25 research outputs found
Photonics and transport in bulk heterojunction organic solar cells
In this thesis, the groundwork is established for a new type of bulk heterojunction (BHJ) organic solar cell geometry that has photonic crystal (PC) photoactive layers. This design is motivated by the need to improve light absorption without increasing active layer thickness, which for many BHJ systems, degrades electrical performance. It is demonstrated that with the right choice of materials and cell dimensions, quasiguided or resonant modes are excited near the band edge of a variety of BHJ blends to enhance absorption. Resonant modes are predicted by first developing a scattering matrix optical model and then observed in wavelength-, polarization-, and angular-dependent reflection and photocurrent measurements. PC cells are fabricated using a facile nanopatterning technique, where highly ordered arrays of submicron features are constructed over large areas in a single step. Optical and electrical function of this new cell architecture is fully explored in this thesis. Through optical measurements and modeling, PC devices show clear enhancements in light absorption. On the other hand, the impact of the nonplanar geometry on electrical performance is not as easily deduced due to the multitude of electrical processes that lead to photocurrent generation. First, the electrical properties of the electron transporting layer that interfaces with the BHJ nanopattern and provides optical contrast in the PC greatly affect parasitic resistances in the solar cell. By including resistance losses in a drift/diffusion numerical model that describes electrical performance, it is shown that these losses greatly influence fundamental steps leading to photocurrent generation. This is confirmed with experiment by comparing two BHJ material systems that have different affinities for exciton separation. Second, significant levels of free carrier recombination are predicted by the electro-optical model due to the relatively long transport paths in the nanopattern features. To test this prediction, an experimental technique is developed to measure the transport lengths of photogenerated electrons and holes in BHJ solar cells. It is found that transport lengths of positive and negative carriers are mismatched and helps explain both PC electrical performance and recent conflicting results of planar BHJ solar cells in the literature
Layerless fabrication with continuous liquid interface production
Despite the increasing popularity of 3D printing, also known as additive manufacturing (AM), the technique has not developed beyond the realm of rapid prototyping. This confinement of the field can be attributed to the inherent flaws of layer-by-layer printing and, in particular, anisotropic mechanical properties that depend on print direction, visible by the staircasing surface finish effect. Continuous liquid interface production (CLIP) is an alternative approach to AM that capitalizes on the fundamental principle of oxygen-inhibited photopolymerization to generate a continual liquid interface of uncured resin between the growing part and the exposure window. This interface eliminates the necessity of an iterative layer-by-layer process, allowing for continuous production. Herein we report the advantages of continuous production, specifically the fabrication of layerless parts. These advantages enable the fabrication of large overhangs without the use of supports, reduction of the staircasing effect without compromising fabrication time, and isotropic mechanical properties. Combined, these advantages result in multiple indicators of layerless and monolithic fabrication using CLIP technology
Layerless fabrication with continuous liquid interface production
Despite the increasing popularity of 3D printing, also known as additive manufacturing (AM), the technique has not developed beyond the realm of rapid prototyping. This confinement of the field can be attributed to the inherent flaws of layer-by-layer printing and, in particular, anisotropic mechanical properties that depend on print direction, visible by the staircasing surface finish effect. Continuous liquid interface production (CLIP) is an alternative approach to AM that capitalizes on the fundamental principle of oxygen-inhibited photopolymerization to generate a continual liquid interface of uncured resin between the growing part and the exposure window. This interface eliminates the necessity of an iterative layer-by-layer process, allowing for continuous production. Herein we report the advantages of continuous production, specifically the fabrication of layerless parts. These advantages enable the fabrication of large overhangs without the use of supports, reduction of the staircasing effect without compromising fabrication time, and isotropic mechanical properties. Combined, these advantages result in multiple indicators of layerless and monolithic fabrication using CLIP technology
Fluorine Substituents Reduce Charge Recombination and Drive Structure and Morphology Development in Polymer Solar Cells
Three structurally identical polymers, except for the
number of
fluorine substitutions (0, 1, or 2) on the repeat unit (BnDT-DTBT),
are investigated in detail, to further understand the impact of these
fluorine atoms on open circuit voltage (<i>V</i><sub>oc</sub>), short circuit current (<i>J</i><sub>sc</sub>), and fill
factor (<i>FF</i>) of related solar cells. While the enhanced <i>V</i><sub>oc</sub> can be ascribed to a lower HOMO level of
the polymer by adding more fluorine substituents, the improvement
in <i>J</i><sub>sc</sub> and <i>FF</i> are likely
due to suppressed charge recombination. While the reduced bimolecular
recombination with raising fluorine concentration is confirmed by
variable light intensity studies, a plausibly suppressed geminate
recombination is implied by the significantly increased change of
dipole moment between the ground and excited states (Δμ<sub>ge</sub>) for these polymers as the number of fluorine substituents
increases. Moreover, the 2F polymer (PBnDT-DTffBT) exhibits significantly
more scattering in the in-plane lamellar stacking and out-of-plane
π–π stacking directions, observed with GIWAXS.
This indicates that the addition of fluorine leads to a more face-on
polymer crystallite orientation with respect to the substrate, which
could contribute to the suppressed charge recombination. R-SoXS also
reveals that PBnDT-DTffBT has larger and purer polymer/fullerene domains.
The higher domain purity is correlated with an observed decrease in
PCBM miscibility in polymer, which drops from 21% (PBnDT-DTBT) to
12% (PBnDT-DTffBT). The disclosed “fluorine” impact
not only explains the efficiency increase from 4% of PBnDT-DTBT (0F)
to 7% with PBnDT-DTffBT (2F) but also suggests fluorine substitution
should be generally considered in the future design of new polymers
Fluorine Substituents Reduce Charge Recombination and Drive Structure and Morphology Development in Polymer Solar Cells
Three structurally identical polymers, except for the
number of
fluorine substitutions (0, 1, or 2) on the repeat unit (BnDT-DTBT),
are investigated in detail, to further understand the impact of these
fluorine atoms on open circuit voltage (<i>V</i><sub>oc</sub>), short circuit current (<i>J</i><sub>sc</sub>), and fill
factor (<i>FF</i>) of related solar cells. While the enhanced <i>V</i><sub>oc</sub> can be ascribed to a lower HOMO level of
the polymer by adding more fluorine substituents, the improvement
in <i>J</i><sub>sc</sub> and <i>FF</i> are likely
due to suppressed charge recombination. While the reduced bimolecular
recombination with raising fluorine concentration is confirmed by
variable light intensity studies, a plausibly suppressed geminate
recombination is implied by the significantly increased change of
dipole moment between the ground and excited states (Δμ<sub>ge</sub>) for these polymers as the number of fluorine substituents
increases. Moreover, the 2F polymer (PBnDT-DTffBT) exhibits significantly
more scattering in the in-plane lamellar stacking and out-of-plane
π–π stacking directions, observed with GIWAXS.
This indicates that the addition of fluorine leads to a more face-on
polymer crystallite orientation with respect to the substrate, which
could contribute to the suppressed charge recombination. R-SoXS also
reveals that PBnDT-DTffBT has larger and purer polymer/fullerene domains.
The higher domain purity is correlated with an observed decrease in
PCBM miscibility in polymer, which drops from 21% (PBnDT-DTBT) to
12% (PBnDT-DTffBT). The disclosed “fluorine” impact
not only explains the efficiency increase from 4% of PBnDT-DTBT (0F)
to 7% with PBnDT-DTffBT (2F) but also suggests fluorine substitution
should be generally considered in the future design of new polymers
Fluorine Substituents Reduce Charge Recombination and Drive Structure and Morphology Development in Polymer Solar Cells
Three structurally identical polymers, except for the
number of
fluorine substitutions (0, 1, or 2) on the repeat unit (BnDT-DTBT),
are investigated in detail, to further understand the impact of these
fluorine atoms on open circuit voltage (<i>V</i><sub>oc</sub>), short circuit current (<i>J</i><sub>sc</sub>), and fill
factor (<i>FF</i>) of related solar cells. While the enhanced <i>V</i><sub>oc</sub> can be ascribed to a lower HOMO level of
the polymer by adding more fluorine substituents, the improvement
in <i>J</i><sub>sc</sub> and <i>FF</i> are likely
due to suppressed charge recombination. While the reduced bimolecular
recombination with raising fluorine concentration is confirmed by
variable light intensity studies, a plausibly suppressed geminate
recombination is implied by the significantly increased change of
dipole moment between the ground and excited states (Δμ<sub>ge</sub>) for these polymers as the number of fluorine substituents
increases. Moreover, the 2F polymer (PBnDT-DTffBT) exhibits significantly
more scattering in the in-plane lamellar stacking and out-of-plane
π–π stacking directions, observed with GIWAXS.
This indicates that the addition of fluorine leads to a more face-on
polymer crystallite orientation with respect to the substrate, which
could contribute to the suppressed charge recombination. R-SoXS also
reveals that PBnDT-DTffBT has larger and purer polymer/fullerene domains.
The higher domain purity is correlated with an observed decrease in
PCBM miscibility in polymer, which drops from 21% (PBnDT-DTBT) to
12% (PBnDT-DTffBT). The disclosed “fluorine” impact
not only explains the efficiency increase from 4% of PBnDT-DTBT (0F)
to 7% with PBnDT-DTffBT (2F) but also suggests fluorine substitution
should be generally considered in the future design of new polymers
Quantifying Charge Extraction in Organic Solar Cells: The Case of Fluorinated PCPDTBT
We introduce a new and simple method
to quantify the effective
extraction mobility in organic solar cells at low electric fields
and charge carrier densities comparable to operation conditions under
one sun illumination. By comparing steady-state carrier densities
at constant illumination intensity and under open-circuit conditions,
the gradient of the quasi-Fermi potential driving the current is estimated
as a function of external bias and charge density. These properties
are then related to the respective steady-state current to determine
the effective extraction mobility. The new technique is applied to
different derivatives of the well-known low-band-gap polymer PCPDTBT
blended with PC<sub>70</sub>BM. We show that the slower average extraction
due to lower mobility accounts for the moderate fill factor when solar
cells are fabricated with mono- or difluorinated PCPDTBT. This lower
extraction competes with improved generation and reduced nongeminate
recombination, rendering the monofluorinated derivative the most efficient
donor polymer
Single-Step Fabrication of Computationally Designed Microneedles by Continuous Liquid Interface Production
<div><p>Microneedles, arrays of micron-sized needles that painlessly puncture the skin, enable transdermal delivery of medications that are difficult to deliver using more traditional routes. Many important design parameters, such as microneedle size, shape, spacing, and composition, are known to influence efficacy, but are notoriously difficult to alter due to the complex nature of microfabrication techniques. Herein, we utilize a novel additive manufacturing (“3D printing”) technique called Continuous Liquid Interface Production (CLIP) to rapidly prototype sharp microneedles with tuneable geometries (size, shape, aspect ratio, spacing). This technology allows for mold-independent, one-step manufacturing of microneedle arrays of virtually any design in less than 10 minutes per patch. Square pyramidal CLIP microneedles composed of trimethylolpropane triacrylate, polyacrylic acid and photopolymerizable derivatives of polyethylene glycol and polycaprolactone were fabricated to demonstrate the range of materials that can be utilized within this platform for encapsulating and controlling the release of therapeutics. These CLIP microneedles effectively pierced murine skin <i>ex vivo</i> and released the fluorescent drug surrogate rhodamine.</p></div