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Conjugated Polymer/Nanocrystal Nanocomposites for Renewable Energy Applications in Photovoltaics and Photocatalysis
(2014-11-26)
Su, Yu-Wei
;
Lin, Wei-Hao
;
Hsu, Yung-Jung
;
Wei, Kung-Hwa
;
材料科學與工程學系
Conjugated polymer/nanocrystal composites have attracted much attention for use in renewable energy applications because of their versatile and synergistic optical and electronic properties. Upon absorbing photons, charge separation occurs in the nanocrystals, generating electrons and holes for photocurrent flow or reduction/oxidation (redox) reactions under proper conditions. Incorporating these nanocrystals into conjugated polymers can complement the visible light absorption range of the polymers for photovoltaics applications or allow the polymers to sensitize or immobilize the nanocrystals for photocatalysis. Here, the current developments of conjugated polymer/nanocrystal nanocomposites for bulk heterojunction-type photovoltaics incorporating Cd- and Pb-based nanocrystals or quantum dots are reviewed. The effects of manipulating the organic ligands and the concentration of the nanocrystal precursor, critical factors that affect the shape and aggregation of the nanocrystals, are also discussed. In the conclusion, the mechanisms through which conjugated polymers can sensitize semiconductor nanocrystals (TiO2, ZnO) to ensure efficient charge separation, as well as how they can support immobilized nanocrystals for use in photocatalysis, are addressed.
Side-Chain-Bulk Effects on the Molecular Packing and Photovoltaic Performance of Benzotrithiophene-Benzooxadiazole Conjugated Copolymers
(2015-04-27)
Lan, Shang-Che
;
Chang, Chiao-Kai
;
Wang, Yi-Chien
;
Wei, Kung-Hwa
;
材料科學與工程學系
Two alternating donor-acceptor conjugated polymers, PBTTBO-C13C11 and PBTTBO-C13C8, comprising 5-alkylbenzo[1,2-b:3,4-b:5,6-d]trithiophene (BTT) as the donor and 4,7-bis(4-dodecylthien-2-yl)benzo[1,2,5]oxadiazole (BO) as the acceptor, with different alkyl side-chain architectures on their BTT units are synthesized, and their bulk heterojunction photovoltaic properties when blended with the fullerene PC71BM are characterized. Even a slight change in the length of the alkyl chain of the BTT units influences the steric bulk to such a degree that it substantially affects the molecular packing of the polymers and the performance of their photovoltaic devices. The bulkier side chains of the polymer PBTTBO-C13C11 not only prevent its crystallization, but also suppress its light-absorption coefficient relative to that of PBTTBO-C13C8, as evidenced by X-ray diffraction and UV/Vis absorption studies, presumably because of weakened intermolecular interactions. Moreover, the polymer bearing bulkier side chains, PBTTBO-C13C11, is less miscible with PC71BM than PBTTBO-C13C8, and this characteristic determines the morphology of their annealed blended films, as shown by TEM studies. The best efficiency is obtained with a device containing an annealed PBTTBO-C13C8/PC71BM (1/2 w/w) active layer that was maintained at 120 degrees C for 10 min, which shows a power conversion efficiency of 6.2%, an open-circuit voltage of 0.75 V, a short-circuit current density of 12.6 mAcm(-2), and a fill factor of 66%.
Synthesis and Characterization of Donor-Acceptor Poly(3-hexylthiophene) Copolymers Presenting 1,3,4-Oxadiazole Units and Their Application to Photovoltaic Cells
(2010-08-01)
Wang, Hsu-Shen
;
Su, Ming-Shin
;
Wei, Kung-Hwa
;
材料科學與工程學系
;
Department of Materials Science and Engineering
We have used Grignard metathesis polymerization to prepare poly(3-hexylthiophene)-based copolymers containing electron-withdrawing 4-tert-butylphenyl-1,3,4-oxadiazole-Phenyl moieties as side chains. We characterized these copolymers using (1)H and (13)C nuclear magnetic resonance spectroscopy, thermogravimetric analysis, and gel permeation chromatography. The band gap energy of copolymer was determined from the onset of the optical absorption. The quenching effects were observed in the photoluminescence spectra of the copolymers incorporating pendant electron-deficient 1,3,4-oxadiazole moieties on the side chains. The photocurrents of devices were enhanced in the presence of an optimal amount of the 1,3,4-oxadiazole moieties, thereby leading to improved power conversion efficiencies. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3331-3339, 2010
Carbazole-Based Conjugated Polymers Incorporating Push/Pull Organic Dyes: Synthesis, Characterization, and Photovoltaic Applications
(2010-11-15)
Hsu, So-Lin
;
Chen, Chia-Min
;
Wei, Kung-Hwa
;
材料科學與工程學系
;
Department of Materials Science and Engineering
We have synthesized and characterized two new carbazole-based conjugated polymers, PCDCN and PCDTA, incorporating two strong light-absorbing organic dyes. These polymers exhibit relatively low band gaps (similar to 1.5 eV) and broad absorption ranges (from 300 to 700 nm). We fabricated polymer solar cells incorporating these polymers as donors and [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) as the acceptor. At a blending ratio of 1: 4, we obtained power conversion efficiencies, under simulated AM 1.5 (100 mW/cm(2)) conditions, of 2.31% and 2.47% for the PCDCN- and PCDTA-based devices, respectively. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5126- 5134, 2010
New Carbazole-Based Conjugated Polymers Containing Pyridylvinyl Thiophene Units for Polymer Solar Cell Applications: Morphological Stabilization Through Hydrogen Bonding
(2011-02-01)
Hsu, So-Lin
;
Chen, Chia-Min
;
Cheng, Yu-Hsin
;
Wei, Kung-Hwa
;
材料科學與工程學系
We have synthesized two conjugated polymers (P1, P2) containing alternating electron-donating and -accepting units, based on N-alkyl-2,7-carbazole, 4,7-di(thiophen-5-yl)-2,1,3-benzothiadiazole and 3-[2-(4-pyridyl)vinyl]thiophene units. These conjugated polymers contained different contents of pyridine units, which were incorporated to form hydrogen bonds with [6,6]-phenyl-C(61)-butyric acid (PCBA). When these hydrogen bonding interactions were present in the polymer thin films, their thermal stability improved; deterioration, which occurred through aggregation of PCBA methyl ester after lengthy annealing times, was also suppressed. The power conversion efficiency of a device incorporating the film featuring hydrogen bonding interactions remained at 75% of the original value after thermal annealing for 5 h at 140 degrees C. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 603-611, 2011
Synthesis and Applications of Cyano-Vinylene-Based Polymers Containing Cyclopentadithiophene and Dithienosilole Units for Photovoltaic Cells
(2011-08-01)
Padhy, Harihara
;
Sahu, Duryodhan
;
Patra, Dhananjaya
;
Pola, Murali Krishna
;
Huang, Jen-Hsien
Two beta-cyano-thiophenevinylene-based polymers containing cyclopentadithiophene (CPDT-CN) and dithienosilole (DTS-CN) units were synthesized via Stille coupling reaction with Pd(PPh(3))(4) as a catalyst. The effects of the bridged atoms (C and Si) and cyano-vinylene groups on their thermal, optical, electrochemical, charge transporting, and photovoltaic properties were investigated. Both polymers possessed the highest occupied molecular orbital (HOMO) levels of about -5.30 eV and the lowest unoccupied molecular orbital (LUMO) levels of about -3.60 eV, and covered broad absorption ranges with narrow optical band gaps (ca. 1.6 eV). The bulk heterojunction polymer solar cell (PSC) devices containing an active layer of electron-donor polymers (CPDT-CN and DTS-CN) blended with an electron-acceptor, that is, [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(61)BM) or [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM), in different weight ratios were explored under 100 mW/cm(2) of AM 1.5 white-light illumination. The PSC device based on DTS-CN:PC(71)BM (1:2 w/w) exhibited a best power conversion efficiency (PCE) value of 2.25% with V(oc) = 0.74 V, J(sc) = 8.39 mA/cm(2), and FF = 0.36. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3417-3425, 2011
Fine Tuning of HOMO Energy Levels for Low-Band-Gap Photovoltaic Copolymers Containing Cyclopentadithienopyrrole and Bithiazole Units
(2011-09-15)
Patra, Dhananjaya
;
Sahu, Duryodhan
;
Padhy, Harihara
;
Kekuda, Dhananjay
;
Chu, Chih-Wei
Five conjugated LBG polymers P1-P5 consisting of a DTP unit as an electron donor and various bithiazole units as electron acceptors are designed and synthesized for photovoltaic applications. The effects of the electron-deficient bithiazole derivatives on the thermal, optical, electrochemical, and photovoltaic properties are investigated. The molecular structures are confirmed and characterized. The resulting polymers have high thermal stabilities and broad absorption bands with low optical bandgaps. The hole and electron mobilities are calculated. PSC devices are fabricated utilizing the polymers as electron donors and PCBM as an electron acceptor. The PSC device with an active layer of P4:PCBM (1:1 by weight) exhibits the best power-conversion efficiency.
Novel narrow-band-gap conjugated copolymers containing phenothiazine-arylcyanovinyl units for organic photovoltaic cell applications
(2008-07-01)
Li, Kuang-Chieh
;
Hsu, Ying-Chan
;
Lin, Jiann-T'Suen
;
Yang, Chang-Chung
;
Wei, Kung-Hwa
A series of novel narrow-band-gap copolymers (P1-P12) composed of alkyl-substituted fluorene (FO) units and six analogous mono- and bis(2-aryl-2-cyano-vinyl)- 10-hexylphenothiazine monomers (M1-M6) were synthesized by a palladium-catalyzed Suzuki coupling reaction with two different feed in ratios of FO to M1-M6 (molar ratio = 3:1 and 1:1). The absorption spectra of polymers P1-P12 exhibited broad peaks located in the UV and visible regions from 400 to 800 nm with optical band gaps at 1.55-2.10 eV, which fit near the wavelength of the maximum solar photon reflux. Electrochemical experiments displayed that the reversible p- and n-doping processes of copolymers were partially reversible, and the proper HOMO/LUMO levels enabled a high photovoltaic open-circuit voltage. As blended with [6,6]-phenyl C-61 butyric acid methyl ester (PCBM) as an electron acceptor in bulk heterojunction photovoltaic devices, narrow-band-gap polymers P1-P12 as electron donors showed significant photovoltaic performance which varied with the intramolecular donor-acceptor interaction and their mixing ratios to PCBM. Under 100 mW/cm(2) of AM 1.5 white-light illumination, the device of copolymer P12 produced the highest preliminary result having an open-circuit voltage of 0.64 V, a short-circuit current of 2.70 mA/cm(2), a fill factor of 0.29, and an energy conversion efficiency of 0.51%. (c) 2008 Wiley Periodicals, Inc.
Soluble Narrow-Band-Gap Copolymers Containing Novel Cyclopentadithiophene Units for Organic Photovoltaic Cell Applications
(2009-04-15)
Li, Kuang-Chieh
;
Hsu, Ying-Chan
;
Lin, Jiann-T'suen
;
Yang, Chang-Chung
;
Wei, Kung-Hwa
Five novel conjugated copolymers (P1-P5) containing coplanar cyclopentadithiophene (CPDT) units (incorporated with arylcyanovinyl and keto groups in different molar ratios) were synthesized and developed for the applications of polymer solar cells (PSCs). Polymers P1-P5 covered broad absorption ranges from U-V to near infrared (400-900 nm) with narrow optical band gaps of 1.38-1.70 eV, which are compatible with the maximum solar photon reflux. Partially reversible p- and n-doping processes of P1-P5 in electrochemical experiments were observed, and the proper molecular design for highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels of P1-P5 induced the highest photovoltaic open-circuit voltage in the PSC devices, compared with those previously reported CPDT-based narrow-band-gap polymers. Powder X-ray diffraction (XRD) analyses suggested that these copolymers formed self-assembled pi-pi stacking and pseudobilayered structures. Under 100 mW/cm(2) of AM 1.5 white-light illumination, bulk hetero-junction PSC devices containing an active layer of electron donor polymers P1-P5 mixed with electron acceptor [6,6]-phenyl C(61) butyric acid methyl ester (PCBM) in the weight ratio of 1:4 were investigated. The PSC device containing P1 gave the best preliminary result with an open-circuit voltage of 0.84 V, a short-circuit current of 2.36 mA/cm(2), and a fill factor of 0.38, offering an overall power conversion efficiency (PCE) of 0.77% as well as a maximal quantum efficiency of 23% from the external quantum efficiency (EQE) measurements. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2073-2092, 2009
Synthesis and Characterization of Donor-Bridge-Acceptor Alternating Copolymers Containing Perylene Diimide Units and Their Application to Photovoltaic Cells
(2010-03-15)
Yuan, Mao-Chuan
;
Su, Ming-Hsin
;
Chiu, Mao-Yuan
;
Wei, Kung-Hwa
;
材料科學與工程學系
We have used Suzuki coupling to prepare a series of alternating copolymers featuring coplanar cyclopentadithiophene and hole-transporting carbazole units. We observed quenching in the photoluminescence spectra of our polymers after incorporating pendent electron-deficient perylene diimide (PDI) moieties on the side chains, indicating more efficient photoinduced electron transfer. Electrochemical measurements revealed that the PDI-containing copolymers displayed reasonable and sufficient offsets of the energy levels of their lowest unoccupied molecular orbitals for efficient charge dissociation. The performance of bulk heterojunction photovoltaic cells incorporating the copolymer/[6,6]-phenyl-C(61)-butyric acid methyl ester blends (1:4, w/w) was optimized when the active layer had a thickness of 70 nm. The photocurrents of the devices were enhanced as a result of the presence of the PDI moieties, thereby leading to improved power conversion efficiencies. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1298-1309, 2010

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