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      • Present Situation and Countermeasures of Ecotourism Resources Development in Tibet

        Fan Gang,Tang Yumin 아시아사회과학학회 2022 Jornal of Asia Social Science Vol.6 No.2

        With the improvement of people s leisure time and the strengthening of the country s development of the western region, the construction of the western region is speeding up, and people s yearning for the mysterious western region is becoming increasingly prominent. Tibet s unique natural ecology and social and historical process have created its unique tourism resources. Plateau, mountains, snow-capped mountains, glaciers, forests, grasslands, lakes, hot springs, geothermal water, etc. constitute a unique natural landscape. Spectacular temples and ancient buildings, strong religious atmosphere and charming eco-tourism resources in Tibet constitute a unique natural wonder, which has great development potential in developing eco-tourism in Tibet. According to the superior conditions of Tibet s eco-tourism resources, this paper starts with the characteristics of Tibet s eco-tourism resources and the development of Tibet s tourism industry, and concludes that there are some problems in the current development of Tibet s eco-tourism resources, such as backward propaganda and development, single types of tourism products, poor infrastructure conditions, lack of effective management, and weak awareness of environmental protection , and analyzes and summarizes the relevant countermeasures for developing Tibet s eco-tourism resources.

      • 1,4-Di(3-alkoxy-2-thienyl)-2,5-difluorophenylene: A Building Block Enabling High-Performance Polymer Semiconductors with Increased Open-Circuit Voltages

        Chen, Jianhua,Yan, Zhenglong,Tang, Linjing,Uddin, Mohammad Afsar,Yu, Jianwei,Zhou, Xin,Yang, Kun,Tang, Yumin,Shin, Tae Joo,Woo, Han Young,Guo, Xugang American Chemical Society 2018 Macromolecules Vol.51 No.14

        <P>A new building block, 1,4-di(3-alkoxy-2-thienyl)-2,5-difluorophenylene (DOTFP) with several desirable features such as high backbone planarity, suitably lying highest occupied molecular orbital (HOMO), and good solubility, was developed by inserting an electron-deficient difluorophenylene into the 3,3′-dialkoxy-2,2′-bithiophene (BTOR) unit. Three regioregular D-A<SUB>1</SUB>-D-A<SUB>2</SUB> type polymers based on DOTFP and benzothiadiazole (BT) derivatives were synthesized and characterized by comparing with a D-A type BTOR-based polymer. The content of highly electron-rich alkoxythiophene is reduced by half in the DOTFP-based polymers versus that of the BTOR-based polymer analogue, which results in a deeper HOMO level and benefits high open-circuit voltage (<I>V</I><SUB>oc</SUB>) in polymer solar cells (PSCs). Consequently, the DOTFP-ffBT-based solar cells exhibited a significantly improved power conversion efficiency (PCE) of 8.7% and an increased <I>V</I><SUB>oc</SUB> of 0.84 V compared to the BTOR-ffBT-based solar cells with a PCE of 2.6% and a <I>V</I><SUB>oc</SUB> of 0.49 V. Additionally, the DOTFP-based polymers showed improved charge transport properties and film morphology than the BTOR-based polymer BTOR-ffBT, resulting in simultaneous enhancement of the short-circuit current (<I>J</I><SUB>sc</SUB>) and fill factor (FF) in PSCs. These results demonstrate the great promise of the DOTFP building block for the construction of high-performance photovoltaic polymer semiconductors with increased <I>V</I><SUB>oc</SUB>s.</P> [FIG OMISSION]</BR>

      • Quinoxaline-Based Wide Band Gap Polymers for Efficient Nonfullerene Organic Solar Cells with Large Open-Circuit Voltages

        Yang, Jie,Uddin, Mohammad Afsar,Tang, Yumin,Wang, Yulun,Wang, Yang,Su, Huimin,Gao, Rutian,Chen, Zhi-Kuan,Dai, Junfeng,Woo, Han Young,Guo, Xugang American Chemical Society 2018 ACS APPLIED MATERIALS & INTERFACES Vol.10 No.27

        <P>We present here a series of wide-band-gap (<I>E</I><SUB>g</SUB>: >1.8 eV) polymer donors by incorporating thiophene-flanked phenylene as an electron-donating unit and quinoxaline as an electron-accepting co-unit to attain large open-circuit voltages (<I>V</I><SUB>oc</SUB>s) and short-circuit currents (<I>J</I><SUB>sc</SUB>s) in nonfullerene organic solar cells (OSCs). Fluorination was utilized to fine-tailor the energetics of polymer frontier molecular orbitals (FMOs) by replacing a variable number of H atoms on the phenylene moiety with F. It was found that fluorination can effectively modulate the polymer backbone planarity through intramolecular noncovalent S···F and/or H···F interactions. Polymers (P2-P4) show an improved molecular packing with a favorable face-on orientation compared to their nonfluorinated analogue (P1), which is critical to charge carrier transport and collection. When mixed with IDIC, a nonfullerene acceptor, P3 with two F atoms, achieves a remarkable <I>V</I><SUB>oc</SUB> of 1.00 V and a large <I>J</I><SUB>sc</SUB> of 15.99 mA/cm<SUP>2</SUP>, simultaneously, yielding a power-conversion efficiency (PCE) of 9.7%. Notably, the 1.00 V <I>V</I><SUB>oc</SUB> is among the largest values in the IDIC-based OSCs, leading to a small energy loss (<I>E</I><SUB>loss</SUB>: 0.62 eV) while maintaining a large PCE. The P3:IDIC blend shows an efficient exciton dissociation through hole transfer even under a small energy offset of 0.16 eV. Further fluorination leads to the polymer P4 with increased chain-twisting and mismatched FMO levels with IDIC, showing the lowest PCE of 2.93%. The results demonstrate that quinoxaline-based copolymers are promising donors for efficient OSCs and the fluorination needs to be fine-adjusted to optimize the interchain packing and physicochemical properties of polymers. Additionally, the structure-property correlations from this work provide useful insights for developing wide-band-gap polymers with low-lying highest occupied molecular orbitals to minimize <I>E</I><SUB>loss</SUB> and maximize <I>V</I><SUB>oc</SUB> in nonfullerene OSCs for efficient power conversion.</P> [FIG OMISSION]</BR>

      • 2,1,3-Benzothiadiazole-5,6-dicarboxylicimide-Based Polymer Semiconductors for Organic Thin-Film Transistors and Polymer Solar Cells

        Yu, Jianwei,Ornelas, Joshua Loroñ,a,Tang, Yumin,Uddin, Mohammad Afsar,Guo, Han,Yu, Simiao,Wang, Yulun,Woo, Han Young,Zhang, Shiming,Xing, Guichuan,Guo, Xugang,Huang, Wei American Chemical Society 2017 ACS APPLIED MATERIALS & INTERFACES Vol.9 No.48

        <P>A series of polymer semiconductors incorporating 2,1,3-benzothiadiazole-5,6-dicarboxylicimide (BTZI) as strong electron-withdrawing unit and an alkoxy-functionalized head-to-head linkage containing bithiophene or bithiazole as highly electron-rich co-unit are designed and synthesized. Because of the strong intramolecular charge transfer characteristics, all three polymers BTZI-TRTOR (P1), BTZI-BTOR (P2), and BTZI-BTzOR (P3) exhibit narrow bandgaps of 1.13, 1.05, and 0.92 eV, respectively, resulting in a very broad absorption ranging from 350 to 1400 nm. The highly electron-deficient 2,1,3-benzothiadiazole-5,6-dicarboxylicimide and alkoxy-functionalized bithiophene (or thiazole) lead to polymers with low-lying lowest unoccupied molecular orbitals (-3.96 to -4.28 eV) and high-lying highest occupied molecular orbitals (-5.01 to -5.20 eV). Hence, P1 and P3 show substantial and balanced ambipolar transport with electron mobilities/hole mobilities of up to 0.86/0.51 and 0.95/0.50 cm(2) V-1 s(-1), respectively, and polymer P2 containing the strongest donor unit exhibited unipolar p-type performance with an average hole mobility of 0.40 cm(2) V-1 s(-1) in top-gate/bottom-contact thin-film transistors with gold as the source and drain electrodes. When incorporated into bulk heterojunction polymer solar cells, the narrow bandgap (1.13 eV) polymer P1 shows an encouraging power conversion efficiency of 4.15% with a relatively large open-circuit voltage of 0.69 V, which corresponds to a remarkably small energy loss of 0.44 eV. The power conversion efficiency of P1 is among the highest reported to date with such a small energy loss in polymer:fullerene solar cells.</P>

      • Backbone Coplanarity Tuning of 1,4-Di(3-alkoxy-2-thienyl)-2,5-difluorophenylene-Based Wide Bandgap Polymers for Efficient Organic Solar Cells Processed from Nonhalogenated Solvent

        Liao, Qiaogan,Yang, Kun,Chen, Jianhua,Koh, Chang Woo,Tang, Yumin,Su, Mengyao,Wang, Yang,Yang, Yinhua,Feng, Xiyuan,He, Zhubing,Woo, Han Young,Guo, Xugang American Chemical Society 2019 ACS APPLIED MATERIALS & INTERFACES Vol.11 No.34

        <P>Halogenated solvents are prevailingly used in the fabrication of nonfullerene organic solar cells (NF-OSCs) at the current stage, imposing significant restraints on their practical applications. By copolymerizing phthalimide or thieno[3,4-<I>c</I>]pyrrole-4,6-dione (TPD) with 1,4-di(3-alkoxy-2-thienyl)-2,5-difluorophenylene (DOTFP), which features intramolecular noncovalent interactions, the backbone planarity of the resulting DOTFP-based polymers can be effectively tuned, yielding distinct solubilities, aggregation characters, and chain packing properties. Polymer DOTFP-PhI with a more twisted backbone showed a lower degree of aggregation in solution but an increased film crystallinity than polymer DOTFP-TPD. An organic thin-film transistor and NF-OSC based on DOTFP-PhI, processed with a nonhalogenated solvent, exhibited a high hole mobility up to 1.20 cm<SUP>2</SUP> V<SUP>-1</SUP> s<SUP>-1</SUP> and a promising power conversion efficiency up to 10.65%, respectively. The results demonstrate that DOTFP is a promising building block for constructing wide bandgap polymers and backbone coplanarity tuning is an effective strategy to develop high-performance organic semiconductors processable with a nonhalogenated solvent.</P> [FIG OMISSION]</BR>

      • Cyano-substituted benzochalcogenadiazole-based polymer semiconductors for balanced ambipolar organic thin-film transistors

        Shi, Shengbin,Wang, Hang,Chen, Peng,Uddin, Mohammad Afsar,Wang, Yuxi,Tang, Yumin,Guo, Han,Cheng, Xing,Zhang, Shiming,Woo, Han Young,Guo, Xugang The Royal Society of Chemistry 2018 Polymer chemistry Vol.9 No.28

        <P>Due to their high-lying lowest unoccupied molecular orbitals (LUMOs), π-conjugated polymers based on benzothiadiazole and its derivatives typically are p-type. We report here the successful development of two narrow bandgap, ambipolar donor-acceptor copolymers, PDCNBT2T and PDCNBSe2T, which are based on new cyano-substituted strong electron acceptors, 4,7-dibromo-5,6-dicyano-2,1,3-benzothiadiazole (DCNBT) and 4,7-dibromo-5,6-dicyano-2,1,3-benzoselenadiazole (DCNBSe), respectively. Compared to their polymer analogues with fluorine substituents, the LUMO was lowered by a big margin of <I>ca.</I> 0.6 eV and the bandgap was reduced by 0.2-0.3 eV for the cyano-substituted polymers. Therefore, the cyano-substituted benzothiadiazole polymers showed very low-lying LUMO levels of <I>ca.</I> 4.3 eV. Benefiting from their narrow bandgaps of 1.1-1.2 eV and appropriately positioned LUMO levels, both polymers exhibit well balanced ambipolar transport characteristics in organic thin-film transistors, which differ from the p-type dominating transport properties of their fluorinated polymer analogues. A balanced hole/electron mobility of 0.59/0.47 cm<SUP>2</SUP> V<SUP>−1</SUP> s<SUP>−1</SUP> was achieved for polymer PDCNBT2T, and a reduced hole/electron mobility of 0.018/0.014 cm<SUP>2</SUP> V<SUP>−1</SUP> s<SUP>−1</SUP> was observed for the benzoselenadiazole-based PDCNBSe2T due to its lower crystallinity. These results show that the electron mobility can be enhanced by approximately two orders <I>versus</I> the electron mobility of the previously reported 4,7-di(thiophen-2-yl)-5,6-dicyano-2,1,3-benzothiadiazole-based polymer. This improvement was achieved by using the new acceptor units without additional electron-rich thiophene flanks, which allow a higher degree of freedom in selecting the donor co-unit and more effective tuning of energy levels of frontier molecular orbitals.</P>

      • Backbone Conformation Tuning of Carboxylate-Functionalized Wide Band Gap Polymers for Efficient Non-Fullerene Organic Solar Cells

        Chen, Jianhua,Wang, Lei,Yang, Jie,Yang, Kun,Uddin, Mohammad Afsar,Tang, Yumin,Zhou, Xin,Liao, Qiaogan,Yu, Jianwei,Liu, Bin,Woo, Han Young,Guo, Xugang American Chemical Society 2019 Macromolecules Vol.52 No.1

        <P>Two carboxylate-functionalized wide band gap polymers, 2TC-TT-BDTFT and 2T-TTC-BDTFT, which feature a fluorinated benzodithiophene (BDTFT)-<I>alt</I>-2,5-di(thiophen-2-yl)thieno[3,2-<I>b</I>]thiophene (2T-TT) backbone having different carboxylate attaching positions, were designed and synthesized. By variation of the substitution position of carboxylate groups on the 2T-TT unit, the backbone conformation of the designed building blocks 2TC-TT and 2T-TTC and their corresponding donor-acceptor polymers was fine-tuned as demonstrated by single crystal study and DFT calculation, thus yielding a large device performance difference in organic solar cells. As a result of the relatively higher planarity of the 2T-TTC unit in which the two carboxylate groups were attached on the inner thieno[3,2-<I>b</I>]thiophene moiety, the 2T-TTC-BDTFT polymer exhibited a red-shifted UV-vis absorption, stronger aggregation, and improved charge transport property than its polymer analogue 2TC-TT-BDTFT, in which the two outer thiophene rings were functionalized with carboxylate groups. Benefiting from the improved exciton dissociation and charge collection efficiency, better film morphology, and higher photoresponse, non-fullerene organic solar cells based on 2T-TTC-BDTFT:m-ITIC achieved a power conversion efficiency (PCE) of 11.15% with a fill factor (FF) of ∼70%, while the 2TC-TT-BDTFT:m-ITIC cells showed a relatively lower PCE of 9.65% and FF of 59.31%. The much higher FF of 2T-TTC-BDTFT-based solar cells reflects the great merit of the carboxylation on thienothiophene moiety rather than the outer thiophene counterpart. Therefore, the modulation of the carboxylate position on polymer backbones is an efficient strategy to tune the backbone conformation, interchain packing, film morphology, and the resulting optical, electrical, and photovoltaic properties. Moreover, both the 2T-TTC-BDTFT:m-ITIC and 2TC-TT-BDTFT:m-ITIC solar cells showed excellent stability during annealing and long-term storage. These results demonstrate that carboxylate-functionalized 2T-TTC and 2TC-TT have great potentials as a weak electron-accepting building block for wide band gap polymers for high-performance non-fullerene organic solar cells, and the carboxylate position on the polymer backbones is critical for performance improvement of organic photovoltaic devices.</P> [FIG OMISSION]</BR>

      • Cyano-Substituted Head-to-Head Polythiophenes: Enabling High-Performance n-Type Organic Thin-Film Transistors

        Wang, Hang,Huang, Jun,Uddin, Mohammad Afsar,Liu, Bin,Chen, Peng,Shi, Shengbin,Tang, Yumin,Xing, Guichuan,Zhang, Shiming,Woo, Han Young,Guo, Han,Guo, Xugang American Chemical Society 2019 ACS APPLIED MATERIALS & INTERFACES Vol.11 No.10

        <P>Polythiophenes, built on the electron-rich thiophene unit, typically possess high-lying energy levels of the lowest unoccupied molecular orbitals (LUMOs) and show hole-transporting properties. In this study, we develop a series of n-type polythiophenes, <B>P1</B>-<B>P3</B>, based on head-to-head-linked 3,3′-dialkoxy-4,4′-dicyano-2,2′-bithiophene (BTCNOR) with distinct side chains. The BTCNOR unit shows not only highly planar backbone conformation enabled by the intramolecular noncovalent sulfur-oxygen interaction but also significantly suppressed LUMO level attributed to the cyano-substitution. Hence, all BTCNOR-based polymer semiconductors exhibit low-lying LUMO levels, which are ∼1.0 eV lower than that of regioregular poly(3-hexylthiophene) (rr-P3HT), a benchmark p-type polymer semiconductor. Consequently, all of the three polymers can enable unipolar n-type transport characteristics in organic thin-film transistors (OTFTs) with low off-currents (<I>I</I><SUB>off</SUB>s) of 10<SUP>-10</SUP>-10<SUP>-11</SUP> A and large current on/off ratios (<I>I</I><SUB>on</SUB>/<I>I</I><SUB>off</SUB>s) at the level of 10<SUP>6</SUP>. Among them, polymer <B>P2</B> with a 2-ethylhexyl side chain offers the highest film ordering, leading to the best device performance with an excellent electron mobility (μ<SUB>e</SUB>) of 0.31 cm<SUP>2</SUP> V<SUP>-1</SUP> s<SUP>-1</SUP> in off-center spin-cast OTFTs. To the best of our knowledge, this is the first report of n-type polythiophenes with electron mobility comparable to the hole mobility of the benchmark p-type rr-P3HT and approaching the electron mobility of the most-studied n-type polymer, poly(naphthalene diimide-<I>alt</I>-bithiophene) (i.e., N2200). The change of charge carrier polarity from p-type (rr-P3HT) to n-type (<B>P2</B>) with comparable mobility demonstrates the obvious effectiveness of our structural modification. Adoption of <I>n</I>-hexadecyl (<B>P1</B>) and 2-butyloctyl (<B>P3</B>) side chains leads to reduced film ordering and results in 1-2 orders of magnitude lower μ<SUB>e</SUB>s, showing the critical role of side chains in optimizing device performance. This study demonstrates the unique structural features of head-to-head linkage containing BTCNOR for constructing high-performance n-type polymers, i.e., the alkoxy chain for backbone conformation locking and providing polymer solubility as well as the strong electron-withdrawing cyano group for lowering LUMO levels and enabling n-type performance. The design strategy of BTCNOR-based polymers provides useful guidelines for developing n-type polythiophenes.</P> [FIG OMISSION]</BR>

      • (Semi)ladder-Type Bithiophene Imide-Based All-Acceptor Semiconductors: Synthesis, Structure-Property Correlations, and Unipolar n-Type Transistor Performance

        Wang, Yingfeng,Guo, Han,Harbuzaru, Alexandra,Uddin, Mohammad Afsar,Arrechea-Marcos, Iratxe,Ling, Shaohua,Yu, Jianwei,Tang, Yumin,Sun, Huiliang,Ló,pez Navarrete, Juan Teodomiro,Ortiz, Rocio Ponce American Chemical Society 2018 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.140 No.19

        <P>Development of high-performance unipolar n-type organic semiconductors still remains as a great challenge. In this work, all-acceptor bithiophene imide-based ladder-type small molecules BTI<I>n</I> and semiladder-type homopolymers PBTI<I>n</I> (<I>n</I> = 1-5) were synthesized, and their structure-property correlations were studied in depth. It was found that Pd-catalyzed Stille coupling is superior to Ni-mediated Yamamoto coupling to produce polymers with higher molecular weight and improved polymer quality, thus leading to greatly increased electron mobility (μ<SUB>e</SUB>). Due to their all-acceptor backbone, these polymers all exhibit unipolar n-type transport in organic thin-film transistors, accompanied by low off-currents (10<SUP>-10</SUP>-10<SUP>-9</SUP> A), large on/off current ratios (10<SUP>6</SUP>), and small threshold voltages (∼15-25 V). The highest μ<SUB>e</SUB>, up to 3.71 cm<SUP>2</SUP> V<SUP>-1</SUP> s<SUP>-1</SUP>, is attained from PBTI1 with the shortest monomer unit. As the monomer size is extended, the μ<SUB>e</SUB> drops by 2 orders to 0.014 cm<SUP>2</SUP> V<SUP>-1</SUP> s<SUP>-1</SUP> for PBTI5. This monotonic decrease of μ<SUB>e</SUB> was also observed in their homologous BTI<I>n</I> small molecules. This trend of mobility decrease is in good agreement with the evolvement of disordered phases within the film, as revealed by Raman spectroscopy and X-ray diffraction measurements. The extension of the ladder-type building blocks appears to have a large impact on the motion freedom of the building blocks and the polymer chains during film formation, thus negatively affecting film morphology and charge carrier mobility. The result indicates that synthesizing building blocks with more extended ladder-type backbone does not necessarily lead to improved mobilities. This study marks a significant advance in the performance of all-acceptor-type polymers as unipolar electron transporting materials and provides useful guidelines for further development of (semi)ladder-type molecular and polymeric semiconductors for applications in organic electronics.</P> [FIG OMISSION]</BR>

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