Brendan T. O'Connor

Organic photovoltaic cells with controlled polarization sensitivity

In this study, we demonstrate linearly polarized organic photovoltaic cells with a well-controlled level of polarization sensitivity. The polarized devices were created through the application of a large uniaxial strain to the bulk heterojunction poly(3-hexylthiophene):Phenyl-C61-butyric acid methyl ester (P3HT:PCBM) film and printing the plastically deformed active layer onto a PEDOT:PSS and indium tin oxide coated glass substrate. The P3HT:PCBM layer is processed such that it is able to accommodate high strains (over 100%) without fracture. After printing the strained films, thermal annealing is used to optimize solar cell performance while maintaining polarization sensitivity. A dichroic ratio and short circuit current ratio of ≈6.1 and ≈1.6 were achieved, respectively.

Strong polymer molecular weight-dependent material interactions: impact on the formation of the polymer/fullerene bulk heterojunction morphology

The performance of polymer–fullerene bulk heterojunction (BHJ) solar cells is highly affected by the morphology of the blend film. Though the structure of the BHJ morphology is well-understood, the relationship between relevant material interactions and BHJ morphological evolutions is poorly understood and seldom explored. In this report, we discuss the impact of polymer molecular weight (MW) on thermodynamic and kinetic phenomena which have a drastic influence on the nanoscale BHJ morphology. The blend film comprises a highly aggregating low bandgap diketopyrrolopyrrole-based polymer PDPP3T and the fullerene electron acceptor molecule PC71BM, cast from a 1,2-dichlorobenzene (DCB) solution with and without the additive 1,8-diiodooctane (DIO). The pair-wise interactions among the components were evaluated by Flory–Huggins interaction parameters (χ). The BHJ blend of PDPP3T and PC71BM exhibited liquid–liquid (L–L) phase separation as a result of strong polymer–fullerene interactions (large χPDPP3T–fullerene) in DCB solution. In contrast, addition of 3% DIO into the DCB solution is found to stimulate polymer aggregation which gives rise to liquid–solid (L–S) phase separation. Large χPDPP3T–fullerene and χPDPP3T–solvent were observed as a result of increasing polymer MW, and these changes promote strong L–L phase separation and polymer aggregation in the blend solution, respectively. The latter interactions have led to low molecular mobility, with an end result of reduced crystallinity and smaller domain size of the BHJ films. The observed dramatic MW-dependent morphological changes were also manifested in solar cell outputs as well as charge carrier dynamics calculated by transient absorption measurements.

Performance and Design Comparison of a Bulk Thermoelectric Cooler With a Hybrid Architecture

This paper compares the economic viability and performance outcomes of two different thermoelectric device architectures to determine the advantages and appropriate use of each configuration. Hybrid thermoelectric coolers (TECs) employ thin-film thermoelectric materials sandwiched between a plastic substrate and form a corrugated structure. Roll-to-roll (R2R) manufacturing and low-cost polymer materials offer a cost advantage to the hybrid architecture at the sacrifice of performance capabilities while conventional bulk devices offer increased performance at a higher cost. Performance characteristics and cost information are developed for both hybrid and conventional bulk single-stage thermoelectric modules. The design variables include device geometry, electrical current input, and thermoelectric material type. The tradeoffs between cooling performance and cost will be explored, and the thermoelectric system configuration is analyzed for both hybrid and conventional bulk TECs.

A direct correlation of x-ray diffraction orientation distributions to the in-plane stiffness of semi-crystalline organic semiconducting films

Large charge mobilities of semi-crystalline organic semiconducting films could be obtained by mechanically aligning the material phases of the film with the loading axis. A key element is to utilize the inherent stiffness of the material for optimal or desired alignment. However, experimentally determining the moduli of semi-crystalline organic thin films for different loading directions is difficult, if not impossible, due to film thickness and material anisotropy. In this paper, we address these challenges by presenting an approach based on combining a composite mechanics stiffness orientation formulation with a Gaussian statistical distribution to directly estimate the in-plane stiffness (transverse isotropy) of aligned semi-crystalline polymer films based on crystalline orientation distributions obtained by X-ray diffraction experimentally at different applied strains. Our predicted results indicate that the in-plane stiffness of an annealing film was initially isotropic, and then it evolved to transv...

Complete intrinsic coincident polarimetry using stacked organic photovoltaics

Measuring the 2 dimensional Stokes vector, to determine the polarization state of light, finds application in multiple areas, including the characterization of aerosol size distributions, target identification, quality control by evaluating the distribution of stress birefringence, resolving data channels in telecommunications, and for evaluating biological tissues in medical imaging. Conventional methods, such as channeled and division of focal plane polarimeters, usually limit spatial resolution, while others, like division of aperture or division of amplitude polarimeters, have higher complexity and less compactness. To help solve these issues, we have developed a system that uses semitransparent organic photovoltaics (OPVs) as photodetectors. The active area of the devices consist of biaxially oriented polymer films, which enables the device to preferentially absorb certain polarized states of incident light, depending on the orientation of the polymer chains. Taking advantage of the cells’ transparency and ease of processing, compared to inorganic materials, enables multiple devices to be “stacked” along the optical axis. Presently, experiments have been conducted to detect linear polarization states of light. We use three stacked OPVs, where each device can measure one of the first three Stokes parameters simultaneously, thereby ensuring high spatial and temporal resolution with inherent spatial registration. In this paper, the fabrication of the OPVs and the design and calibration technique is documented, along with experimental data, supporting the hypothesis.

Monolithic intrinsic Coincident polarimeter using organic photovoltaics

Polarimeters have broad applications in remote sensing, astronomy, and biomedical imaging to measure the emitted, reflected, or transmitted state of polarization (SOP). An Intrinsic Coincident full-Stokes Polarimeter (ICP) was previously demonstrated by our group, in a free space configuration, by using stain-aligned polymer-based organic photovoltaics (OPVs). These were tilted to avoid back-reflection cross-talk. In this paper, we present a theoretical model of a monolithic ICP which considers the back-reflection’s influence. This includes a comparison between the free space model to the new monolithic model. Experimental demonstrations yield less than 3% error between our model and the experiment data.

Crystallization of non-fullerene acceptor might cause catastrophic failure in ductile organic solar cells (Conference Presentation)

Organic solar cell (OSC) technology has recently achieved over 13% efficiency through the synthesis of novel non-fullerene small molecule acceptors (NFAs), which can be processed from benign solvents as low-cost third generation photovoltaics[1,2]. Of critical importance to OSCs is understanding the morphological and thermal stability of the active layers governed by thermodynamics and kinetics as an intrinsic stability process which cannot be controlled by encapsulation[3,4]. Here we highlight the importance of ductility of donor polymers on nucleation and growth of micro-size small molecule crystals which leads to the catastrophic failure of the solar cells in the long-term operating condition We consider three high performance polymers P3HT, PBnDBT-FTAZ, and PffBT4T-C9C13 blended with EH-IDTBR as the model systems to investigate the thermal stability of state of the art non-fullerene OSCs, where elevated temperatures were used to accelerate the crystal formation and imitate the long-term operation conditions of OCSs. We also propose an easy accessible method using differential scanning calorimetry (DSC) to investigate the thermal behavior of NFA in the blends. Although non-fullerene solar cells have shown to have better overall morphological stability compared to their fullerene counterparts, our results suggest that catastrophic failure due to micro-size crystal formation in non-fullerene systems can happen at a rate similar to fullerene systems unless the right donor polymer is chosen to suppress the crystallization of small molecule. It is also shown and argued that the growth rate of small molecule crystals can be reduced upon mixing of NFAs with semi-crystalline polymers, such as P3HT with a higher overall density compared to amorphous donor polymers, i.e. PBnDT-FTAZ. Our findings may pave a way to understand and predict the morphological stability of non-fullerene OSCs. References [1] L. Ye, Y. Xiong, Q. Zhang, S. Li, C. Wang, Z. Jiang, J. Hou, W. You, H. Ade, Adv. Mater. 2017, DOI: 10.1002/adma.201705485. [2] S. Holliday, R. S. Ashraf, A. Wadsworth, D. Baran, S. A. Yousaf, C. B. Nielsen, C.-H. Tan, S. D. Dimitrov, Z. Shang, N. Gasparini, M. Alamoudi, F. Laquai, C. J. Brabec, A. Salleo, J. R. Durrant, I. McCulloch, Nat. Commun. 2016, 7, 11585. [3] M. Ghasemi, L. Ye, Q. Zhang, L. Yan, J. H. Kim, O. Awartani, W. You, A. Gadisa, H. Ade, Adv. Mater. 2017, 29, 1604603. [4] L. Ye, H. Hu, M. Ghasemi, T. Wang, B. A. Collins, J.-H. Kim, K. Jiang, J. Carpenter, H. Li, Z. Li, T. McAfee, J. Zhao, X. K. Chen, J. Y. L. Lai, T. Ma, J.-L. Bredas, H. Yan, H. Ade, Nat. Mater. 2018, DOI: 10.1038/s41563-017-0005-1.

Viscoelastic polymer semiconductors for stretchable electronics: the importance of interfaces on mechanical behavior (Conference Presentation)

Viscoelastic polymer semiconductors have the potential to be effective components in stretchable electronics. These malleable materials provide a simple and effective approach to realize stretchable field effect transistors and sensors.[1] For successful operation, the polymer film must be able to withstand large cyclic strains while maintaining electrical properties. Here, we show that in the stretching process, the elastomer substrate plays a critical role in the mechanical response of the semiconductor film. In particular, we explore the role of adhesion and near-surface modulus of a PDMS elastomer on the ability to achieve stretchable PDPP-4T films. We also show the use of PDMS tension on the stability of the film. We find that the increase in near-surface modulus of the PDMS and maintaining the PDMS in tension limits film wrinkling under large cyclic strain, and that an increase adhesion greatly reduces film delamination and propensity to tear. We show that through proper engineering of the elastomer substrate, the PDD-4T film has a surface roughness consistently below 3 nm for a strain range of 50% and for over 100 strain cycles. The local morphology and charge transport of the semicrystalline DPP-4T is also characterized in detail and shown to vary in a systematic and stable manner under this large strain range. These results demonstrate the ability to use low glass transition temperature polymers for intrinsically stretchable semiconductors given appropriate interactions with adjacent elastomer layers. [1] T. Sun, B. O’Connor, et al, Adv. Electron. Mater. 1600388, 2017.

Intrinsic coincident full-Stokes polarimeter using stacked organic photovoltaics and architectural comparison of polarimeter techniques

An intrinsic coincident full-Stokes polarimeter is demonstrated by using stain-aligned polymer-based organic photovoltaics (OPVs) which can preferentially absorb certain polarized states of incident light. The photovoltaic-based polarimeter is capable of measuring four stokes parameters by cascading four semitransparent OPVs in series along the same optical axis. Two wave plates were incorporated into the system to modulate the S3 stokes parameter so as to reduce the condition number of the measurement matrix. The model for the full-Stokes polarimeter was established and validated, demonstrating an average RMS error of 0.84%. The optimization, based on minimizing the condition number of the 4-cell OPV design, showed that a condition number of 2.4 is possible. Performance of this in-line polarimeter concept was compared to other polarimeter architectures, including Division of Time (DoT), Division of Amplitude (DoAm), Division of Focal Plane (DoFP), and Division of Aperture (DoA) from signal-to-noise ratio (SNR) perspective. This in-line polarimeter concept has the potential to enable both high temporal (as compared with a DoT polarimeter) and high spatial resolution (as compared with DoFP and DoA polarimeters). We conclude that the intrinsic design has the same ~√2 SNR advantage as the DoAm polarimeter, but with greater compactness.

Charge transport in highly aligned conjugated polymers (Presentation Recording)

Charge transport in conjugated polymers has a complex dependence on film morphology. Aligning the polymer chains in the plane of the film simplifies the morphology of the system allowing for insight into the morphological dependence of charge transport. Highly aligned conjugated polymers have also been shown to lead to among the highest reported field effect mobilities in these materials to date. In this talk, a comparison will be made between aligned polymer films processed using two primary methods, nanostructured substrate assisted growth and mechanical strain. A number of polymer systems including P3HT, pBTTT, N2200, and PCDTPT are considered, and the processed films are analyzed in detail with optical spectroscopy, AFM, TEM, and X-ray scattering providing insight into the molecular features that allow for effective alignment. By contrasting the morphology of these films, several insights into underlying charge transport limitations can be made. A number of key morphological features that lead to high field effect mobility and charge transport anisotropy in these films will be discussed. In addition, several unique features of organic thin film transistor device behavior in these systems will be examined including the commonly observed gate voltage dependence of saturated field effect mobility.