5 Å 30) is F8ZnPc exhibit a similar magnitude but a different sign of Qπ.
reached. The strong IE shift can be explained by the formation of Figure 3b shows the electrostatic correction Δ+ of IE for ZnPc
an ordered monolayer in edge-on orientation, leading to an and F8ZnPc blended with C60. While Δ+ differs strongly between
increase of the magnitude of EQ due to charge−quadrupole ZnPc and F8ZnPc in pure layers, this difference reduces
interactions along the π−π-stacking direction. In good agree- continuously with increasing C60 concentration, and Δ+ finally
ment, the change of IE scales with the Qπ value of the respective approaches −0.6 eV. This value is also observed for very small
ZnPc derivative (Supplementary Fig. 6c). Note that the change coverages of (F8)ZnPc, indicating that the charge−quadrupole
in IE until the first edge-on monolayer is formed can occur for interaction energy EQ approaches 0 for high C60 contents (see
different growth modes, such as island growth or transition of Fig. 2d for comparison). Therefore, we attribute the decrease
molecular orientation from face-on to edge-on. (increase) of IE of F8ZnPc (ZnPc) with increasing C60 content
After having demonstrated the strong effect of Qπ on the to the interaction of charges with a reduced number of Qπ
energy levels in model systems based on ZnPc derivatives, we components of the donor.
further analyse its impact in donor:acceptor blends which are The dominance of charge−quadrupole interactions along the π
typically used in OSCs. Such blended structures usually exhibit −π-stacking direction is attributed to the shorter intermolecular
significant structural disorder and phase separation that both can distance in this direction for the ZnPc derivatives. To verify
change with mixing ratio13,32,35,36. Previous studies found whether this simple model is also valid for other materials, we
changes of energy levels with donor:acceptor mixing ratio, which extend our investigation to other molecules that show a strong
were assigned to changes in crystal size and to electrostatic dependence of IE on molecular orientation in neat films13,14,38–41
changes13,15,37. We trace back these energetic changes to the or on mixing ratio in donor:acceptor blends15,37 (see Fig. 1 for
influence of the molecular tuning parameter Qπ. chemical structures). We calculate their QPMs and observe that
We measure the energy levels of F8ZnPc:C60 blends at different for both cases the change in IE scales linearly with the respective
mixing ratios (see UPS spectra in Supplementary Fig. 7). As Qπ (Supplementary Fig. 8). Notably, the slope is surprisingly
shown in Fig. 3a, IE of F8ZnPc decreases by more than similar to the one observed for intermixed blends of different
300 meV with increasing C60 content. IE of C60 shows a similar ZnPc derivatives20 (Supplementary Fig. 9). Charge−quadrupole
change, which suggests that a large amount of donor and interactions are also relevant for polymers. Similar to

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a ZnPc/F4ZnPc F16ZnPc c
0.6 0.6
F16ZnPc

EQ,edge-on – EQ,face-on [eV]

IEedge-on – IEface-on [eV]
0.4 F8ZnPc 0.4

0.2 F4ZnPc 0.2

Au Au

0.0 0.0
ZnPc
–0.2 –0.2
Experiment
–0.4 F4*ZnPc Simulation –0.4
p-BPAPF p-BPAPF
–80 –60 –40 –20 0 20 40 60 80
b Qπ [ea02]
Face-on
Edge-on
d 5.0
ZnPc
IEs
5.5
Intensity [a.u.]

6.0 F4ZnPc
IE

IE [eV]
IE0
ZnPc 6.5 F8ZnPc

7.0

Interface
IE0 IE F8ZnPc
7.5 F16ZnPc

9 8 7 6 5 4 0 2 4 6 20
Binding energy w.r.t. Evac [eV] Layer thickness [nm]

Fig. 2 Dependence of IE on charge−quadrupole interactions along the π−π-stacking geometry: a Sketch of the film structure of ZnPc, F4ZnPc and F16ZnPc,
showing the difference in molecular orientation between two different substrates. b UPS spectra of thin films of ZnPc (top) and F8ZnPc (bottom) in edge-
on orientation (substrate: p-doped BPAPF on silver) and face-on orientation (substrate: gold). The different quadrupole moments of ZnPc and F8ZnPc
cause electrostatic shifts in opposite directions from the gas-phase IE (IE0, obtained with DFT) to the IE value of thin films (obtained with UPS).
c The difference in IE between edge-on and face-on orientation in UPS experiments (violet squares) scales with the calculated quadrupole component
perpendicular to the molecular plane (Qπ). The green solid line shows the difference in the charge−quadrupole interaction energy EQ between both
orientations, as obtained from simulation. d IE of FnZnPc on p-doped BPAPF, obtained by subtracting the substrate spectrum from the superimposed
spectra (see Supplementary Fig. 6a), changes strongly during the formation of the first monolayer in edge-on orientation due to charge−quadrupole
interactions along the π−π-stacking direction. The slight changes of IE from 3 to 20 nm are also observed in simulation and can be explained by increased
interactions with other quadrupole components than Qπ. IEs (dotted lines) is attributed to molecules with EQ ≈ 0, being 0.6 eV smaller than IE0

sexithiophene (alpha-6T), poly-3-hexylthiophene (P3HT) shows We further calculate for ZnPc/C60 and F4ZnPc/C60 the Coulomb
a smaller IE for end-on orientation with the polymer chain binding energies of the energetically relaxed ion pairs and find
perpendicular to the substrate plane42. This analysis indicates that they differ up to several 10 meV between ZnPc and F4ZnPc
that the impact of Qπ on thin film energy levels is relevant for because of their different charge distributions43 (see Methods
many organic materials including varying molecular structures section and Supplementary Fig. 10a). We calculate from these
and different morphologies of their (blend) films. parameters the expected variation of ECT from ZnPc:C60 to
F4ZnPc:C60 (dashed line in Fig. 4b and Supplementary Fig. 10b).
Experimental values of ECT obtained from Gaussian fits to
Impact of Qπ at donor−acceptor interfaces in solar cells. The sensitively measured external quantum efficiency (see Supple-
functionality of OSCs is linked to the formation of charge- mentary Fig. 11) and electroluminescence spectra44. In good
transfer (CT) states of a donor cation and an acceptor anion at agreement with the calculations, the experimental values increase
their interface (Fig. 4a), mediating charge carrier dissociation and with F4ZnPc content (purple squares in Fig. 4b). However, the
recombination in OSCs7,8. In the following, we demonstrate how measured shift of ECT is 0.1 eV larger than expected from the
molecular quadrupole moments can influence the CT state energy variation of molecular parameters, which can be partly attributed
(ECT) as well as its difference to the energy of separated charges to the larger static energetic disorder at high ZnPc contents,
(ECS). For this purpose, we analyse ZnPc:F4ZnPc:C60 solar cells reducing ECT (Supplementary Fig. 12). In addition to energetic
based on bulk heterojunctions (BHJ) with two electron donating disorder, charge−quadrupole interactions lower the effective IE
molecules (ZnPc and F4ZnPc) and one acceptor (C60) with a fixed of the donor and further reduce ECT at large amounts of ZnPc.
volume content of the acceptor (60%). Different mixing ratios To verify the impact of charge−quadrupole interactions on
between ZnPc and F4ZnPc are used to selectively change the ECT, we additionally fabricate solar cells with a planar hetero-
average of the molecular parameters in the donor phase. junction (PHJ) between a ZnPc:F4ZnPc blend layer with varying
For analysing ECT, we obtain the relevant gas-phase energy mixing ratio and a neat C60 layer. The ZnPc:F4ZnPc layer
levels of donor and acceptor molecules (IE0,D and EA0,A) as well is grown on p-doped BPAPF to ensure edge-on orientation of
as the intramolecular relaxation energies of their ions by DFT. the donor molecules, causing a large change of IE induced by

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a a ZnPc:F4ZnPc
6.5
F8ZnPc

+ – C60
+ –
IE [eV]

7.0

C60 + +
–
–
7.5

0.0 0.2 0.4 0.6 0.8 1.0

C60 content
Donor (D)
b 0.0

–0.2 F8ZnPc Acceptor (A)

Δ+ = IE – IE0 [eV]

–0.4
b 1.6
Δ+,s
–0.6 Ternary blend
Bilayer
–0.8 ZnPc
1.4

ECT [eV]
–1.0
0.0 0.2 0.4 0.6 0.8 1.0
C60 content
1.2
Fig. 3 Electronic levels in donor:acceptor blends: a IE of F8ZnPc and C60 at
different molar contents of C60, as obtained by UPS. b With increasing C60
content, the electrostatic corrections Δ+ of ZnPc and F8ZnPc, being the 1.0
difference in IE between the thin film and the gas-phase, shift towards
0.0 0.2 0.4 0.6 0.8 1.0
−0.6 eV. This value is expected for negligible charge−quadrupole
interaction energy (see results in Fig. 2d for very small film coverages). c
Experimental IE values of ZnPc:C60 blends are taken from the study by
Tietze et al.13 0.8
Voc [V]

charge−quadrupole interactions (see Fig. 2b and Supplementary

Fig. 9). At high ZnPc contents, the planar devices exhibit a 0.6
significantly lower ECT (green circles in Fig. 4b) than the ternary
BHJ devices. This can be explained by extended long-range order,
which increases the charge−quadrupole interaction energy and 0.4
reduces IE of the donor for large ZnPc contents. The change of
ECT with donor mixing ratio directly influences Voc because 0.0 0.2 0.4 0.6 0.8 1.0
charge carriers recombine via CT states at open-circuit9. There- F4ZnPc content
fore, the different shifts of ECT in BHJ and PHJ devices upon
changing the donor content is reflected in a similar difference in Fig. 4 Charge-transfer state energies at bulk and planar heterojunctions:
Voc shift, demonstrating the relevance of charge−quadrupole a Simplified sketch of the interface between donor and acceptor phase
interactions for important device parameters (Fig. 4c). in a bulk heterojunction (BHJ). The black arrows sketch a representative
The generation efficiency of photocurrent depends on the dissociation process of a charge-transfer (CT) exciton. b Experimental
dissociation barrier of CT excitons (ΔEdiss), which depends on change of ECT as a function of the molar content of F4ZnPc in the
the difference between ECS and ECT11. We next discuss how intermixed donor phase (ZnPc:F4ZnPc), forming a ternary BHJ (purple
quadrupole moments can induce electrostatic gradients at the squares) or a planar heterojunction (green circles) with the acceptor C60.
donor−acceptor interface that lead to a lower ΔEdiss. In the case of ECT values for the solar cells are obtained from Gaussian fits to sensitively
a negative quadrupole component Qπ,D of the donor, charge measured external quantum efficiency (see Supplementary Fig. 11) and
−quadrupole interactions along the π−π-stacking direction electroluminescence spectra44. The dashed black line is the shift of ECT,
reduce IED and EAD of donor molecules within the donor phase as calculated from the change of molecular parameters (see Eq. 4 in the
(green arrows in Fig. 5a). This shift is smaller at the interface with Methods section). The black arrow highlights the decrease of ECT at large
C60 due to the interaction with its neutral Qπ,A components. The ZnPc contents, which we attribute to charge−quadrupole interactions.
negative Qπ,D influences the energies of acceptor molecules (IEA c Change of Voc, measured at 1 sun illumination intensity, as a function
and EAA) close to the interface, as indicated by the UPS of F4ZnPc content for both solar cell architectures. Note that the voltage
measurements on donor−acceptor blends in Fig. 3. Therefore, losses (ΔVoc = ECT/e − Voc) are slightly lower for planar heterojunctions
the negative Qπ,D induces an electrostatic potential gradient from due to the reduced interfacial area58
the donor to the acceptor phase, which directly reduces ΔEdiss.
To analyse ΔEdiss in ZnPc:F4ZnPc:C60 solar cells, we obtain
the difference between IED and EAA in ternary blends with charge−quadrupole interactions can reduce ΔEdiss. For PHJs, we
UPS and take this as an estimate for ECS45. The results in observe a similar increase of ΔEdiss for higher F4ZnPc contents
Fig. 5b show that ECS increases more strongly with Qπ,D as (Supplementary Fig. 13). We perform TDCF measurements11
compared to ECT, indicating a rise of ΔEdiss from high ZnPc on ternary solar cells to investigate how the increase of ΔEdiss
to high F4ZnPc contents and verifying our considerations that affects the generation efficiency of free charge carriers. In this

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a c 0 0
ZnPc:F4ZnPc:
S1 CS 1:0 1:3
EAD CT

Current density [mA cm–2]

– 3:1 1:9
EAA –2 10
ECT 1:1 0:1
ECS
+
IED
ED* ECT ECS –4

EGE [%]
20
IEA
CT state –6
GS
Qπ,D < 0, Qπ,A = 0 30

–8
b 2.0 40
ZnPc:F4ZnPc:C60
–10
–2 –1 0 1
ECS,peak, ECT,peak [eV]

Voltage [V]
1.8
d 10 60
FF
ECS, peak 8 jsc 50

jsc [mA/cm2]

FF [%]
6 40
1.6 ECT, peak
4 30

2 20

1.4 0 10
–60 –50 –40 –30 –20 –10 0 –60 –50 –40 –30 –20 –10 0
Qπ,D [ea02] Qπ,D [ea02]

Fig. 5 CT exciton dissociation facilitated by quadrupole moments: a Simplified sketch of the donor and acceptor energy levels at the interface (CT state),
highlighted by the grey area, and in the bulk of donor and acceptor phase for Qπ,D = 0 (dashed lines) and Qπ,D < 0 (solid lines). The green arrows illustrate
the energy shifts due to charge−quadrupole interactions, reducing the CT dissociation barrier (ΔEdiss), i.e. the difference between the energy of separated
charges (ECS) and ECT. The right panel sketches the change of ECT and ECS together with the singlet state (S1) energy and the ground state (GS). b ECS,peak,
estimated from UPS measurements, increases stronger with the averaged Qπ,D as compared to the peak energy of the CT state (ECT,peak), indicating an
enhancement of ΔEdiss with increasing Qπ,D, i.e. with larger F4ZnPc contents. ECS,peak and ECT,peak are obtained from peak positions to exclude energetic
disorder and experimental broadening from the analysis. Furthermore, ECS,peak is reduced by 0.6 eV to account for the polarisation difference between
surface and bulk59,60. The solid lines are guides to the eye. c Time-delayed collection field (TDCF) measurements show that the reduction in photocurrent
and fill factor (FF) for large F4ZnPc contents is caused by field-dependent photocurrent generation. The solid lines and left axis show the current-density/
voltage characteristics of the solar cells, whereas the symbols and right axis depict the external generation efficiency (EGE) of the photocurrent. d The
increase of ΔEdiss with Qπ,D, as shown in (b), causes a reduction of the short-circuit current density (jsc) and FF of the respective solar cells measured
at 1 sun illumination conditions

method, donor molecules are excited by a short laser pulse. difference between Qπ,D and Qπ,A (Supplementary Fig. 15). These
After a delay of 8 ns, when all geminate recombination has results indicate that a precise adjustment of Qπ,A being larger than
taken place46,47 (Supplementary Fig. 14), the charges are Qπ,D should be considered when designing efficient non-fullerene
extracted by applying a large negative bias voltage. As shown acceptor molecules. For example, Qπ,A can be increased by adding
in Fig. 5c, the amount of collected charges follows the current- electron withdrawing side groups to the acceptor. In literature,
density/voltage characteristics of the solar cells, revealing that there are already examples of efficient acceptors having such
the reduced photocurrent at high F4ZnPc contents is predomi- side groups50,51, where a larger degree of fluorination resulted in
nantly due to a field-dependent free charge carrier generation11. an improved charge extraction52. Furthermore, the results of a
We attribute the increased field-dependence to the increased recent study indicate that quadrupole moments also affect
ΔEdiss. The increase of ΔEdiss with Qπ,D causes a significant polymer solar cells. Here, an improved charge generation in
reduction of the device parameters FF and jsc once Qπ,D is P3HT/PCBM bilayer solar cells was observed when P3HT was
larger than −30 ea02 (Fig. 5d). This finding explains the oriented end-on42, which can be explained by the reduced
observation in previous studies where the use of F4*ZnPc relevance of the positive quadrupole component along the
(a variant of F4ZnPc, see Fig. 1 for the chemical structure) polymer chain (see quadrupole components of alpha-6T in
as donor in combination with C60 yields well-performing Supplementary Table 1 for comparison). Therefore, quadrupole
solar cells48. In contrast to F4ZnPc, F4*ZnPc has a more negative moments and molecular orientation should be taken more into
Qπ,D of −41.6 ea02, being sufficiently low to ensure efficient CT account for the design of future photovoltaic materials such as
exciton separation. small molecules, oligomers and polymers.
The correlation of FF and jsc with Qπ is not restricted to this
particular system. We further calculate Qπ,D and Qπ,A values for
three donors (SubNc, ZnPc, F4*ZnPc) each combined with one Discussion
non-fullerene acceptor (Cl4SubPc or Cl6SubPc). In PHJ devices49, In conclusion, we show that charge−quadrupole interactions
FF and jsc increase for all donors when the acceptor Cl4SubPc is along the π-π-stacking direction can induce large electrostatic
substituted by Cl6SubPc, which can be explained by the increased energy shifts to the electronic levels of molecular films, depending

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NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-10435-2 ARTICLE

on molecular orientation and blend composition. Due to the The EQE is determined by dividing the photocurrent of the OSC by the flux
sensitivity of the interaction energy to the local morphology, the of incoming photons, which was measured using a calibrated Si and InGaAs
photodiode. The measurements are performed at room temperature.
electronic levels of blends strongly depend on the mixing ratio.
Utilising the example of OSCs, we show the dependency of
Electroluminescence (EL). EL measurements were obtained at room temperature
the charge-transfer state energy at donor-acceptor interfaces on with an Andor SR393i-B spectrometer equipped with a cooled Si and cooled
the quadrupole component in π−π-stacking direction. Moreover, InGaAs CCD detector array (DU420A-BR-DD and DU491A-1.7, UK). The spec-
we present a strategy to tune the driving force for free-charge- tral response of the setup was calibrated with a reference lamp (Oriel 63355). The
carrier generation by adjusting the respective quadrupole com- emission spectrum of the OSCs was recorded at different injection currents with
respect to voltages, which were lower than or at least similar to the Voc of the device
ponents, which can be used to optimise non-fullerene acceptor at 1 sun illumination.
molecules. A similar correlation is found for other materials
than ZnPc derivatives, suggesting that our findings can be applied Time-delayed collection field. In TDCF measurements, the device is excited while
to a large variety of small molecules and polymers. These results held at a varying pre-bias and after a delay time of 8 ns a collection bias of 2.5 V is
highlight the necessity to consider the quadrupole moment as an applied. The excitation was generated with a diode-pumped, Q-switched Nd:YAG
important molecular parameter in future material design for laser (NT242, EKSPLA, 500 Hz rep-rate, 5.2 ns pulse duration, 590 nm wave-
high-performing organic semiconductor devices. length). Also, to compensate for the internal latency of the pulse generator, the
laser pulse was delayed and homogeneously scattered in an 85 m long silica fibre
(LEONI). An Agilent 81150A pulse generator was employed to apply the pre-bias
Methods and collection bias to a homebuilt amplifier directly connected to the sample. The
Ultraviolet photoelectron spectroscopy. The spectra are acquired by a PHOIBOS current through the device was measured via a grounded 10 Ω resistor in series
100 analyser system (Specs, Berlin, Germany) at a base pressure of 10−11 mbar with the sample and recorded with an Agilent DSO9104H oscilloscope.
using He I excitation lines (21.22 eV) and an energy resolution of around 150 meV.
By repeating the sample production under the same experimental conditions, the Density functional theory. The simulations are performed to calculate the
experimental error for the position of the obtained energetic states is estimated to molecular quadrupole moments, the ionisation energy, and the intramolecular
be 50 meV. The Fermi level positions of all spectra are calibrated to the Fermi edges relaxation energy in gas-phase of the relevant molecules. The quadrupole tensor
of the gold or silver substrates. All samples are thermally (co-)evaporated at rates of components Qij are obtained from following definition:
0.1–0.2 Å s−1 in UHV at a base pressure of 10−8 mbar using individual quartz Z  
crystal monitors for each material. As substrates, sputter-cleaned gold foils are used Qij ¼ pðrÞ  3ri rj  jrj2 δij  d3 r: ð2Þ
for face-on orientation and silver foils covered by 5 nm of an amorphous layer of p-
doped BPAPF (3 wt%, doped with NDP9) for edge-on orientation29. NDP9 is a The ionisation energy was determined as the difference of the total energy of the
commercial p-dopant supplied by Novaled GmbH, Germany. The layer thickness positively charged molecule and the neutral molecule in the relaxed geometry of
of the organic layers under investigation is always 20 nm. IE values are obtained the neutral molecule. The intramolecular relaxation energy is determined as the
from the sum of the work function and the maximum position of the HOMO peak. difference in total energy between the negatively (positively) charged molecule in
The work function is extracted from the onset of the high binding energy cut-off. its optimised geometry and its energy in the geometry of the neutral molecule. We
used the M06-2x exchange-correlation functional53 and the correlation-consistent
X-ray scattering. The experiments are performed at the ESRF, France (beamline basis set cc-pVTZ54 as implemented in the computational chemistry package
ID03), with a photon energy of E = 22.0 keV. The reciprocal space maps (RSM) are NWChem55.
measured under grazing incidence geometry with an angle of incidence of αi =
0.07°. Each RSM is assembled from 16 single images recorded with a PILATUS 300k Charge−quadrupole interaction energy calculation. The energy is calculated for
area detector. All measurements are performed in air. The samples are thermally a given molecule at site rj as a discrete sum including all other molecules (at sites ri)
(co-)evaporated at rates of 0.1−0.2 Å s−1 in UHV at a base pressure of 10−8 mbar in the considered geometry, according to
using individual quartz crystal monitors for each material. As substrates, glass    
substrates covered by 1 nm of chromium and 30 nm of gold are used for face-on   X q ri  rj  τk  Qi  ri  rj  τk
j;k
orientation and glass substrates covered by 5 nm of an amorphous BPAPF are used EQ rj ¼  5 ð3Þ
8πϵ0 ϵr  
for edge-on orientation29. The layer thickness of the FnZnPc layers is 20 nm. i;k ri  rj  τk 

with the quadrupole tensor Qi of molecule i and the relative dielectric permittivity
Solar cell device preparation. The solar cells are thermally evaporated at ultra- (assuming εr = 2.856 for all FnZnPcs). Hereby, qj,k is the fractional excess charge
high vacuum (base pressure < 10−7 mbar) on a glass substrate with a pre-structured at atom k of the molecule j and rj + τk is its position. The quadrupole tensor and the
indium tin oxide (ITO) contact (Thin Film Devices, USA). The layer stacks of the fractional excess charges are obtained in gas phase for all molecules in
ternary bulk heterojunction solar cells are: Glass/ITO/BPAPF:NDP9 (40 nm, 5 wt their respective relaxed structures. The charge distributions and the resulting
%)/ZnPc:F4ZnPc (5 nm, varying ratio)/ZnPc:F4ZnPc:C60 (38 nm, varying ZnPc: quadrupole moments might slightly differ in the film phase due to the surrounding
F4ZnPc ratio, 60 vol% of C60)/C60 (15 nm)/C60:W2(hpp)4 (8 nm, 3 wt%)/Al (100 polarisable medium. The film structure was generated according to the crystal
nm). The layer stacks for planar heterojunctions are: Glass/ ITO/ BPAPF:NDP9 structure of CuPc57 (see Supplementary Figs. 1–4). We assume a simplified
(20 nm, 10 wt%)/ZnPc:F4ZnPc (10 nm, varying ratio)/C60 (40 nm)/BPhen (8 nm)/ orthorhombic lattice and take the intermolecular distances (approximately constant
Al (100 nm). NDP9 is a commercial p-dopant supplied by Novaled GmbH, Ger- 3.8 Å and 13.5 Å) from literature28,30. For face-on geometry, a film thickness of 20
many. All the organic materials were purified 2−3 times by sublimation. The nm implies that we take into account 53 layers along the surface normal. We restrict
device area of 6.44 mm2 is defined by the geometrical overlap of the bottom and the the summation in lateral directions to a large area of 400 nm × 400 nm, which is
top contact, verified with a profilometer. To avoid exposure to ambient conditions, sufficient for convergence. For edge-on geometry, we have 15 layers in the direction
the organic part of the device is covered by a small glass substrate which is glued on of the surface normal for a 20 nm film, while the lateral dimension of the integration
top. The relative content of donor and acceptor phases in ternary blends is esti- region is equally big. To investigate the relevant range for the interaction energy, we
mated to have a precision of better than ±5 wt%. vary the summation in lateral direction between 10 and 200 nm (Supplementary
Fig. 5). In addition, we reduced the thickness of the film in edge-on orientation from
Current−voltage characteristics. The current−voltage characteristics in dark 20 to 3 nm and observe an increase of the interaction energy by 10% for ZnPc, in
and under solar illumination are measured with a source measure unit (Keithley good agreement to the change of IE observed in experiment (Fig. 2d).
2400, USA) at room temperature. For the latter condition, the solar cells are
illuminated with a spectrally mismatch-corrected intensity of 100 mW cm−2 Energy change of CT states due to molecular parameters. We estimate the
(AM1.5G) provided by a sun simulator (16 S-150 V.3 Solar Light Co., USA) and variation of the CT state energy (ECT) from the change of molecular parameters
masked to avoid edge effects and to precisely define the area. The intensity is when replacing ZnPc with F4ZnPc using following expression:
monitored with a calibrated Hamamatsu S1337 silicon photodiode.
ECT ¼ IE0;D  EA0;A  Ecoul;CT  λD  λA ; ð4Þ
Sensitive external quantum efficiency (sEQE). The light of a quartz halogen where IE0,D is the gas-phase ionisation energy of the donor (ZnPc/F4ZnPc) and
lamp (50 W) is chopped at 141 Hz and coupled into a monochromator (Newport EA0,A is the gas-phase electron affinity of the acceptor (C60). Ecoul,CT is the Cou-
Cornerstone 260 1/4m, USA). The resulting monochromatic light is focused onto lomb binding energy between the donor cation and the acceptor anion, which is
the solar cell, of which the short-circuit current is fed to a current pre-amplifier screened by a mean dielectric constant of εr = 3.6, obtained from εr = 2.8 for ZnPc
before it is analysed with a lock-in amplifier (Signal Recovery 7280 DSP, USA). and εr = 2.8 for C60 56. For a detailed description how Ecoul,CT is obtained, we refer
The time constant of the lock-in amplifier was chosen to be 0.5 s or 1.0 s and the the reader to a our previous publication43. λD is the intramolecular relaxation
amplification of the pre-amplifier was increased to resolve low photocurrents. energy of the donor cation and λA is the intramolecular relaxation energy of the

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Acknowledgements Open Access This article is licensed under a Creative Commons

We thank Beatrice Beyer for providing F4ZnPc and F16ZnPc. M.S. acknowledges financial Attribution 4.0 International License, which permits use, sharing,
support by the German Research Foundation (DFG) through the project MatWorldNet adaptation, distribution and reproduction in any medium or format, as long as you give
LE-747/44-1. F.O. would like to thank the DFG for financial support (project OR-349/1). appropriate credit to the original author(s) and the source, provide a link to the Creative
The TDCF setup in Potsdam was partially financed by the DFG through INST 336/94-1 Commons license, and indicate if changes were made. The images or other third party
FUGG. This work was supported by the German Federal Ministry for Education and material in this article are included in the article’s Creative Commons license, unless
Research (BMBF) grant InterPhase (FKZ 13N13661) and through the InnoProfile project indicated otherwise in a credit line to the material. If material is not included in the
“Organische p-i-n Bauelemente 2.2” (03IPT602X). Moreover, the project received article’s Creative Commons license and your intended use is not permitted by statutory
funding from the NMP-20-2014—“Widening materials models” programme under regulation or exceeds the permitted use, you will need to obtain permission directly from
Grant Agreement No. 646259 (MOSTOPHOS). K.L. is a fellow of the Canadian Institute the copyright holder. To view a copy of this license, visit http://creativecommons.org/
for Advanced Research (CIFAR). We gratefully acknowledge grants for computing time licenses/by/4.0/.
from the Zentrum für Informationsdienste und Hochleistungsrechnen Dresden (ZIH).
The X-ray scattering experiments were performed on beamline ID3 at the European
Synchrotron Radiation Facility (ESRF), Grenoble, France. We are grateful to Maciej © The Author(s) 2019

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