Browsing by Author "Tsao, Cheng-Si"

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Cofacial Versus Coplanar Arrangement in Centrosymmetric Packing Dimers of Dipolar Small Molecules: Structural Effects on the Crystallization Behaviors and Optoelectronic Characteristics
(2016-07-20)
Chou, Shu-Hua
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Kang, Hao-Wei
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Chang, Shu-Ting
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Wu, Kuan-Yi
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Bazan, Guillermo C.
Two D-pi-A-A molecules (MIDTP and TIDTP) composed of an electron-rich ditolylamino group (D) and an electron-deficient 5-dicyanovinylenylpyrimidine (A-A) fragment bridged together with indeno[1,2-b]thiophene (IDT) were synthesized. These molecules provide an opportunity to examine in-depth the impact of side-chain variations (methyl vs p-tolyl) on the crystallization behaviors, solid-state morphology, physical properties, and optoelectronic characteristics relevant for practical applications. X-ray analyses on single-crystal structures indicate that methyl-substituted MIDTP forms coplanar antiparallel dimers via C-H center dot center dot center dot S interactions and organizes into an ordered slip-staircase arrays. In contrast, p-tolyl-bearing TIDTP shows cofacial centrosymmetric dimers via pi-pi interactions and packs into a less-ordered layered structures. The X-ray diffraction analyses upon thermal treatment are consistent with a superior crystallinity of MIDTP, as compared to that of TIDTP. This difference indicates a greater propensity to organization by introduction of the smaller methyl group versus the bulkier p-tolyl group. The increased propensity for order by MIDTP facilitates the crystallization of MIDTP in both solution-processed and vacuum-deposited thin films. MIDTP forms solution-processed single-crystal arrays that deliver OFET hole mobility of 6.56 x 10(-4) cm(2) V-1 s(-1), whereas TIDTP only forms amorhpous films that gave lower hole mobility of 1.34 x 10(-5) cm(2) V-1 s(-1). MIDTP and TIDTP were utilized to serve as donors together with C-70 as acceptor in the fabrication of small-molecule organic solar cells (SMOSCs) with planar heterojunction (PHJ) or planar-mixed heterojunction (PMHJ) device architectures. OPV devices based on higher crystalline MIDTP delivered power conversion efficiencies (PCEs) of 2.5% and 4.3% for PHJ and PMHJ device, respectively, which are higher than those of TIDTP-based cells. The improved PCEs of MIDTP-based devices are attributed to better hole-transport character.
Distribution of Crystalline Polymer and Fullerene Clusters in Both Horizontal and Vertical Directions of High-Efficiency Bulk Heterojunction Solar Cells
(2013-06-26)
Liu, Chih-Ming
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Su, Ming-Shin
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Jiang, Jian-Ming
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Su, Yu-Wei
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Su, Chun-Jen
In this study, we used (i) synchrotron grazing-incidence small-/wide-angle X-ray scattering to elucidate the crystallinity of the polymer PBTC12TPD and the sizes of the clusters of the fullerenes PC61BM and ThC61BM and (ii) transmission electron microscopy/electron energy loss spectroscopy to decipher both horizontal and vertical distributions of fullerenes in PBTC12TPD/fullerene films processed with chloroform, chlorobenzene and dichlorobezene. We found that the crystallinity of the polymer and the sizes along with the distributions of the fullerene clusters were critically dependent on the solubility of the polymer in the processing solvent when the solubility of fullerenes is much higher than that of the polymer in the solvent. In particular, with chloroform (CF) as the processing solvent, the polymer and fullerene units in the PBTC12TPD/ThC61BM layer not only give rise to higher crystallinity and a more uniform and finer fullerene cluster dispersion but also formed nanometer scale interpenetrating network structures and presented a gradient in the distribution of the fullerene clusters and polymer, with a higher polymer density near the anode and a higher fullerene density near the cathode. As a result of combined contributions from the enhanced polymer crystallinity, finer and more uniform fullerene dispersion and gradient distributions, both the short current density and the fill factor for the device incorporating the CF-processed active layer increase substantially over that of the device incorporating a dichlorobenzene-processed active layer; the resulting power conversion efficiency of the device incorporating the CF-processed active layer was enhanced by 46% relative to that of the device incorporating a dichlorobenzene-processed active layer.
Engineering the Core Units of Small-Molecule Acceptors to Enhance the Performance of Organic Photovoltaics
(1970-01-01)
Wang, Hao-Cheng
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Chen, Chung-Hao
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Li, Ren-Hao
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Lin, Yu-Che
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Tsao, Cheng-Si
Understanding the chemical structures of next-generation small molecules is a critical step for increasing the performance of organic photovoltaics (OPVs); an OPV's small molecule determines not only the extent of light absorption but also the morphology. Herein, four small molecules featuring different cores-indaceno dithiophene, dithienoindeno indaceno dithiophene (IDTT), substituted IDTT, and dithienothiophene-pyrrolobenzothiadiazole-denoted as ID-4Cl, IT-4Cl, m-ITIC-OR-4Cl, and Y7, respectively, are selected to form active layers with poly(quinoxaline) (PTQ10) and poly(benzodithiophene-4,8-dione) (PM6). The Y7 devices exhibit the best performance in both systems, with the power conversion efficiency (PCE) reaching 14.5%; in comparison, ID-4Cl device gives a PCE of 10.0% for blending with PTQ10 and a relative efficiency enhancement of 45%. The same trend occurs for the cases of PM6 blend devices. This enhancement is attributed to i) the improved short-circuit current density that is provided by the greater degree of conjugation in S, N-heteroarenes ladder-type fused-ring cores of Y7, ii) an induced face-on Y7 orientation and smaller domain sizes that result from the sp(2)-hybridized nitrogen side chain, and iii) smaller energy loss. This study reveals the importance of the core structure on the device performance and provides guidelines for the design of new materials for OPV technologies.
Enhancing photovoltaic performance by tuning the domain sizes of a small-molecule acceptor by side-chain-engineered polymer donors
(2019-02-21)
Lin, Yu-Che
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Lu, Yi-Ju
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Tsao, Cheng-Si
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Saeki, Akinori
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Li, Jia-Xing
This paper reports two new fluorine-substituted polymer donors (BO2FC8, BO2FEH), with different side-chain architectures, and a new chlorine-substituted small-molecule acceptor (m-ITIC-OR-4Cl) that are capable of simultaneous charge and energy transfer as the binary blend active layer for organic photovoltaics. We first resolved the single-crystal structure of m-ITIC-OR-4Cl and then used simultaneous grazing-incidence wide-and small-angle X-ray scattering to decipher the multi-length-scale structures-such as the shape and size of aggregated domains and molecular orientation-of the blends of BO2FEH and BO2FC8 with m-ITIC-OR-4Cl. The linear side chains of BO2FC8 facilitated its packing and, thus, induced m-ITIC-OR-4Cl to form smaller disc-shaped aggregated domains (thickness: 2.9 nm) than its aggregate domain (thickness: 5.4 nm) in the blend of the branched BO2FEH. That is, the binary blend system of linear-side-chain BO2FC8 with m-ITIC-OR-4Cl featured larger interfacial areas and more pathways for charge transfer and transport, as evidenced by their carrier mobilities. The highest power conversion efficiency (PCE) of 11.0% was that for the BO2FC8: m-ITIC-OR-4Cl device, being consistent with the predicted PCE of 11.2% using machine learning based on random forest algorism; in comparison, the PCE of the BO2FEH:m-ITIC-OR-4Cl device was 6.4%. This study has not only provided insight into the photovoltaic performances of new polymer donor/small-molecule acceptor blends but has also, for the first time, deciphered the hierarchical morphologies-from molecule orientation to nano-domain shape and size-of such blend systems, linking the morphologies to the photovoltaic performances. The use of side-chain architectures suggests an approach for tuning the morphology of the polymer/small-molecule binary blend active layer for use in organic photovoltaics.
Fractal aggregates of conjugated polymer in solution state
(2006-12-19)
Li, Yen-Cheng
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Chen, Kuei-Bai
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Chen, Hsin-Lung
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Hsu, Chain-Shu
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Tsao, Cheng-Si
Semirigid conjugated polymers have received much scientific and technological interest due to their unique electrical and photonic semiconducting properties. Spectroscopic studies have indicated that these polymers underwent interchain aggregation in the solution state even at large dilution; however, the origin of this event and the structure of the resultant aggregates remained the crucial issues to be resolved. In the present study, we revealed that the interchain aggregation of a conjugated polymer, poly(2,3-diphenyl-5-hexyl-1,4-phenylenevinylene) (DP6-PPV), in solutions with chloroform and toluene generated network aggregates with the hydrodynamic radii of several micrometers. Small angle neutron scattering (SANS) demonstrated that the internal structure of these aggregates could be characterized by the mass fractal dimensions of 2.2-2.7. The networks were looser in chloroform but became highly compact in the poorer toluene solvent due to severe segmental association. Increasing the temperature alleviated the segmental association in toluene while largely retaining the mass fractal dimension of the aggregates. However, the interchain aggregation was never completely dissipated by the heating, suggesting the existence of two types of segmental association with distinct stability. The highly stable segmental association that could neither be solvated by chloroform nor be disrupted thermally in toluene was attributed to the d-d complex already present in the DP6-PPV powder used for the solution preparation. The chains tied firmly by this complex formed network aggregates in the solution and hence reduced the entropy of mixing of the polymer. In the poorer toluene solvent, further segmental association took place within the preexisting aggregates, making the networks more compact. This type of segmental association could be disrupted by moderate heating, and its occurrence was ascribed to the poor affinity of the aliphatic side chains of DP6-PPV for toluene.
Hydrogen plasma-treated MoSe2 nanosheets enhance the efficiency and stability of organic photovoltaics
(2019-10-07)
Wang, Hao-Cheng
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Lin, Yu-Che
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Chen, Chung-Hao
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Huang, Chi-Hsien
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Chang, Bin
In this paper we report the effect on the power conversion efficiency (PCE) and stability of photovoltaic devices after incorporating hydrogenated two-dimensional (2D) MoSe2 nanosheets into the active layer of bulk heterojunction (BHJ) organic photovoltaics (OPV). The surface properties of 2D MoSe2 nanosheets largely affect their dispersion in the active layer blend and, thus, influence the carrier mobility, PCE, and stability of corresponding devices. We treated MoSe2 nanosheets with hydrogen plasma and investigated their influence on the polymer packing and fullerene domain size of the active layer. For the optimized devices incorporating 37.5 wt% of untreated MoSe2, we obtained a champion PCE of 9.82%, compared with the champion reference PCE of approximately 9%. After incorporating the hydrogen plasma-treated MoSe2 nanosheets, we achieved a champion PCE of 10.44%-a relative increase of 16% over that of the reference device prepared without MoSe2 nanosheets. This PCE is the one of the highest ever reported for OPVs incorporating 2D materials. We attribute this large enhancement to the enhanced exciton generation and dissociation at the MoSe2-fullerene interface and, consequently, the balanced charge carrier mobility. The device incorporating the MoSe2 nanosheets maintained 70% of its initial PCE after heat-treatment at 100 degrees C for 1 h; in contrast, the PCE of the reference device decreased to 60% of its initial value-a relative increase in stability of 17% after incorporating these nanosheets. We also incorporated MoSe2 nanosheets (both with and without treatment) into a polymer donor (PBDTTBO)/small molecule (IT-4F) acceptor system. The champion PCEs reached 7.85 and 8.13% for the devices incorporating the MoSe2 nanosheets with and without plasma treatment, respectively-relative increases of 8 and 12%, respectively, over that of the reference. These results should encourage a push toward the implementation of transition metal dichalcogenides to enhance the performances of BHJ OPVs.
Performance Characterization of Dye-Sensitized Photovoltaics under Indoor Lighting
(2017-04-20)
Chen, Chia-Yuan
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Jian, Zih-Hong
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Huang, Shih-Han
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Lee, Kun-Mu
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Kao, Ming-Hsuan
Indoor utilization of emerging photovoltaics is promising; however, efficiency characterization under room lighting is challenging. We report the first round-robin interlaboratory study of performance measurement for dye-sensitized photovoltaics (cells and mini-modules) and one silicon solar cell under a fluorescent dim light. Among 15 research groups, the relative deviation in power conversion efficiency (PCE) of the samples reaches an unprecedented 152%. On the basis of the comprehensive results, the gap between photometry and radiometry measurements and the response of devices to the dim illumination are identified as critical obstacles to the correct PCE. Therefore, we use an illuminometer as a prime standard with a spectroradiometer to quantify the intensity of indoor lighting and adopt the reverse-biased current voltage (I-V) characteristics as an indicator to qualify the I-V sampling time for dye-sensitized photovoltaics. The recommendations can brighten the prospects of emerging photovoltaics for indoor applications.
Quantitative Characterization and Mechanism of Formation of Multilength-scale Bulk Heterojunction Structures in Highly Efficient Solution-Processed Small-Molecule Organic Solar Cells
(2015-07-23)
Huang, Yu-Ching
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Tsao, Cheng-Si
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Huang, Tzu-Yen
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Cha, Hou-Chin
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Patra, Dhananjaya
In this study we used simultaneous grazing-incidence small- and wide-angle X-ray scattering (GISAXS and GIWAXS, respectively) to probe the multilength-scale structures of thin active layers comprising the linear A-D-A-type pi-conjugated donor molecule TBDTCNR and the fullerene acceptor molecule PC61BM for use in solution-processed small-molecule-based organic solar cells (SMOSCs). We found that the pseudo-two-dimensional fractal-like networks in the bulk heterojunction (BHJ) structure were determined by mutual interactions between the small-molecule (SM) crystallites and the nanoscale PC61BM clusters during their formation and phase separation, and deduced quantitatively, at multiple length scales, the BHJ structures comprising these SM crystallites and PC61BM clusters. We also conducted in situ GIWAXS measurements to study the temporal behavior and kinetics of SM crystallization from solution to the solid film state. Our GISAXS/GIWAXS study revealed that the multilength-scale BHJ structures in the thin films could be tuned effectively by varying the amount of incorporated PC61BM and the annealing temperature. This study provides fundamental information relating to the mechanism of formation of hierarchical BHJ structures through relatively rapid crystallization of a highly crystalline SM, as well as the relationships among the hierarchical structure, the photovoltaic performance, and the mechanism of formation, thereby allowing greater control over BHJ structures in SMOSCs with optimized fabrication and performance.
Realizing Efficient Charge/Energy Transfer and Charge Extraction in Fullerene-Free Organic Photovoltaics via a Versatile Third Component
(2019-08-01)
Cheng, Hao-Wen
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Zhang, Huotian
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Lin, Yu-Che
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She, Nian-Zu
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Wang, Rui
Solution-processed organic photovoltaics (OPVs) based on bulk-heterojunctions have gained significant attention to alleviate the increasing demend of fossil fuel in the past two decades. OPVs combined of a wide bandgap polymer donor and a narrow bandgap nonfullerene acceptor show potential to achieve high performance. However, there are still two reasons to limit the OPVs performance. One, although this combination can expand from the ultraviolet to the near-infrared region, the overall external quantum efficiency of the device suffers low values. The other one is the low open-circuit voltage (V-OC) of devices resulting from the relatively downshifted lowest unoccupied molecular orbital (LUMO) of the narrow bandgap. Herein, the approach to select and incorporate a versatile third component into the active layer is reported. A third component with a bandgap larger than that of the acceptor, and absorption spectra and LUMO levels lying within that of the donor and acceptor, is demonstrated to be effective to conquer these issues. As a result, the power conversion efficiencies (PCEs) are enhanced by the elevated short-circuit current and V-OC; the champion PCEs are 11.1% and 13.1% for PTB7-Th:IEICO-4F based and PBDB-T:Y1 based solar cells, respectively.
Structural Evolution of Crystalline Conjugated Polymer/Fullerene Domains from Solution to the Solid State in the Presence and Absence of an Additive
(2015-02-12)
Su, Yu-Wei
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Liu, Chih-Ming
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Jiang, Jian-Ming
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Tsao, Cheng-Si
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Cha, Hou-Chin
The power conversion efficiencies of polymer/fullerene solar cells are critically dependent on the nanometer-scale morphologies of their active layers, which are typically processed from solution. Using synchrotron wide- and small-angle X-ray scattering, we have elucidated the intricate mechanism of the structural transitions from solutions to solid films of the crystalline polymer poly[bis(dodecyl)thiophene-thieno[3,4-c]pyrrole-4,6-dione] (PBTTPD) and [6,6]-phenyl-C-71-butyric acid methyl ester (PC71BM), including the effect of the solvent additive 1,6-diiodohexane (DIH). We found that the local assembly of rigid-rod PBTTPD segments that formed in solution instantly and then relaxed within several hundred seconds upon cooling to room temperature from 90 degrees C could re-emerge and develop into seeds for subsequent crystallization of the polymer in the solid films. At room temperature (25 degrees C), the presence of DIH in chlorobenzene slightly enhanced the formation of local assembly PBTTPD segments in the supersaturated PBTTPD in PBTTPD/PC71BM blend solution. Two cases of films were subsequently developed from these blend solutions with drop-casted and spin-coated methods. For spin-coated thin films (90 nm thick), which evolve quickly, polymers crystallinity and the fullerene packing in the solid-state thin films were enhanced in the case of involving DIH. Regarding the effect of DIH for processing the drop-casted thick films (2.5 mu m thick), which evolve slowly, DIH has no observable effect on PBTTPD/PC71BM structure. Our results provide some understanding of the mechanism behind the structural development of polymer/fullerene blends upon their transitions from solution to the solid state, as well as the key functions of the additive.