1
Supporting Information
2
S1 Analyzing the substrate systems
3
In order to model the pristine and blended films of different polymers and nanoparticles, at
4
first the optical constants of the substrates must be analyzed. We used a commercial ITO glass
5
substrate (Thin Film Devices) combined with a spin cast PEDOT:PSS (CLEVIOS HIL 1.3,
6
Heraeus Precious Materials). In a first step, the ITO was etched off and the blank glass
7
substrate was measured (SE, DP and T) and modeled. A generalized oscillator model was
8
applied, composed of three Gaussian oscillators to model the imaginary part of the dielectric
9
constant ( = 1 + i2). Each oscillator is defined by three fit parameters (amplitude, energetic
10
position and broadening). Absorption structures out of the measuring range were represented
11
by so-called Sellmeier-Poles. Absorptions with energy position out of the measuring range
12
but with tails in the investigated region typically show strong correlation of the energy
13
position parameter and the amplitude. In order to obtain unique results and to reduce the total
14
number of fit parameters the energy position was fixed for the out-of-range oscillators. Notice
15
that no reliable physical information can be extracted of the out-of-range values of amplitude,
16
energy position and broadening. The real part is obtained by Kramer-Kronig-consistency
17
(KK) [1]. For quantification of model quality the mean squared error (MSE) between
18
measured data (SE, DP and T) normalized on the total amount of free fit parameters was used
19
[1]. MSE weighting by factor 6:1 was adjusted to compensate the outnumbered T
20
measurements. The applied software WVASE32 uses the Levenberg-Marquardt algorithm to
21
find the minimal MSE in the multi-parameter space [1]. In addition the correlation between fit
22
parameters was investigated. Models with parameter correlation above ± 0.92 were discarded.
23
The parameters describing the glass oscillators are listed in Table S1.
24
The following equations describe the Gaussian and Lorentzian oscillators, and the Sellmeier
25
Poles [1]:
1
1
2
  2 ln 2 E  E   2
 2 ln 2 Eph  Ec   
ph
c





 2,Gauss  Aexp 
 exp 


 
 
B
B


 
 
2
 2,Lorentz 
3
 1,Pole 
E
2
AB 2 Eph
2
ph

2
2
 Ec2  B 2 Eph
A
EC2  Eph2
4
In these equations A is the amplitude in arbitrary units, B is the broadening in eV, Eph is the
5
light energy and Ec is the energy position of the oscillator in eV. Poles in the UV and IR act as
6
additional offset and curvature terms for the calculation of ε1. For further details see [1].
7
In the next step the ITO film was analyzed, using the film thickness of a mechanical
8
profilometer (Veeco Dektak 150) as a start and reference value. Again SE, DP and T Data
9
were modeled with a generalized oscillator model, using one Gaussian for the UV and one
10
Lorentzian for the NIR absorption. Both energy positions were out of the measuring range.
11
Thus both energy positions were fixed at 5.5 eV and 0.1 eV, respectively. We did not use a
12
Drude-oscillator for the free carrier absorption in the (N)IR, as it causes occasional software
13
errors during the fit procedure. A continuous layer could not sufficiently fit the measured data
14
in the NIR, which is often observed for sputtered ITO layers. Thus gradients of Lorentzian
15
amplitude were allowed in the optical model. A linear gradient allows for sufficient model
16
quality. The parameters of the oscillators are listed in Table S1.
17
As the last step in substrate analysis, a thin (30 nm) PEDOT:PSS layer was spin cast on a
18
substrate. The ITO substrate was previous masked and etched, so that one part of the sample
19
was the blank glass, the other part glass+ITO. The uniaxial anisotropic PEDOT:PSS was
20
modeled according to Pettersson et al. [2], using two independent generalized oscillator
21
layers. The first layer represents the optical constants in the plane of the film (xy), the other
22
optical constants parallel to the surface normal (z). SE, DP and T were measured at the glass
23
and the glass+ITO position. Two models with the respective substrate were built and coupled,
2
1
which means the optical constants of the PEDOT:PSS were the same in both models. Again
2
we avoided the Drude-oscillator in order to improve the software stability during the fit
3
procedure. Finally the parameters of the oscillators were fit in order to match the measured
4
data of both measuring positions at the same time. As good agreement of modeled and
5
measured data was observed for both substrate configurations, the optical properties of
6
PEDOT:PSS seems to have no significant dependency on surface energy. The parameters of
7
the in-plane and out-of-plane oscillators are listed in Table S1.
8
3
1
S2 Modelling Ellipsometric data of pristine films
2
The strategy was to start with a GenOsc layer on top of the previously well characterized
3
glass/PEDOT:PSS and glass/ITO/PEDOT:PSS substrate, placed on the same sample. The
4
optical constants of the investigated film were coupled in both models in order to realize the
5
multi-sample-analysis for increased information and decreased parameter coupling. The fact,
6
that the normal transmission is only sensitive to the in-plane optical constants allows for a
7
separation of the xy- and z-oscillator model, at least to obtain good starting values. Thus we
8
started with fitting the xy- oscillators to the transmission data. Starting in the transparent
9
region, the range was increased step by step to the absorption region, subsequently adding
10
Gaussian oscillators if MSE starts to increase significantly. Afterwards a point-by-point (pbp)
11
fit over the full wavelength range was performed, using the KK-consitent GenOsc Model as
12
start values. The pbp result was used to readjusted and sort out the oscillators, followed by a
13
fit of that new GenOsc model on the measured data. These values were used as start values
14
for the z-direction, followed by fit procedures on the complete set of measured data (SE, T).
15
Again several loops of pbp-fits, readjustment of oscillators and oscillator-fits were performed
16
— in case of anisotropic material for both the in-plane and out-of-plane OC — until no
17
further improvement in MSE was found.
18
Finally MSE improvement of additional surface roughness and back side reflection were
19
tested, followed by readjustment of oscillators by the above mentioned routine. For most
20
films a thin surface roughness improved the fit quality, using a Bruggeman effective medium
21
approximation (EMA) with 50 : 50 volume ratio of film OC and void (n = 1, k = 0). The
22
surface roughness was rather small (< 3 nm) for all investigated pristine films. A final pbp fit
23
was performed with fixed layer thicknesses and the resulting OC were used for the EMA
24
models.
25
Figures S2 to S7 show the experimental data and the fit results of the pristine films on
26
glass/PEDOT:PSS
substrate
and
for
the
4
anisotropic
polymer
films
also
on
1
glass/ITO/PEDOT:PSS together with the modeled results of the oscillator models and the
2
final point-by-point fit results. The excellent agreement of the optical constants obtained from
3
the pbp- and the oscillator models ensure KK-consistent and thus physical results of the pbp
4
fit. The final oscillators used as star values for the pbp-fit procedure for the polymers are
5
listed in Table S2, those for the nanoparticle films in Table S3. Oscillators out of the
6
measuring range again use fixed energy position in order to avoid parameter correlation of
7
oscillator amplitude, energy position and broadening. Despite the high number of fit
8
parameters unique fit results could be obtained by the MSA of two different sample positions
9
with different substrate layer sequence and combined analysis of SE, DP and T
10
measurements.
11
12
S3 EMA model for blend layers
13
EMA was used to fit the blend layer with the pbp-results of the pristine films. We used
14
Bruggeman EMA with variable screening factor (q), where q = 0 represents a side-by-side
15
configuration of P3HT and QD domains, q = 0,333 spherical domain shapes and q = 1 a
16
stacked configuration. For a review on EMA models see for example [3]. The EMA
17
composed of the OC of the pristine films was modeled on measured data, again using MSA of
18
two measuring position to increase information and thus to reduce parameter correlation. We
19
used coupled volume fractions and screening factor for the in-plane and out-of-plane OC and
20
tested single layers, gradients and surface roughness on fit quality.
21
Figure S8, S9 and S10 show the experimental results of Ψ, Δ and T of samples with 10 wt.%
22
polymer in QD with pyridine capping ligand on glass/PEDOT:PSS and on glass/ITO/PEDOT
23
substrates together with results of the EMA model using linear gradients of volume ratios. For
24
comparison in the lower part of the figures the optical constants of a free point-by-point fit are
25
shown together with the results of the graded EMA models. The pbp fit does not allow for
26
taking gradients into account. Thus the pbp-results are a kind of mean optical constants along
5
1
the blend layer thickness. In each case, the pbp-results are within the range spanned by the
2
gradient of the EMA-model. This agreement demonstrates the applicability of the EMA for
3
these blend films.
4
We found a linear gradient of the concentration combined with a surface roughness to fit most
5
of the blend films best. Other shapes of the gradient like exponential or Gaussian causes
6
partly improved MSE values, but increases also the parameter correlation and thus did not
7
allow unique fit results. The gradient was generated by a stepwise change of composition,
8
where the number of steps was increased until no further effect on MSE was accomplished.
9
Typically three to eight steps were required. The reported volume ratio was finally calculated
10
by the mean value over layer thickness, including the impact of surface roughness layers.
11
Details on the gradients and a comparison with high resolution TEM images will be reported
12
elsewhere.
13
It should be noted, that the EMA fails if the temperature during post-thermal annealing was
14
close to or above the polymers glass transition temperature. In this case the EMA can not fit
15
the experimental data sufficiently, and free pbp-fits show shifts in absorption structures that
16
can not be described by any EMA.
17
18
S4 Equation for ligand layer thickness
19
Assuming the QD to consist of a spherical CdSe core with radius rCdSe and volume
20
21
22
23
24
VCdSe 
4
3
 rCdSe
3
; mCdSe   CdSeVCdSe
(SI 1)
and a ligand layer shell of thickness dL and volume

4
3
3
VL   d L  rCdSe   rCdSe
3

; mL   LVL
.
(SI 2)
The mass ratio (m) is defined as
m
m Poly
mQD

m Poly
mCdSe  m L
,
(SI 3)
6
1
the volume ratio (v) as
v
2
3
VPoly
VQD

VPoly
VCdSe  VL
.
(SI 4)
Using Eqs. (SI 4) and (SI 3) a mass density ratio can be found
A
4
v mCdSe  mL VPoly

.
m VCdSe  VL mPoly
(SI 5)
5
Replacing the masses with their respective mass densities and volumes and using the volume
6
expressions of Eqs. (SI 1) and (SI 2) leads to
A
7


3
3
rCdSe
 CdSe  d L  rCdSe   rCdSe
L
3
d L  rCdSe 
3
 Poly
.
(SI 6)
8
Reorganizing Eq. (SI 6) finally leads to Eq. (3).
9
Assuming the CdSe-NR particles to consist of a cylinder capped with half spheres at the ends,
10
an analogue formulation can be found. Here the volume of the inorganic core is the sum of the
11
sphere volume with radius rCdSe and the cylinder volume of length lCdSe, the ligand volume is
12
the sum of the hollow cylinder and the sphere shell.
13
4 3
2
VCdSe  rCdSe
l CdSe  rCdSe
3
4
2
3
VL   rCdSe  d L  l CdSe   rCdSe  d L   VCdSe
3
14
Substitution of Eq. (SI 8) in Eq. (SI 5) leads to an expression with dL and L. To bring it in the
15
form of a function dL(L) is not trivial, as in this model terms of lower order remain and the
16
3rd root. Using free available software for linear algebra [4] and excluding the imaginary
17
solutions the result is:
18
dL  
19
with
1
123 2
z
2
3lCdSe
l
 rCdSe  CdSe
5/3
4
2 z
(SI 8)
(SI 9)
7
2
3
3
6
2  2916lCdSe
z    1296 gl CdSe rCdSe
 1728 grCdSe
 54l CdSe


2
3
3
1296 gl CdSe rCdSe
 1728 grCdSe
 54l CdSe
1
g

1
3
(SI 10)
 L   CdSe
 L  A poly
2
3
S5 Thermogravimetric analysis of ligand layer
4
For several samples we studied the composition of the ligand layer by thermogravimetric
5
analysis (TGA) coupled with time-of-flight mass spectroscopy (MS). Heating films of the
6
nanoparticles causes partially evaporation of the ligands because the ligands, strongly bonded
7
on the nanoparticle surface, evaporate at an elevated temperature, higher than the annealing
8
temperature of the samples, due to the binding energy between ligands and nanoparticle
9
surfaces. The corresponding temperature level allows for an evaluation of binding energies of
10
the detected species within the film. Similar studies were already reported for example by
11
Kuno et al. [5] and Iqbal et al. [6]. This analysis allows to identify the ligand species and by
12
comparisons to evaluate the success of ligand exchange procedures.
13
Figure S11 shows a TGA-MS spectrum of the unwashed TOP/OA capped QD with a particle
14
diameter of approximately 5 nm. Three temperature regimes can be found, indicated green,
15
yellow and red. At temperatures between 100 and 200 °C (green regime) free or weakly
16
bound TOP/OA (original ligands from the CdSe QD synthesis) evaporates. This accounts for
17
15-20 wt.% of the film, and can be completely removed by MeOH-n-Hexane washing. In the
18
temperature regime between 200 and 350 °C (yellow regime) a medium bound TOP/OA-layer
19
evaporates. This layer accounts for 3-5 wt.% of the film, and can partially be removed by the
20
combination of pre-washing with MeOH-n-Hexane and pyridine refluxing procedure. For
21
temperatures above approximately 350 °C (red regime) a third ligand regime can be found.
22
Higher binding energies can be interpreted as a layer closer packed to the nanoparticle
8
1
surface. This inner layer of TOP/OA accounts for 12-18 wt.% and can partially be removed
2
during the washing and pyridine refluxing processes.
3
For the washed and pyridine capped particles some TOP/OA can still be found by TGA-MS.
4
We estimate the amount of extant TOP/OA to be in the order of 10 wt.% for particles with a
5
diameter of approximately 5 nm.
6
7
9
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
SI References
[1]
Johs, B.; Herzinger, C.; Guenther, B. WVASE for Windows, J.A.Woollam Co. Inc.
Lincoln, NE, 2005
[2]
Pettersson, L.A.A.; Gosh, S.; Inganäs, O. Org. Electron. 2002, 3, 143–148
[3]
Fujiwara, H. In Spectroscopic Ellipsometry; John Wiley & Sons, Ltd 2007 Chapter 5,
pp 177–181
[4]
Wolframalpha computational knowledge engine
(accessed April 23, 2011)
http://www.wolframalpha.com
[5]
Kuno, J.; Lee, J. K.; Dabbousi, B. O.; Mikulec, F. V.; Bewendi, M. G. J. Chem. Phys.
1997, 106 (23), 9869-9882
[6]
Iqbal, M.; McLachlan, J.; Jia, W.; Braidy, N.; Botton, G.; Eichhorn, S. H. J. Therm.
Anal. Calorim. 2009, 96 (1), 15-20
10
1
Overview of figures
2
(all films on PEDOT:PSS)
Figure
Material
Annealing
Symmetry
Thickness [nm]
S1
Illustration of fit strategy
--
--
--
S2
NR@pyridine
140 °C (15 min) isotropic
70.9
S3
QD@pyridine
140 °C (15 min) isotropic
74.5
S4
QD@HA treated HDA
140 °C (15 min) isotropic
42.4
S5
P3HT
140 °C (15 min) anisotropic
62.0
S6
PCPDTBDT
140 °C (15 min) anisotropic
61.7
S7
PCPDTBT
210 °C (20 min) anisotropic
67.4
S8
10wt.% P3HT, QD
140 °C (15 min) anisotropic
63.3
S9
10wt.% PCPDTBDT, QD
140 °C (15 min) anisotropic
71.3
S10
10wt.% PCPDTBT, QD
210 °C (20 min) anisotropic
69.0
S11
TGA results
--
--
--
3
4
11
1
2
3
Figure S1. Schematic fit strategy. In (a) and (b) the measurement results of pristine films of
4
QD and the polymer P3HT were fitted with the parameter intensive KK-consistent
5
generalized oscillator model. The blend film in (c) was modeled using the constant OC
6
obtained by final pbp fit results of (a) and (b) in an EMA and thus strongly reduced number of
7
fit parameters.
8
12
1
2
3
4
5
6
7
8
9
10
Figure S2: Film of pyridine-capped NR on glass/PEDOT:PSS after post-thermal
annealing for 15 minutes at 140 °C
Experimental results (dashed black) of the ellipsometric angles Ψ, Δ under various angles of
incidence and Transmission (T) at normal incidence together with the model results using an
isotropic oscillator model (green), and results of a point-by-point fit procedure (red). The
obtained isotropic optical constants (n, k) are shown in the lower graph in corresponding
colors.
13
1
2
3
4
5
6
7
8
9
Figure S3: Film of pyridine-capped QD on glass/PEDOT:PSS after post-thermal
annealing for 15 minutes at 140 °C
Experimental results (dashed black) of the ellipsometric angles Ψ, Δ under various angles of
incidence and Transmission (T) at normal incidence together with the model results using an
isotropic oscillator model (green), and results of a point-by-point fit procedure (red). The
obtained isotropic optical constants (n, k) are shown in the lower graph in corresponding
colors.
14
1
2
3
4
5
6
7
8
Figure S4: Film of HAD-capped QDs after the HA treatment on glass/PEDOT:PSS after
post-thermal annealing for 15 minutes at 140 °C
Experimental results (dashed black) of the ellipsometric angles Ψ, Δ under various angles of
incidence and Transmission (T) at normal incidence together with the model results using an
isotropic oscillator model (green), and results of a point-by-point fit procedure (red). The
obtained isotropic optical constants (n, k) are shown in the lower graph in corresponding
colors.
15
1
2
3
4
5
6
7
8
9
10
11
12
Figure S5: P3HT (layer thickness 62.0 nm) on PEDOT:PSS after post-thermal annealing
at 140 °C (15 minutes).
top: Experimental results (dashed black) of the ellipsometric angles Ψ and  under various
angles of incidence, and the transmission T at normal incidence in comparison with
generalized oscillator model results (solid red) using a linear gradient of the volume fraction.
The plots on the left show the results of the blend film on glass (1 mm) / PEDOT:PSS
(30 nm), the right side shows results of the film on glass (1 mm) / ITO (150 nm) /
PEDOT:PSS (30 nm).
bottom: Refractive index (n) and extinction coefficient (k) obtained by a point-by-point fit
(green) and the oscillator model (red). The in-plane results are plotted as solid lines, out-ofplane results as dashed lines.
16
1
2
3
4
5
6
7
8
9
10
11
12
Figure S6: PCPDTBDT (layer thickness 61.7 nm) on PEDOT:PSS after post-thermal
annealing at 140 °C (15 minutes).
top: Experimental results (dashed black) of the ellipsometric angles Ψ and  under various
angles of incidence, and the transmission T at normal incidence in comparison with
generalized oscillator model results (solid red) using a linear gradient of the volume fraction.
The plots on the left show the results of the blend film on glass (1 mm) / PEDOT:PSS
(30 nm), the right side shows results of the film on glass (1 mm) / ITO (150 nm) /
PEDOT:PSS (30 nm).
bottom: Refractive index (n) and extinction coefficient (k) obtained by a point-by-point fit
(green) and the oscillator model (red). The in-plane results are plotted as solid lines, out-ofplane results as dashed lines.
17
1
2
3
4
5
6
7
8
9
10
11
12
13
Figure S7: PCPDTBT (layer thickness 67.4 nm) on PEDOT:PSS after post-thermal
annealing at 210 °C (20 minutes).
top: Experimental results (dashed black) of the ellipsometric angles Ψ and  under various
angles of incidence, and the transmission T at normal incidence in comparison with
generalized oscillator model results (solid red) using a linear gradient of the volume fraction.
The plots on the left show the results of the blend film on glass (1 mm) / PEDOT:PSS
(30 nm), the right side shows results of the film on glass (1 mm) / ITO (150 nm) /
PEDOT:PSS (30 nm).
bottom: Refractive index (n) and extinction coefficient (k) obtained by a point-by-point fit
(green) and the oscillator model (red). The in-plane results are plotted as solid lines, out-ofplane results as dashed lines.
18
1
2
3
4
5
6
7
8
9
10
11
12
13
Figure S8: P3HT blended with pyridine-capped QD using a mass ratio of 1:9 and postthermal annealing at 140 °C (15 minutes).
top: Experimental results (dashed black) of the ellipsometric angles Ψ and  under various
angles of incidence, and the transmission T at normal incidence in comparison with EMA
model results (solid red) using a linear gradient of the volume fraction. The plots on the left
show the results of the blend film on glass (1 mm) / PEDOT:PSS (30 nm), the right side
shows results of the film on glass (1 mm) / ITO (150 nm) / PEDOT:PSS (30 nm).
bottom: Refractive index and extinction coefficient obtained by a point-by-point fit (solid red)
and the EMA-model, respectively. The linear gradient of the volume ratio in the EMA model
causes a change of optical constants along the layer thickness. The results at the substrate
interface are shown (dashed red) as well as the results at the interface to the ambient (dashdotted red).
19
1
2
3
4
5
6
7
8
9
10
11
12
13
Figure S9: PCPDTBDT blended with pyridine-capped QD using a mass ratio of 1:9 and
post-thermal annealing at 140 °C (15 minutes).
top: Experimental results (dashed black) of the ellipsometric angles Ψ and  under various
angles of incidence, and the transmission T at normal incidence in comparison with EMA
model results (solid red) using a linear gradient of the volume fraction. The plots on the left
show the results of the blend film on glass (1 mm) / PEDOT:PSS (30 nm), the right side
shows results of the film on glass (1 mm) / ITO (150 nm) / PEDOT:PSS (30 nm).
bottom: Refractive index and extinction coefficient obtained by a point-by-point fit (solid red)
and the EMA-model, respectively. The linear gradient of the volume ratio in the EMA model
causes a change of optical constants along the layer thickness. The results at the substrate
interface are shown (dashed red) as well as the results at the interface to the ambient (dashdotted red).
20
1
2
3
4
5
6
7
8
9
10
11
12
13
Figure S10: PCPDTBT blended with pyridine-capped QD using a mass ratio of 1:9 and
post-thermal annealing at 210 °C (20 minutes).
top: Experimental results (dashed black) of the ellipsometric angles Ψ and  under various
angles of incidence, and the transmission T at normal incidence in comparison with EMA
model results (solid red) using a linear gradient of the volume fraction. The plots on the left
show the results of the blend film on glass (1 mm) / PEDOT:PSS (30 nm), the right side
shows results of the film on glass (1 mm) / ITO (150 nm) / PEDOT:PSS (30 nm).
bottom: Refractive index and extinction coefficient obtained by a point-by-point fit (solid red)
and the EMA-model, respectively. The linear gradient of the volume ratio in the EMA model
causes a change of optical constants along the layer thickness. The results at the substrate
interface are shown (dashed red) as well as the results at the interface to the ambient (dashdotted red).
21
1
2
Figure S11: Thermogravimetric analysis with time-of-flight mass spectroscopy of a thin
3
film of quantum dots with a diameter of approximately 5 nm with the synthesis ligand
4
TOP/OA on glass. The highlighted temperature regimes indicate different binding energies of
5
the ligand that can be interpreted as different layers of the capping layer.
6
22
1
Table S1. Parameters for the poles and oscillators used for representation of the ε2 for glass,
2
ITO and the anisotropic PEDOT:PSS.
Oscillator
glass
Gaussian 1
Gaussian 2
Gaussian 3
Gaussian 4
Pole
Energy
(eV)
Broadening Amplitude
(eV)
(a.u.)
1.1021
3.2494
4.6378
5.1439
11 (fixed)
0.92089
0.09516
0.79971
0.68626
n.a.
1.27E-05
9.51E-07
9.15E-04
1.40E-03
149.48
0.1 (fixed)
5.5 (fixed)
11 (fixed)
0.001 (fixed)
0.2655
1.6080
n.a.
n.a.
34.163…61.438*
3.9311
247.25
1.6983
0.5 (fixed)
1.1240
4.6837
5.5 (fixed)
11 (fixed)
0.7587
1.9073
5.0434
5.5 (fixed)
11 (fixed)
0.7776
1.6723
0.3523
0.5897
n.a.
0.5300
0.8707
0.3479
1.2665
n.a.
1.0517
0.1749
0.0358
1.5084
179.08
0.4952
0.0604
0.2420
1.6888
209.26
ITO
Lorentzian 1
Gaussian 1
Pole 1
Pole 2
PEDOT:PSS
Gaussian 1, xy
Gaussian 2, xy
Gaussian 3, xy
Lorentzian 1, xy
Pole 1, xy
Gaussian 1, z
Gaussian 2, z
Gaussian 3, z
Lorentzian 1, z
Pole 1, z
3
4
* For ITO a linear gradient of the Amplitude was applied. The first value is the amplitude at
5
the glass interface, the second is the amplitude at the ambient interface. The linear gradient
6
was represented by stepwise changes of the amplitude value in 11 steps.
7
23
1
Table S2. Parameters for the poles and oscillators used for representation of the anisotropic ε2
2
for the in-plane (xy) and out-of-plane (z) orientation of the investigated neat polymer films.
Oscillator
P3HT
Gaussian 1, xy
Gaussian 2, xy
Gaussian 3, xy
Gaussian 4, xy
Gaussian 5, xy
Gaussian 6, xy
Gaussian 7, xy
Pole, xy
Gaussian 1, z
Gaussian 2, z
Gaussian 3, z
Gaussian 4, z
Gaussian 5, z
Pole, z
Energy
(eV)
Broadening Amplitude
(eV)
(a.u.)
2.0484
2.1900
2.2755
2.5068
2.6911
3.1005
5.5 (fixed)
11 (fixed)
2.1033
2.4976
2.9556
4.9741
7.0 (fixed)
11 (fixed)
0.1288
0.1342
0.3492
0.3664
0.6765
1.3147
2.0228
n.a.
0.4527
0.4558
0.5450
0.4679
3.3710
n.a.
1.1767
0.7785
2.0233
0.7117
0.4326
0.2316
0.6243
146.1
0.3997
0.4314
0.1873
1.8210
0.6512
136.02
2.1441
2.2611
2.4151
2.7273
5.5 (fixed)
11 (fixed)
2.3011
3.0314
3.9029
4.4770
6 (fixed)
11 (fixed)
0.1485
0.2974
0.4198
0.8528
3.4935
n.a.
0.5458
0.4787
0.5510
0.4011
0.6718
n.a.
0.8339
1.6437
1.1890
0.6114
0.6115
139.2
0.3474
0.1592
0.2029
0.1971
2.1231
114.04
1.6712
1.7918
1.9973
2.9069
2.9917
4.8589
11 (fixed)
1.7764
2.1446
2.9288
3.9110
4.8177
11 (fixed)
0.1464
0.2587
0.4955
1.6455
0.3946
1.8283
n.a.
0.4760
0.3367
0.4777
3.7381
0.4707
n.a.
1.2077
1.5180
0.9251
0.2608
0.3940
0.4149
141.4
1.1588
0.3594
0.3267
0.2092
0.1793
117.47
PCPDTBDT
Gaussian 1, xy
Gaussian 2, xy
Gaussian 3, xy
Gaussian 4, xy
Gaussian 5, xy
Pole, xy
Gaussian 1, z
Gaussian 2, z
Gaussian 3, z
Gaussian 4, z
Gaussian 5, z
Pole, z
PCPDTBT
Gaussian 1, xy
Gaussian 2, xy
Gaussian 3, xy
Gaussian 4, xy
Gaussian 5, xy
Gaussian 6, xy
Pole, xy
Gaussian 1, z
Gaussian 2, z
Gaussian 3, z
Gaussian 4, z
Gaussian 5, z
Pole, z
3
4
24
1
Table S3. Parameters for the poles and oscillators used for representation of the isotropic ε2
2
for the neat nanoparticle films.
Energy
Oscillator
(eV)
QD@pyridine
Broadening Amplitude
(eV)
(a.u.)
Gaussian 1
Gaussian 2
Gaussian 3
Gaussian 4
Gaussian 5
Pole
0.1156
0.1425
0.3831
0.8583
2.6201
n.a.
0.2589
0.1290
0.2618
0.4810
3.4801
165.84
0.1218
0.4186
0.6833
2.1350
1.7274
n.a.
0.2441
0.2235
0.2368
1.3635
3.4640
196.81
0.1603
0.4984
0.9010
0.5637
2.7368
n.a.
0.1971
0.3325
0.6460
0.6038
4.1925
141.29
2.0450
2.1256
2.4117
2.8844
5.2433
11 (fixed)
QD@HA treated HDA
Gaussian 1
Gaussian 2
Gaussian 3
Gaussian 4
Gaussian 5
Pole
1.9861
2.2995
2.6981
3.6115
5.1094
11 (fixed)
NR@pyridine
Gaussian 1
Gaussian 2
Gaussian 3
Gaussian 4
Gaussian 5
Pole
1.9356
2.2627
2.8244
4.7773
5.3065
11 (fixed)
3
25