Nannan Ding1, Ian D Hosein1. 1. Department of Biomedical and Chemical Engineering, Syracuse University, Syracuse, New York 13244, United States.
Abstract
We report the synthesis and characterization of a polymer thin-film structure consisting of two intersecting broadband optical waveguide lattices, and its performance in wide-angle optical energy collection and conversion in silicon solar cells. The structures are synthetically organized via the concurrent irradiation of photoreactive polymer blends by two arrays of intersecting, microscale optical beams transmitted through the medium. Through optical beam-induced photopolymerization and photopolymerization-induced phase separation, well-organized lattices are produced comprising of cylindrical core-cladding waveguide architectures that intersect one another. The optical waveguide properties of the lattices transform the transmission characteristics of the polymer film so that incident optical energy is collected and transmitted along the waveguide axes, rather than their natural directions dictated by refraction, thereby creating efficient light-collecting capability. The embedded structures collectively impart their wide-angle acceptance ranges to enable the film to efficiently collect and interact with light over a large angular range (±70°). When employed as the encapsulant material for a commercial silicon solar cell, the novel light collection and transmission properties result in greater wide-angle conversion efficiency and electrical current density, compared to a single vertically aligned waveguide array. The sustained and greater conversion of light afforded by the encapsulating optical material promises to increase solar cell performance by enabling ultrawide-angle solar energy conversion.
We report the synthesis and characterization of a polymer thin-film structure consisting of two intersecting broadband optical waveguide lattices, and its performance in wide-angle optical energy collection and conversion in silicon solar cells. The structures are synthetically organized via the concurrent irradiation of photoreactive polymer blends by two arrays of intersecting, microscale optical beams transmitted through the medium. Through optical beam-induced photopolymerization and photopolymerization-induced phase separation, well-organized lattices are produced comprising of cylindrical core-cladding waveguide architectures that intersect one another. The optical waveguide properties of the lattices transform the transmission characteristics of the polymer film so that incident optical energy is collected and transmitted along the waveguide axes, rather than their natural directions dictated by refraction, thereby creating efficient light-collecting capability. The embedded structures collectively impart their wide-angle acceptance ranges to enable the film to efficiently collect and interact with light over a large angular range (±70°). When employed as the encapsulant material for a commercial silicon solar cell, the novel light collection and transmission properties result in greater wide-angle conversion efficiency and electrical current density, compared to a single vertically aligned waveguide array. The sustained and greater conversion of light afforded by the encapsulating optical material promises to increase solar cell performance by enabling ultrawide-angle solar energy conversion.
Solar cells continue to play an important
role in sustainable,
renewable energy conversion to support a green, cleaner energy grid.
Toward advancing solar cell technologies, increasing the total solar
energy captured and converted into electricity is an attractive option.
One approach is to deploy light management and light collection strategies,
to increase total light capture and mitigate potential losses, thereby
maximizing conversion and electrical output. From an optics perspective,
this can be achieved using new types of dielectric structures that
elicit novel or stronger light–matter interactions via such
effects as antireflection, optical mode coupling, geometric refractive
optics, plasmonics, and even ray-steering. Such effects have been
realized using optical material structures such as nanoparticle surface
coatings,[1] nanostructured diffractive,
diffuse and scattering layers,[2−5] gratings,[6] nanotexturing,[7] geometric optical structures,[3,8] one-dimensional
(1D) and two-dimensional (2D) lens arrays,[9−11] microscale
patterning,[12] or even more sophisticated
methods such as contact cloaking,[13−16] modified front-contact shape,[17] and alternatively designing back-contact architectures[18] and transparent electrodes.[19]The above approaches have focused primarily on maximizing
collection
efficiencies and total current output particularly for direct solar
irradiation, namely, light at or close to normal incidence. However,
there remain significant opportunities in the development of optical
structures that increase the capture of non-normally incident light.
Commercial front-contact solar cells show drastically reduced conversion
efficiency and output at increasingly greater incident angles (relative
to the surface normal) owing in part to significant shading losses
from the screen-printed metallic contacts in addition to increased
reflection at the solar cell surface.[20] Consequently, as the sun moves along its diurnal trajectory, both
over the course of a day and across seasons, solar irradiation at
more glancing angles yields reduced conversion efficiency owing to
these shading effects and nonoptimal ray propagation. Additionally,
owing to geographic or infrastructure restraints, solar panel installations
may be placed in nonoptimal locations (e.g., ill-aligned, slanted
rooftops, city locations, etc.) or even around transportation infrastructure,
consequently necessitating further the need for better “omni-directional”
collection of solar irradiation. Hence, there remain opportunities
to develop optical materials that help sustain and manage light collection
over a greater range of incident angles, and, particularly, for wide
incident angle radiation (i.e., >40°). Importantly, the loss
in efficiency and performance at wider angles is so strong that even
marginal increases in light capture and conversion can aid to increase
overall solar cell output. Currently, wide-angle energy conversion
in solar cells remains a relatively unexplored area of research, with
only a few studies having examined possible performance enhancements
through such methods as surface texturing, micro-lensing, and transparent
electrodes.[9−12,19,21]Employing optical waveguiding structures provides another
straightforward
approach to manage light transmission over a solar cell.[22] This approach exploits the inherent angular
acceptance range for incident light[23] of
a waveguide structure (particularly across the air–structure
interface) and subsequent guided transmission along the waveguide’s
long axis as a means to control the direction of light propagation.
Creating waveguide structures in a planar film could then serve the
dual objectives of both the encapsulation material and a means to
alter and manage the transmission properties of light, providing more
favorable, direct incident angles and greater transmission flux when
light finally reaches the solar cell. We have investigated the fabrication
of polymer films consisting of a single array of waveguide elements
such as embedded air prisms,[13] 1D waveguide
slabs,[8] vertically aligned microfiber arrays,[24−28] and submillimeter cylindrical waveguides (WGs) in embedded matrices.[20,24,29,30] All such structures provide some, but only a mild enhancement in
light capture at greater incident angles compared to a uniform (i.e.,
nonstructured) encapsulating resin, but the concept nonetheless is
promising. Specifically, arrays or even bundles of cylindrical waveguide
architectures, namely, those with a high-index cylindrical core embedded
in a low-index cladding, have provided many examples of their capability
to collect and alter light transmission. The arrays of cylindrical
waveguides can be produced via the irradiation of photopolymerizable
media with an array of microscale optical beams, which undergo self-trapping
and induce self-writing of the cylindrical core geometry along their
length.[31,32] These arrays show novel light collection
and manipulation capabilities.[8,33,34] We previously exploited the waveguide collection optics of cylindrical
waveguides in a vertically aligned array (i.e., parallel to the surface
normal) synthesized in photoreactive polymer blends.[20,24,30] Through optimizations of array
spacing (i.e., lattice period) and blend composition, the total light
captured could be increased for incident angles up to 40°,[29] but performance still drops dramatically for
incident angles >40°.The collection capabilities of
optical waveguide structures, across
an air–material interface, are limited by their acceptance
“cone”, an interval of incident angles entering the
waveguide core that will satisfy the total internal reflection requirement
to enable optical waveguiding. The concept of “light collection”
using a waveguide works by collecting light within this acceptance
cone, followed by confinement inside the waveguides which restricts
transmission along its axis across the material’s thickness.
In the theoretical case of a vertically aligned waveguide embedded
in a thin-film medium and having an acceptance range of ±θ,
light would assume an effective transmitted direction of 0° in
side the medium, reaching the solar cell at this effective angle on
the other side of the film. The more light propagates at effectively
normal incidence, the greater the boost to collection efficiency.[29] The waveguide acceptance range (Δθ)
for a cylindrical waveguide aligned with its axis normal to the air–material
interface is calculated based on the refractive index of the waveguide
core (n1) and the surroundings (i.e.,
cladding) (n2) according to .[23] The acceptance
cone is symmetric about the surface normal, and the width is dictated
by the refractive index difference between the core and the cladding
materials. Using the refractive index values of the polymers employed
in our previous work (n1: 1.653, n2: 1.412),[29] a maximum
acceptance range of ±30° is possible. What this implies
is that light incident within an angular range of ±30° can
be collected by and guided along the waveguide axis to the other side
of the material; however, beyond that angular range, the beneficial
enhancement to collection efficiency drops significantly. Hence, appropriate
variations in the structure are needed to enable collect at ultrawide
angles (i.e., >40°), which are beyond the fundamental acceptance
cone of vertically aligned waveguides.One solution is to produce
waveguides at slanted orientations in
encapsulation materials so as to rotate the acceptance cone to collect
light to more glancing incident angles. This approach has been considered
with multiple-waveguide arrangements possessing different orientations
to sweep the collection window over a greater angular range.[33−35] Also, waveguides with monotonically varying radial orientations
have also been shown suitable for beam steering.[34,35] Multiwaveguide lattices have also been produced in single-component
media with multidirectional transmission properties.[36−38] Hence, the use of slant-oriented waveguide can provide the opportunity
to suitably position the acceptance ranges of the waveguide arrays
to enable the capture of light at even wider incident angles.Here, we propose the synthesis and application of thin films comprising
two symmetrically arranged intersecting waveguide lattices, oriented
at non-normal incident angles relative to the air–film interface,
to enable ultrawide-angle light capture and increased conversion in
solar cells. In this work, the two intersecting waveguide lattices
are prepared through photopolymerization of photoreactive polymer
blends via irradiation with two arrays of microscale visible-light
optical beams. The optical beams drive the polymerization of cylindrical
channels along their propagation length[31] and eventually cause spatially-controlled polymerization-induced
phase separation (PIPS) of the blend.[39−41] The optical beams become
self-trapped in the polymerizing higher-index medium (both free-radical
and cationic systems),[31,39,42] preserving its collimated nature, in a process referred to as light-induced
self-writing.[43] Thereby, each cylindrical
channel evolves into a high-index core and low-index cladding architecture,
essentially developing a refractive index difference to function as
optical waveguides. We have proposed their formation as well as correlated
their structural quality to different blend and polymerization parameters
in Multiphysics simulations.[44] Unlike previous
work which elicits the formation of such structures in single-component
media, herein, the phase evolution of a binary blend of high- and
low-index polymers enables such structures to achieve larger refractive
index differences (∼Δn of 0.01 vs 0.001),
which significantly widens the waveguide’s acceptance range.
Their slanted orientation rotates their acceptance ranges to more
glancing angles, i.e., closer to the air–film interface, enabling
ultrawide-angle incident light to be accepted and transmit along the
waveguide axes. Their effective transmission in the material occurs
at a smaller incident angle relative to their entry, thereby providing
a more direct path toward the solar cell and mitigating any possible
flux over top contacts. We have already demonstrated the capability
to produce single vertically aligned arrays of cylindrical optical
waveguides.[32] Herein, this is the first
demonstration of intersecting waveguides produced from polymer blends,
revealing the advanced nature of the synthetic organization of the
structures via photopolymerization and PIPS. We explore four different
polymer blend formulations in terms of component weight fractions
and photoinitiator concentration to reveal correlations between the
polymer blend and photopolymerization conditions to the optical properties
of the structures and performance of encapsulated solar cells. We
show enhancements in both the conversion efficiency and electrical
output as a function of incident angle relative to the comparative
baseline of a single vertical array of waveguides. This work demonstrates
a straightforward approach to produce complex optical waveguide structures
with ultrawide-angle light collection capabilities toward their application
in enhanced solar light capture and conversion in solar cells.
Experimental Methods
Materials
As the components of the photopolymerizable
polymer blends, a high-refractive-index Norland Optical Adhesive 65
(NOA65) was purchased from Norland Products, Inc. and a low-refractive-index
epoxide-terminated poly(dimethylsiloxane) (PDMS) oligomer from Gelest,
and camphorquinone (CQ) free-radical photoinitiator from Sigma-Aldrich.
The cationic initiator (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate
(OPPI) was purchased from Hampford Research, Inc. All chemicals were
used without further purification.
Mixture Preparation
Polymer blends with two different
weight fractions (50/50, 20/80, wt %/wt % of total mixture, PDMS/NOA65)
were explored herein, along with two different free-radical photoinitiator
(CQ) concentrations (1.5 and 2.5 wt % of total mixture), respectively,
and a corresponding OPPI of 2.5 wt % of the mixture. The photocurable
formulations were prepared by thoroughly mixing NOA65, PDMS, CQ, and
OPPI with their respective weight fractions in an aluminum-foil-wrapped
vial. A magnetic stir bar was added to facilitate the formation of
a homogeneous mixture under isolated conditions from ambient air and
light. The mixture was stirred for 24 h before use. The mixture was
injected into a Teflon ring cell (2 mm thickness) to its full volume
for photopolymerization.
Photopolymerization
A single chrome mask (Photosciences,
Inc.) consisting of a square array of apertures of diameter 40 μm
and spacing of 200 μm was used to generate the arrays of optical
beams. Two collimated light-emitting diode (LED) light sources were
aligned on an optical board on opposite sides of the mask and oriented
to pass their light through the mask from below at the same incident
angle, resulting in the symmetric formation and projection of two
arrays of optical beams above the photomask. The orientation of the
LEDs was ∼±45° with respect to the surface normal
of the mask. The photocurable mixture in the ring cell was placed
approximately over the center of the confocal region (i.e., the common
region where the LED “spotlight” impinges on the mask).
After placement, the mixture was then exposed to the collimated blue
light (λ = 470 nm) generated from the LEDs (∼12–13
mW cm–2).The irradiation procedure consisted
first of alternating exposure of the mixture to one of the LEDs, followed
by simultaneous irradiation. In more detail, the photopolymerizable
mixture was alternately irradiated by each individual LED (with the
other turned off) for a 5 min duration, and this process was repeated
10 times, resulting in a total of 50 min exposure of the mixture to
each LED. This provided the opportunity for each individual array
of optical beams to inscribe their initial structure unabated by the
optical beams generated from the other LED. Subsequently, both LEDs
were turned on simultaneously to irradiate the medium until the photopolymer
blend was fully cured.
Characterization
A Zeiss Axioscope equipped with an
Axiocam 105 color camera operated by Zeiss imaging software was used
to capture images of the cured polymer blends. All samples were imaged
in reflection mode. The transverse spatial intensity profile of incandescent
light from a QTH source transmitted through the materials was captured
with a CCD camera, using an optics setup described previously.[31,33]
Solar Cell Characterization
A planar multicrystalline
silicon screen-printed solar cell (5 cm × 5 cm × 0.5 mm)
with a measured short-circuit current density of 35.5 mA/cm2 was used in experiments. The photopolymerized samples were laminated
on the solar cell (15 cm, 5 cm, 0.5 mm), which was first covered with
a 0.12 mm layer of PDMS (Sylgard). External quantum efficiency (EQE)
spectra and total external quantum efficiency were measured and calculated,
respectively, as described previously.[29] Angle-resolved measurements were performed as also described in
our previous work.[30] All measurements were
conducted on the same region of the solar cell. Current density–voltage
(J–V) curves of the encapsulated
solar cell were collected under solar simulated irradiation (AM 1.5
G).[30]
Results
Figure illustrates
the procedure for synthetically organizing two waveguide lattices,
with symmetrically oriented directions (i.e., ±θ) with
respect to the mask surface normal. A photocurable binary component
resin is cast over a transparent substrate, which lies on a photomask
(Figure a). LED illumination
is directed through the photomask at a non-normal incident angle (Figure b). The mask transforms
the initially uniform LED illumination into an array of microscale
optical beams that propagate through the resin at a refracted angle.
The individual beams in both arrays all induce the photopolymerization
of cylindrical fibers aligned in the propagation direction of the
beams (Figure c) and
comprise predominately of polymerizing NOA65, owing to its faster
free-radical polymerization. Over time, the PDMS polymer component
is expelled, via PIPS,[32] into the dark
regions surrounding the propagating optical beams. Thereby, overall,
the entire resin is organized into a structure possessing multiple
(i.e., two) intersecting optical waveguide lattices. Polymer films
of 2 mm thickness were selected owing to similar thicknesses with
commercial encapsulations. The selected thickness is also sufficient
to allow the formed cylindrical cores to be long enough to operate
as waveguides (rather than just short cylinder dielectric structures)
as well as for the film to be mechanically robust. The as-synthetized
thin film is then placed on a front-contact solar cell (Figure d), which was first encapsulated
with a very thin PDMS layer to planarize the surface and ensure intimate
contact with the film. This process has the benefit of not requiring
any structural changes to the native photovoltaic cell, and all processing
is during the encapsulation stage. Ideally, any front-contact solar
cell of any composition can be encapsulated, enabling the streamlining
of the encapsulation procedure in photovoltaic panel manufacture.
Figure 1
Schematic
of the production of a multiwaveguide lattice structure,
consisting of two symmetrically oriented waveguide arrays (±θ
relative to the surface normal). The process for their fabrication
is as follows: (a) a photopolymerizable blend is cast over a thin
transparent (glass) substrate, which is positioned over an optical
photomask pattern. (b) Two LED light sources are transmitted through
the mask into the resin from the bottom, creating two arrays of intersecting
optical beams. (c) Over the duration of light exposure, the blend
evolves into its two intersecting waveguide (2W) array structure with
a binary phase morphology consisting of the high-refractive-index
polymer in the regions of irradiation and the low-refractive-index
polymer in the dark regions (i.e., nonilluminated ). (d) Processed
optical materials are placed over a silicon solar cell whose surface
has been planarized with a thin protective PDMS layer. (e) Schematic
of the operational principle of the waveguide lattice structure, whereby
light (red rays) in a uniform medium that would hit a front contact
is now accepted by the waveguide lattice structure (black rays) and
transmitted along a more direct optical pathway toward the solar cell
at a smaller incident angle than its initial one when refracted through
the air–material interface.
Schematic
of the production of a multiwaveguide lattice structure,
consisting of two symmetrically oriented waveguide arrays (±θ
relative to the surface normal). The process for their fabrication
is as follows: (a) a photopolymerizable blend is cast over a thin
transparent (glass) substrate, which is positioned over an optical
photomask pattern. (b) Two LED light sources are transmitted through
the mask into the resin from the bottom, creating two arrays of intersecting
optical beams. (c) Over the duration of light exposure, the blend
evolves into its two intersecting waveguide (2W) array structure with
a binary phase morphology consisting of the high-refractive-index
polymer in the regions of irradiation and the low-refractive-index
polymer in the dark regions (i.e., nonilluminated ). (d) Processed
optical materials are placed over a silicon solar cell whose surface
has been planarized with a thin protective PDMS layer. (e) Schematic
of the operational principle of the waveguide lattice structure, whereby
light (red rays) in a uniform medium that would hit a front contact
is now accepted by the waveguide lattice structure (black rays) and
transmitted along a more direct optical pathway toward the solar cell
at a smaller incident angle than its initial one when refracted through
the air–material interface.Conceptually, in terms of the optics, unlike a
single vertically
aligned waveguide array for which the collection range is symmetric
about the surface normal (±θ),[30] in this multiwaveguide lattice structure, the collection ranges
of the slant-oriented waveguides rotate clockwise and counterclockwise
for waveguides with positive and negative angle orientations, relative
to the surface normal (positive-wise in this case is clockwise rotation),
as shown in Figure e. As schematically illustrated for optical rays at a large incident
angle, in a uniform resin, such light rays (represented by red in Figure e) may be ill-fated
to impinge on a contact, which can induce reflective losses, thereby
reducing total light conversion. This is especially the case at large
incident angles, where there is a greater fractional area of the solar
cell screened by the contacts (via a line-of-sight principle), and
hence more light is lost. However, using a polymer film composed of
optical waveguides (WGs), those same light rays (now represented by
black in Figure e)
now can be collected by the individual cylindrical waveguides in an
array. This effect of collection now allows light transmission along
the waveguide core’s long axis, via optical waveguiding and
total internal reflection effects indicated by the black rays bouncing
off the waveguide core–cladding interface. Because the waveguides
have a smaller angle than the initial incident angle of light, they
provide a more direct pathway (i.e., smaller, less oblique effective
incident angle) toward the active regions of the solar cell. As a
result, by lowering the incident angle of incoming light rays, by
now transmitting them along the waveguides, they will experience less
fractional area of the screening top contacts (i.e., less top contact
shading) at the solar cell surface. Hence, more incident light collected
by the waveguides will be converted by solar cells (black rays) compared
to a uniform coating (red rays). Shading losses are especially exacerbated
at very high incident angles where there is more screening;[13] hence, the waveguide lattice structure would
prominently mitigate this effect, thereby enhancing total energy conversion
at ultrawide angles and providing an overall very large angular range
of operation (i.e., −70 to +70°).Figure shows optical
microscopy images of the cross sections of the multiwaveguide lattices
produced with two different relative weight fractions of the polymer
components and two different photoinitiator (i.e., CQ) concentrations.
The measured angles of the waveguides were θ ≈ 25°,
which is in accordance with the expected propagation angle of the
optical beams when refracted into the polymer medium. Specifically,
according to Snell’s law, a 45° incident angle leads to
an ∼25° internal angle in an initially homogeneous resin
with average refractive indices of ∼1.6 and ∼1.5 for
20/80 and 50/50 blends, respectively. The intersecting nature of the
two arrays (orientations at approximately −25 and +25°)
is clearly revealed in the optical microscopy images. The core clad
architecture is visible in both the top and bottom images of the multidirectional
waveguide arrays produced from both 50/50 and 20/80 blends (Figure a,c); however, the
circular cross-section is clearer for 20/80 blends. Likewise, the
cross-sectional images reveal that the waveguide cylinders become
splayed with streak-like features or more divergent further along
their cylindrical axes, to the extent that they are not as easily
distinguishable at the end of the film. However, the waveguide cylindrical
geometry is quite easily delineated over the depth of the sample for
the 20/80 blends, although broadening of the diameter is still observed.
With regard to CQ content, higher concentrations (2.5 vs 1.5 wt %)
produced clearer intersecting structures for both blend fractions
(i.e., 20/80 and 50/50). These two observations, in terms of weight
fraction and CQ content, indicate the importance of selecting the
relative weight fractions of the two components and photoinitiator
concentration in the formulation to produce intersecting waveguide
structures of better structural quality, which is associated with
the phase separating properties, as will be discussed later. Overall,
the presence of the intersecting structures in all samples lends itself
to the examination of their optical waveguide properties for the transmission
of light and their light collection performance in solar cell encapsulants.
While the optical microscopy images reveal insight into the formation
of the intersecting structure in terms of the polymer blend formulation,
they should not be overinterpreted with regard to the dielectric structure
of the waveguide lattices. Their optical properties, and the core–cladding
structure, are best analyzed through optical transmission studies.
Figure 2
Optical
microscopy images of the intersecting waveguide lattice
structures. Structures are shown in three-series images of top, bottom,
and cross-sectional views. Polymer blend parameters are: (a–c)
20/80 and 2.5 wt % CQ, (d–f) 20/80 and 1.5 wt % CQ, (g–i)
50/50 and 2.5 wt % CQ, and (j–l) 50/50 and 1.5 wt % CQ. Cross-sectional
images are oriented right side up, with the LED light having propagated
upward to synthesize the structures.
Optical
microscopy images of the intersecting waveguide lattice
structures. Structures are shown in three-series images of top, bottom,
and cross-sectional views. Polymer blend parameters are: (a–c)
20/80 and 2.5 wt % CQ, (d–f) 20/80 and 1.5 wt % CQ, (g–i)
50/50 and 2.5 wt % CQ, and (j–l) 50/50 and 1.5 wt % CQ. Cross-sectional
images are oriented right side up, with the LED light having propagated
upward to synthesize the structures.Figure shows CCD
images of the transverse optical intensity profile of transmitted
incandescent white light through the intersecting waveguide lattice
structures and a single vertically aligned waveguide array (for comparison)
as a function of incident angle. The spotted nature of the profiles
for specific incident angles indicates transmitted light is predominantly
confined to the waveguide cores and exits them to form these localized
spot intensities shown in the CCD images. The well-ordered intensity
pattern also correlates to an underlying well-formed waveguide array
structure.[33] At incident angles beyond
the acceptance ranges, the transmitted light appears to exit the film
outside of the waveguide cores and the spot intensities begin to overlap
or smear into one another. This indicates a transition to lossy mode
transmission, in which a portion of light that enters the waveguides
will refract out of it and enter an adjacent waveguide, repeating
this process to form a “smeared” intensity pattern.
The remaining portion of the light may remain reflected within the
waveguide cores, resulting in some resemblance of the spot pattern
for
incident angles beyond the acceptance range. The portion of light
no longer confined to the waveguides (i.e., lossy transmission) increases
as the incident angle moves further away from the collection range,
where eventually light simply cuts through the waveguides, resulting
in transmission profiles appearing as lamellae of high-intensity light.
The multidirectional waveguide lattice structure consists of intersecting
waveguides on a common plane, and such planes stack in the vertical
direction. Hence, beyond the acceptance range, these stacked layers,
or slabs, operate more like higher-index layers, relative to the interstices
in between the layers, and confine light to this layer, which explains
why there is in turn the appearance of “stacked layers”
of dark regions.
Figure 3
Transverse intensity profiles of transmitted incandescent
light
(exiting the samples) as a function of angle of incidence (for light
entering the samples) for multidirectional waveguide lattices prepared
from (a) 20/80 and (b) 50/50 blends with 1.5 and 2.5 wt % CQ and corresponding
single vertically aligned waveguide array (for comparison). All samples
were irradiated at an optical intensity of 12 mW/cm2. Incident
angle ranges visually indicative of waveguiding (green) and lossy
transmission (red) are shown above the images for each sample.
Transverse intensity profiles of transmitted incandescent
light
(exiting the samples) as a function of angle of incidence (for light
entering the samples) for multidirectional waveguide lattices prepared
from (a) 20/80 and (b) 50/50 blends with 1.5 and 2.5 wt % CQ and corresponding
single vertically aligned waveguide array (for comparison). All samples
were irradiated at an optical intensity of 12 mW/cm2. Incident
angle ranges visually indicative of waveguiding (green) and lossy
transmission (red) are shown above the images for each sample.The transverse intensity profiles of transmission
light at the
exit of the film show how confinement of optical intensity to the
waveguides occurs at greater incident angles (ca. 30–70°)
for intersecting waveguide arrays, in accordance with the slant waveguide
orientations (25°) rotating their collection range to accept
light at greater incident angles (i.e., more oblique, away from the
surface normal). At high incident angles, the spots appear to overlap
due to their closer proximity when viewing their profiles at such
glancing angles. However, the circular-shaped intensity spot profiles
are still discernible and would indicate the persistence of waveguided
transmission at very large incident angles, as will be further evidenced
when calculating their experimental collection angles, as discussed
later. The multidirectional waveguide structures produced from 20/80
blends show clear spots from the onset of light collection (∼25°)
up to 70°, indicating confinement and emission from their waveguide
cores over this very large angular range. In the case of the 50/50
blends, the periodically ordered arrangement of the transmission spots
begins to deteriorate, unlike with the 20/80 blends. One explanation
could be the decreasing quality of the cylindrical geometry of the
waveguide structures produced with the 50/50 blends consequently leading
to a loss in the capability to confine light. However, the transmission
profiles for moderate incident angles (20–40°) appear
to be visually as good as for structures produced from the 20/80 blends.
Hence, a more convincing explanation might be that at greater incident
angles, light will couple into higher-order modes of the waveguides,
which are more sensitive to the quality and uniformity of the waveguide
core,[32,41] and consequently will not be as efficiently
confined. In simpler terms, with increasing incident angle, the capability
for the waveguide structures to effectively confine collected light
becomes more sensitive to the quality of the waveguide structures.
In the case of the single-waveguide arrays (0°), produced from
either of the weight fractions, collection and waveguided transmission
occur at lower incident angles (ca. 0–20°), but this capability
is lost at greater incident angles. Importantly, the intersecting
waveguide structures prepared from both 20/80 and 50/50 blends rotationally
shift the collection capabilities to greater incident angles relative
to the control, all be it with different effectiveness. The collection
properties for each waveguide array in the structure (i.e., −25
and 25°) showed no difference (see the Supporting Information), and hence the irradiation setup was able to produce
structures with truly symmetric optical properties. When comparing
the optical transmission between blends prepared with 2.5 and 1.5
wt %, blends prepared with higher CQ concentration confine light more
tightly, with their CCD images showing a sharper spot pattern (i.e.,
smaller size spots) in the regime of waveguided transmission. This
is most evident, for example, when examining incident angles of 30
and 40°. Also, in the case of the 40° incident angle, the
50/50 blend prepared at 1.5 wt % CQ produces a smeared CCD pattern,
whereas the corresponding 2.5 wt % CQ still shows a spotted pattern.
It is also possible that the formation of lamellae for 50/50 blends
prepared with 1.5 wt % CQ is also a result of the lower quality of
the waveguide ends produced with this formulation, as shown in the
corresponding optical microscopy images. These observations point
toward 20/80 blends with 2.5 wt % CQ as the formulation that produces,
visually, the sharpest, highest-quality transmission patterns over
the greatest angular range. Examination of these intensity profiles
is suitable for observation of light confinement as a function of
incident angle, but not necessarily the total light transmitted, which
may differ based on other aspects, such as scattering, absorbance,
etc. Hence, while light collection regimes are indicated by the CCD
images, examining the solar cell response will indicate the combined
performance of the efficient collection, transmission, and finally
conversion when the polymer structures are employed as encapsulants,
which will be discussed later.The observed collection intervals
(and their range) are directly
correlated to the refractive indices of the waveguide cores and cladding
(i.e., their index difference, Δn), which is
in turn related to the relative volume fractions of the blends, and
thus can be used to infer degrees of phase separation in the core
and cladding. To model the observed acceptance angle range for the
waveguides in a slant orientation, we first correlate the boundaries
of the acceptance range to the refractive index difference (Δn) between the polymer waveguide cores and their surroundings
(consider as the cladding). This refractive index difference is expressed
in terms of the refractive index of the core and cladding, both of
which depend on the volume fraction of each polymer in their respective
regions. To begin, we define the bulk volume fraction (φbulk) as that of the free-radical polymerizing component, NOA65
in our case, which is fixed by the initial formulation (50 or 80%),
and may be expressed as:where f is the volume fraction
occupied by the waveguide cores, and fcore and fcladd are the volume fraction of
the high-index polymer (NOA65) in the waveguide core and surrounding
medium (i.e., the cladding of the waveguide), respectively. With the
densities of the polymers being ∼1 g/cm2, the volume
fractions are nominally the same as the weight fractions expressed
herein. During phase separation, fcore is expected to increase owing to the phase separation (i.e., expulsion)
of PDMS into the surroundings and concurrent diffusion of NOA65 (to
preserve mass balance) into the polymerizing waveguide cores. Likewise, fcladd will decrease as NOA65 is lost to the
polymerizing cores and PDMS content increases (via gaining PDMS expelled
from the polymerizing regions). The volume fraction occupied by the
waveguides based on a model of two intersecting cylinders along a
common plane within a rectangular unit cell iswhere Vcylinder is the volume of a slanted cylinder in a rectangular prism cell, Vcommonvolume is the common volume or volume
of overlap of the two cylinders with the same radius,[45] which must be subtracted so as not doubly count cylinder
occupancy, and Vcell is the volume of
the rectangular unit cell. Equation expands to be expressed in terms of the waveguide
cylindrical radius (r), mask aperture spacing (S), which defines the square base of the unit cell, and
the orientation angle of the waveguide (θ) relative to the surface
normalThe theoretical fraction dictated by the mask
(r = 20, S = 200, and θ =
25°), i.e., if the waveguides have the same diameter as the mask
apertures, is approximately 5.4%. Measurements of the waveguides show
their diameter is approximately 46 μm, which gives a volume
fraction of 7.0%. Next, the volume-averaged refractive indices of
the waveguide cores and surroundings arewhere n1 and n2 are the refractive indices of NOA65 and PDMS,
respectively. The boundaries for the angular acceptance range (θa) for a slant waveguide of angle θw at the
air–core interface can be determined to beBriefly, the approach to derive eq is to first calculate the boundaries
of the acceptances angle of a core immersed in the cladding medium,
rotate those bounds by the waveguide orientation angle (i.e., addition
of θ), and then determine their respective values considering
refraction at the air–core interface. Hence, given the collection
angles determined experimentally, the angle of orientation of the
waveguides, and volume fraction of the waveguides in the array, one
can predict the polymer volume fractions in the waveguide and surrounding
regions. In more detail, the volume fraction of the core (fcore) can be used as fit parameter via eqs –6 to regress the experimental boundaries of the acceptance
range. The CCD images of transmission intensity would indicate an
approximate lower bound to the acceptance range of ∼25 to ∼30°
and up to approximately 70°, for 20/80 and 50/50 blends, respectively.
In the case of the lower bound, this is determined by the angle at
which there is approximately the first instance of distinct (i.e.,
nonoverlapping) spots in the optical intensity profiles. Since the
experiment was limited to observing incident angles up to 70°,
and the spot patterns appear to persist beyond this angle, the upper
bound of the acceptance range is uncertain and could be higher than
70°. Hence, the lower bound angle of the acceptance cone was
used as the angle to fit. For the 20/80 blend, using a lower bound
of 25° as input, the refractive indices of the core and the cladding
are determined to be 1.627 and 1.603 (Δn =
0.024), respectively. This would indicate that the upper bound to
the acceptance range is approximately 85°. The volume fractions
of NOA65 that account for these refractive index values for the waveguide
core and surroundings would be 89.4 and 79.3%, respectively. Hence,
the waveguide cores become enriched from the initial 80% of the bulk
mixture (prior to irradiation) by 9.4%, and the surrounding mixture
becomes diluted by 0.7%. This low dilution in the surrounding regions
is a result of the small volume fraction of the growing waveguides
in the medium from which PDMS may be expelled. In other words, the
volume of PDMS expelled from the regions of irradiation is so small
that it leads to a very small change in the polymer blend composition
in the nonirradiated regions. Likewise, for 50/50 blends using a lower
bound of ∼30° as input, the refractive index of the core
and the cladding are determined to be approximately 1.54 and 1.53
(Δn = 0.01), respectively, indicating an ∼53.7%
NOA65-rich core and 49.7% NOA65 in the surroundings. Once again, the
waveguide is enriched, less so than with the 20/80 blend, and the
surroundings are slightly diluted. In terms of the refractive index
profile, therefore, the waveguide structures consist of cores enriched
with NOA65 that are embedded in a bulk medium that is only slightly
lower in refractive index than the original bulk mixture. Nevertheless,
the refractive index difference is sufficient to yield wide acceptance
ranges for light collection. As a comparison, the acceptance range
for the single vertical waveguide array, assuming the maximum collection
angle is ∼20° (observed in the CCD images) yields a 95%
NOA65 volume fraction in the cores (f = 3.5%) and
79% in the surroundings. This is in good agreement with measurements
of degrees of phase separation in previous work.[29,40] As the collection ranges were not significantly different between
the two CQ concentrations, the collection angles could not be used
to back-calculate any difference in the degrees of phase separation
of the blends when using different CQ amounts. It is possible that
differences observed in subsequent solar cell performance (to be discussed
in the next section) are a result more so of internal waveguide morphology.
The varied collection ranges to the extent at which they can be used
to infer phase separation simply indicates an evident difference when
preparing intersecting waveguide structures from blends with different
fractions of the polymer components. The similar CCD intensity patterns
as a function of incident angle observed for the other waveguide in
the array (see the Supporting Information) indicate that it would also have the same collection ranges and
degrees of separation determined herein.One explanation for
the higher degree of phase separation in the
single-waveguide array over the multiwaveguide array may be the greater
overall exposure of the medium for the latter, resulting in greater
degrees of cure, which can slow down the dynamics of phase separation.
However, for the concentration of NOA65 to reach 95% in the multidirectional
waveguide lattice structures, the boundaries of the acceptance range
should be ca. 20–90° and ca. 14–90° for 20/80
and 50/50 blends, respectively, notably decreasing the lower bound
of the acceptance range. This additional enhancement to the lower
bound of the acceptance range is not necessary: Light within the 0–20°
can be sufficiently collected and converted in the solar cell; rather,
wide-angle capture is the important operational feature of the slanted
waveguides. Likewise, beyond incident angles of 70°, significant
Fresnel reflection at the air–polymer interface plays a greater
role in the loss of light than any shading or loss effects at the
solar cell surface. Hence, the boundaries of the acceptance range
as achieved with the structures herein are sufficient, compared to
what might possibly be achieved with greater degrees of phase separation,
and certainly sufficient to demonstrate the concept of enhancing wide-angle
light collection compared to single vertically aligned waveguide arrays,
as indicated by the following discussion on solar cell performance.
Finally, it is important to note that discerning collection ranges
for the boundaries of the acceptance range from the transmission intensity
profiles are only a visual approximation. There is no sharp transition
between the regimes of waveguiding and lossy transmission, but rather
with an increased angle (away from the acceptance range), a greater
portion of light will be able to pass through the waveguides. Hence,
the selection of 25 and 30° as the lower bound for the 20/80
blend was a middle number from the observed approximate transition
from what visually appeared to be the formation of distinct spots.
Likewise, the selection of 30° for the 50/50 blend was an approximate
for the transition to the profile possessing a strong spotted pattern.Figure shows angle-resolved
EQE spectra for the multiwaveguide arrays and single vertical waveguide
arrays for both 50/50 and 20/80 weight fractions. The spectral curves
naturally drop with increased incident angle both because of unavoidable
Fresnel reflection at the air–polymer interface and the shading
losses from the silicon solar cell top contacts.[13,20] We have already shown that the single vertical waveguide array shows
a lesser drop than a uniform coating.[20]Figure now shows
that the multidirectional waveguide lattice structures enable the
EQE to drop less, evident in the most responsive region of the solar
cells (i.e., EQE plateaus at ca. 600–900 nm), compared to the
single vertically aligned waveguide array. This enhancement is observed
especially at higher incident angles, 50–70° down to an
incident angle of 40° showing spectra positioned among those
for smaller incident angles. These EQE curves showing higher values
clearly indicate an enhancement in the incident angle-dependent conversion
efficiency. The multiwaveguide lattice structures produced with 1.5
and 2.5 wt % CQ both visually show similar angle-dependent EQE responses,
both of which are greater than that achieved with a single vertically
aligned waveguide array.
Figure 4
Angle-resolved EQE spectra of solar cells encapsulated
with waveguide
structures. (a, b) Intersecting waveguide structures produced from
50/50 polymer blends with 2.5 and 1.5 wt % CQ, respectively. (c) Single
vertical waveguide array produced from 50/50 polymer blends with 2.5
wt % CQ. (d, e) Intersecting waveguide structures produced from 20/80
polymer blends with 2.5 and 1.5 wt % CQ, respectively. (f) Single
vertical waveguide array produced from 20/80 polymer blends with 2.5
wt % CQ. Single vertical waveguide arrays shown in (c) and (f) are
used for comparison to the intersecting waveguide structures produced
with the same polymer blend fractions.
Angle-resolved EQE spectra of solar cells encapsulated
with waveguide
structures. (a, b) Intersecting waveguide structures produced from
50/50 polymer blends with 2.5 and 1.5 wt % CQ, respectively. (c) Single
vertical waveguide array produced from 50/50 polymer blends with 2.5
wt % CQ. (d, e) Intersecting waveguide structures produced from 20/80
polymer blends with 2.5 and 1.5 wt % CQ, respectively. (f) Single
vertical waveguide array produced from 20/80 polymer blends with 2.5
wt % CQ. Single vertical waveguide arrays shown in (c) and (f) are
used for comparison to the intersecting waveguide structures produced
with the same polymer blend fractions.To more closely and quantitatively describe the
enhancements, Figure a shows plots the
percent increase in the maximum EQE value (found at ∼770 nm
within the spectral plateau) for the EQE curves in Figure for the multiwaveguide arrays
relative to the single-waveguide array. Indeed, all multiwaveguide
arrays show enhancements in conversion efficiency, specifically an
increasing enhancement (i.e., percent increase) with increased incident
angle. Structures produced from 20/80 blends show greater enhancement
than those produced from the 50/50 blends. Likewise, structures produced
with 2.5 wt % CQ perform better than those produced with 1.5 wt %
CQ. We further calculated the total EQE across the entire response
spectrum as a function of incident angle, as shown in Figure b. Once again, the 20/80 blend
outperforms the 50/50, but the difference between the use of 1.5 and
2.5 wt % CQ in the formulations on the total EQE values is not clear.
Specifically, structures from 20/80 blends with 2.5 wt % CQ yield
a marginally greater total EQE compared with using 1.5 wt % CQ, which
diminishes with increased angle of incidence. On the other hand, for
50/50 blends, using 1.5 wt % shows a slightly greater total EQE compared
with 2.5 wt % CQ, which also diminishes with a greater incident angle.
The difference between the enhancements revealed by examining the
EQE plateau and the total EQE (Figure a,b) may be a result of the selection of the middle
of the EQE curve plateaus as a more subjective indication of enhancement,
with the total EQE over the entire response spectrum being more representative
of performance. Hence, the EQE curves represent more of an indication
of the presence of enhancement, but the total EQE should be used for
a more accurate assessment. Hence, Figure c shows the percent increase in total EQE
as a function of incident angle for the multiwaveguide structures
relative to the single vertically aligned waveguide array. The plots
show that structures produced from both 20/80 and 50/50 blends with
either 1.5 or 2.5 wt % CQ provide enhancement in the total EQE. Interestingly,
all structures show an approximate constant improvement of ca. 6–7%
for low incident angles of 0–30°. The percent increase
in the total EQE then begins to rise after 30°, which is within
the calculated acceptance cone of the slanted waveguides (>25°)
of the multiwaveguide structure and beyond that for the single vertically
aligned waveguide array (<∼20°). This results in the
steady monotonic increase in the gained total EQE as collection effectively
persists for the multidirectional waveguides but drops for the single-waveguide
array. The combined results of the transverse intensity profiles and
the EQE response as well as the predicted collection ranges of the
structures provide compelling evidence that the multiwaveguide array
structures provide an enhancement in wide-angle energy conversion
by virtue of the structure-light collection properties.
Figure 5
Quantitative
analysis of encapsulated solar cell performance. (a)
Percent increase in EQE (examined at ∼770 nm in the spectra)
of intersecting waveguide encapsulant structures (produced with two
different CQ concentrations) with respect to their single vertical
waveguide array as a function of angle of incidence; 770 nm was selected
as the region of approximate maximal response of the solar cells.
(b) Total EQE as a function of incident angle for both intersecting
waveguide lattices and singe vertical waveguide array encapsulants.
(c) Percent increase in total EQE for intersecting waveguide structures
with respect to single vertical waveguide arrays.
Quantitative
analysis of encapsulated solar cell performance. (a)
Percent increase in EQE (examined at ∼770 nm in the spectra)
of intersecting waveguide encapsulant structures (produced with two
different CQ concentrations) with respect to their single vertical
waveguide array as a function of angle of incidence; 770 nm was selected
as the region of approximate maximal response of the solar cells.
(b) Total EQE as a function of incident angle for both intersecting
waveguide lattices and singe vertical waveguide array encapsulants.
(c) Percent increase in total EQE for intersecting waveguide structures
with respect to single vertical waveguide arrays.It is interesting to note that all intersecting
waveguide structures
provide a constant, baseline improvement to the total EQE over the
single vertically aligned waveguide array for the low incident angle
range of 0–20°. One explanation is that transmitted light
beyond the waveguide acceptance range still interacts with the waveguide
structures, cutting through them at low incident angles beyond their
acceptance range, but still possibly being collected to some extent
(lossy transmission) or even possibly scattered by the internal waveguide
morphology. The confinement into the high-refractive-index planes
of intersection of the waveguides is already demonstrated at low angles
in Figure . Hence,
any interaction (e.g., scattering or collection as lossy modes) that
possibly enables light to reach the solar cell surface at a non-normal
incidence can aid in total light collected. This is a well-known phenomenon
employed in solar cells: scattering light internally away from normal
incidence, which is often achieved by surface texturing the solar
cell surface. When light is redirected away from the normal incident
pathway, it is more likely to be confined within the encapsulant because
the light will bounce within the encapsulant at angles outside of
the “loss cone”. The loss cone is a range of incident
angles of light inside the encapsulant whereby a portion of which
will be lost by refraction back through the air–encapsulant
interface. Hence, in addition to its light collecting properties when
light is within the acceptance cone, beyond the acceptance cone, the
structures appear to provide the capability to still collect, confine,
and possibly scatter light, thereby providing interactions and enabling
transmission properties of light to be advantageously altered toward
improving total energy conversion efficiency. Such effects have been
revealed in previous simulation studies.[20,24]Figure shows
the
current density–voltage (J–V) curves of the encapsulated solar cells under AM 1.5 G
solar irradiation. The curves show the natural decrease in the current
output, as indicated by the drop in the short-circuit current density
(JSC, at 0 V). However, the curves reveal
small increases in the short-circuit current density of the multidirectional
waveguide arrays vs the corresponding single vertically aligned waveguide
arrays. To show this enhancement more clearly, plots of JSC vs incident angle (Figure a,b) indicate that solar cells with multidirectional
waveguide encapsulations provide a small but consistent increase in
the current density relative to a single vertically aligned waveguide
array, which becomes more pronounced with increased incident angle.
The average increase in the short-circuit current density of the entire
incident angular range was 0.36 and 0.60 mA/cm2 for 20/80
blends with 1.5 and 2.5 wt % CQ, respectively, and likewise, the average
increase in the short-circuit current density was 0.22 and 0.80 mA/cm2 for 50/50 blends with 1.5 and 2.5 wt % CQ, respectively.
These nominal increases could also be expressed as average percent
increases: 1.91 and 3.03% for 20/80 blends with 1.5 and 2.5 wt % CQ,
respectively, and 1.00 and 3.98% for 50/50 blends with 1.5 and 2.5
wt % CQ, respectively. If only the ultrawide angles (50–70°)
are considered, the increases in short-circuit current density are
0.55 (3.6%) and 0.69 (4.91%) for 20/80 blends and 0.14 (1.14%) and
0.79 (5.84%) for 50/50 blends, both for 1.5 and 2.5 wt % CQ, respectively.
The percent increases in the short-circuit current density as a function
of incident angle are plotted in Figure c. While the values visually appear to fluctuate,
there is indeed a positive trend to the increase in the short-circuit
current density with increased incident angle. The trends once again
confirm that formulations prepared with 2.5 wt % CQ as well as those
from 20/80 blends provided the greatest increase in the current output;
yet comparatively, all multidirectional lattices provide an overall
improvement compared to a single-waveguide array both for moderate
as well as very wide incident angles. It is notable that current output
is enhanced even below the lower bound of the acceptance range, confirming
that light can still positively interact with the multidirectional
waveguide lattice structure. It is also notable that there are instances
of no improvement or loss in performance in the percent increase of JSC of some encapsulant structures, such as 50/50
with 1.5 wt % CQ, which would indicate the importance of selecting
the better weight fraction (and CQ concentration) to improve the encapsulant
properties, to improve electrical performance.
Figure 6
Angle-resolved current
density–voltage (J–V) curves of solar cells encapsulated with
waveguide structures. (a, b) Intersecting waveguide structures produced
from 50/50 polymer blends with 2.5 and 1.5 wt % CQ, respectively.
(c) Single vertical waveguide array produced from 50/50 polymer blends
with 2.5 wt % CQ. (d, e) Intersecting waveguide structures produced
from 20/80 polymer blends with 2.5 and 1.5 wt % CQ, respectively.
(f) Single vertical waveguide array produced from 20/80 polymer blends
with 2.5 wt % CQ. Single vertical waveguide arrays shown in (c) and
(f) are used for comparison to the intersecting waveguide structures
produced with the same polymer blend fractions.
Figure 7
Analysis of electrical output in encapsulated solar cells.
(a,
b) Short-circuit current density (JSC)
as a function of incident angle for encapsulants produced from (a)
50/50 and (b) 20/80 polymer blends. (c) Percent increase in JSC of intersecting waveguides with respect to
a single vertical waveguide array as a function of incident angle.
The dashed line aids to identify positive and negative performance
changes when employing intersecting multiwaveguide structures.
Angle-resolved current
density–voltage (J–V) curves of solar cells encapsulated with
waveguide structures. (a, b) Intersecting waveguide structures produced
from 50/50 polymer blends with 2.5 and 1.5 wt % CQ, respectively.
(c) Single vertical waveguide array produced from 50/50 polymer blends
with 2.5 wt % CQ. (d, e) Intersecting waveguide structures produced
from 20/80 polymer blends with 2.5 and 1.5 wt % CQ, respectively.
(f) Single vertical waveguide array produced from 20/80 polymer blends
with 2.5 wt % CQ. Single vertical waveguide arrays shown in (c) and
(f) are used for comparison to the intersecting waveguide structures
produced with the same polymer blend fractions.Analysis of electrical output in encapsulated solar cells.
(a,
b) Short-circuit current density (JSC)
as a function of incident angle for encapsulants produced from (a)
50/50 and (b) 20/80 polymer blends. (c) Percent increase in JSC of intersecting waveguides with respect to
a single vertical waveguide array as a function of incident angle.
The dashed line aids to identify positive and negative performance
changes when employing intersecting multiwaveguide structures.It is important to note that both waveguide arrays
in the structure
(i.e., ±25° orientations) show similar performance in terms
of solar cell efficiency enhancement and the electrical output (see
the Supporting Information). Hence, symmetric
structures with symmetric optical properties and solar cell performance
indicate that ultrawide-angle light capture (−70 to 70°)
can be achieved through the photopolymerization approach employing
two LED sources.
Discussion
The combined characterization of the structure,
light acceptance
ranges, solar cell conversion efficiency, and current output provides
insights into the overall processing–structure–property–performance
relationship, for which the photopolymerization and phase separation
of the blend are central. The formation of the waveguides entails
first the propagation of polymerized fiber/rod-shaped structure across
the medium, then subsequent polymerization and increased molecular
weight, which induces the blend in the irradiated region to become
thermodynamically unstable and to phase-separate.[32] This phase separation occurs while the molecular weights
of the components continue to grow, which increases the system viscosity
and elasticity, thereby reducing the diffusivity of the blend components.
The kinetic and dynamic balance between photopolymerization and phase
separation allows well-shaped cylindrical phases to form, which possess
high degrees of phase separation, in other words, polymer blends with
well-defined and well-patterned structures and binary phase morphologies.
For the dynamics of phase separation to proceed quicker than it takes
for the system to increase molecular weight, to reduce those dynamics,
it is possible that the phase-separated morphology can deviate from
the cylindrical pattern dictated by the optical beams. Likewise, if
the polymerization rate is too high, the sample can solidify before
any significant phase separation is possible.The results indicate
that the relative weight fractions of the
blend (i.e., 20/80 vs 50/50) play a greater role in the quality of
the cylindrical waveguide geometry. This is especially the case when
considering the depth dependence, where the 50/50 blends show waveguide
cores that diverge or “splay” more so at their ends.
This is associated with the lag in the polymerization rate and molecular
weight increase at greater depths in the blend,[32] allowing phase separation to proceed more than at lesser
depths, and possibly, as in this case, causing the blend morphology
to deviate from the cylindrical geometry. However, the greater concentration
of the free-radical polymer (NOA65) in the 20/80 blends allows the
entire length of the waveguide cores to retain a uniform cylindrical
shape. Furthermore, the 20/80 blends have a more direct thermodynamic
pathway toward phase separation (i.e., 80 100), as the blend will
favor increasing NOA65 and expelling PDMS. This would also enable
the system to more quickly and easily achieve a greater refractive
index, which aids in keeping light confined to the irradiated region,
to enable cylindrical cores to grow with a more uniform width over
its length within the polymer medium. It is also possible that the
diverging morphology in the 50/50 blend captures an imprint of the
diverging nature of the light at very large depths. Greater CQ results
in greater photoinitiation and polymerization rate, which can increase
the molecular weight faster, enabling a greater cross-linking density,
whereby the waveguide core’s integrity in terms of cylindrical
shape and morphology is maintained during phase separation. It can
also in turn cause the refractive index difference of the growing
waveguide to rise quicker, which aids in confining light (i.e., less
divergence at the ends). This is more so the case with 20/80 blends,
with its greater NOA65 content forming robust waveguide cores and
expelling the PDMS without losing the quality of its structure. This
is in accordance with previous work which revealed that symmetric
blends (i.e., 50/50) have a tendency to undergo phase evolution unmitigated
by the optical beams and that weight fractions with higher asymmetry
in the relative weight fractions mitigate phase evolution and are
more suitable for capturing the intended pattern of the optical beams.[32,41] Greater polymerization degrees drive phase separation and increase
the refractive index difference, which provides better collection
and waveguiding of light over a larger acceptance range. The observation
of more asymmetric polymer blends and greater polymerization rates
producing better quality waveguides provides experimental verification
of our theoretical predictions from our Multiphysics framework on
structure and morphology formation.[44] It
is also possible that there are variations in the degree of polymerization
between regions irradiated by a single beam and regions in which two
beams overlap, as well as the dark regions, as indicated in our simulation
work.[44] Detailed investigation of the spatially
resolved conversion in different regions of the structure is currently
underway and will be reported in the future.The model between
collection angle, blend volume fraction, and
refractive index difference shows that the cores show a significant
degree of phase separation but not complete phase separation and that
the surroundings are only mildly changed in terms of blend composition
and refractive index. Hence, the structure is best described as one
in which there is an NOA65-rich core, and a mildly richer PDMS cladding.
This contrasts with the 95% NOA65 observed for vertically aligned
single-waveguide arrays, most likely achieved by the lower and more
isolated exposure by a single array of optical beams allowing more
time and mobility to achieve a greater degree of phase separation,
in contrast to herein where there is double the total exposure using
two LEDs. Their slant angles also give them a greater path length,
thus exposing more of the medium to irradiation, which can increase
the photopolymerization rate and thoroughness of the cure.While
the volume fraction of the NOA65 has increased (and PDMS
decreased) in the waveguide cores owing to the phase separation, the
lack of complete phase separation implies that some PDMS remains in
the cores. Also, the volume fraction in the surrounding medium is
only slightly lower than the bulk volume fraction of 80%, owing to
the very low volume fraction of the PDMS in the cores only minutely
diluting the NOA65 in the surroundings. This indicates a correlation
between waveguide density in the array (not explored herein, but to
make the point) and potential refractive index difference: the more
waveguides form in a volume (i.e., waveguide density), the greater
the volume of PDMS that can be expelled into the surroundings, allowing
greater dilution and greater achievable refractive index differences
between the core and cladding. However, more dense arrays will require
mask patterns with density aperture patterns, which increases the
overall exposure of the medium during photopolymerization (i.e., denser
arrays of optical beams), with the unintended result being faster
curing kinetics quickly arresting the very phase separation dynamics
needed to evolve the high-refractive-index difference to yield wide
acceptance ranges. This is most likely why the collection angles do
not vary significantly between sparse or density waveguide arrays[29] because any potentially greater collection window
from a greater refractive index from denser waveguides is inhibited
by the greater light exposure and arrested phase separation dynamics
owing to greater exposure hindering their formation. Nevertheless,
the dependence of the waveguide structure and collection properties
on waveguide size and density is the subject of continued work that
will be reported in the future.Note that the degree of separation
does not imply that the waveguides
themselves are uniform in the blend distribution throughout the cross
section and length of the waveguide cores. It is certainly possible
that phase separation has occurred internally and that the refractive
index properties of the cores are related more so to a volume average
of the smaller phases. The presence of “streaks” or
“striations” along the lengths of the waveguides might
be indicative of internal morphology in the waveguide cores. This
may also be the case, more so, for the 50/50 blends, which can produce
more random phase separation or a coarser morphology in the waveguide
cores, which, while not significantly affecting the apparent collection
angles, can affect the energy conversion and electrical output. Nevertheless,
modulations in light transmission and improvements in solar cell performance
are still observed. This indicates that it is not necessary to obtain
“perfect” uniformity in the waveguides to significantly
modulate light transmission, or, on the other hand, this may indicate
potential opportunities for improved performance if the processing
conditions can produce a more uniform core–cladding geometry.
Simulations indicate that a high polymerization rate is favorable
for achieving well-defined intersecting structures.[44] Hence, increased photoinitiator or light intensity may
be considered, so long as they are not too high to rapidly cure the
blend such that phase separation is arrested or significantly inhibited.
We produced our structures at the maximum intensity of our LED sources,
and a higher CQ content might not be desirable owing to the possible
remnant CQ absorbing in the blue region of solar radiation. One approach
going forward would be to employ UV LEDs for the combination of rapid
curing and use of an efficient UV photoinitiator, which may provide
higher polymerization rates and non-visible-light absorbance, to enable
better quality waveguides to be produced, and such studies are currently
underway. Combining these multidirectional waveguide structures with
some type of micro-lens array placed on top of it might aid with collection
at extreme incident angles (i.e., 60–70°) by providing
stronger re-steering into the film at smaller angles, as an approach
to reduce losses from Fresnel reflection at the planar air–polymer
interface, but this additional advance to encapsulant architecture
is beyond the scope of this work.Overall, through the selection
of appropriate relative weight fractions
of the blend and the photoinitiator concentration, high-quality waveguides
may be produced, with well characterized and modeled acceptance ranges
that correlate to their capability to enable greater wide-angle light
collection, conversion, and electrical output when employed as solar
cell encapsulants. It is important to note that improvements in the
current density even on the order of ∼1 mA/cm2 is
significant, especially when considering the total area of a solar
cell and solar panel. For example, as of 2020, current individual
solar cells are 21 cm × 21 cm, and panels may contain either
60 or 72 cells. Hence, a nominal increase of 0.6 mA/cm2 achieved with an encapsulant produced from 20/80 blends and 2.5
wt % CQ, for example, translates to an increase in current output
of approximately 15.9 and 19.1 A per 60- and 72-cell panel, respectively.
These output currents would also scale with the number of panels in
a solar farm. Solar panels placed in nonoptimized locations (building
or residential roofs) would also see a benefit from these enhanced
collection properties. Long-term rooftop studies of collection, conversion,
and electrical output of encapsulated solar cells over the course
of the day and over seasons are currently planned and will be reported
in the future.
Conclusions
We have produced multiple intersecting
waveguide array structures
in photopolymerizable polymer blends to enable wide-angle light capture
and waveguide-based light transmission in thin polymer films as novel
encapsulation materials for solar cells. The structures demonstrate
the capability to accept very high incident angle radiation, enabling
their transmission and incidence on the solar cell surface at angles
smaller than those dictated by natural refraction. Thereby, more direct
incident radiation mitigates front-contact losses, thereby sustaining
energy conversion and current output over a larger angular range,
and especially at wide incident angles up to 70°. The structure
and performance of the multidirectional waveguide array structures
are correlated to the relative weight fractions of the polymer blend
components and free-radical photoinitiator concentration: greater
fractions of high-refractive-index polymer and photoinitiator correlate
to better waveguide structures and improved light collection, transmission,
energy conversion, and solar cell output. These blend parameters allow
for better evolution of the medium into higher-quality core–cladding
architectures for the collection, confinement, and waveguide-based
transmission of light. Improved performance is also observed for small
incident angles, beyond the acceptance range, owing to increased interactions
of the waveguide structures with light. This work demonstrates the
capability to design advanced multiple-waveguide architectures in
thin films with novel transmission properties toward improved solar
energy collection and conversion in solar cells. This capability can
extend and sustain solar cell performance over the course of the day
and across seasons, as the incident angle of solar irradiation varies,
enabling greater total power output, which can increase the capability
of clean, renewable solar energy to contribute power to the grid.
Authors: Yeong Jae Kim; Young Jin Yoo; Dong Eun Yoo; Dong Wook Lee; Min Seok Kim; Hyuk Jae Jang; Ye-Chan Kim; Jae-Hyung Jang; Il Suk Kang; Young Min Song Journal: ACS Appl Mater Interfaces Date: 2019-09-18 Impact factor: 9.229