• Title/Summary/Keyword: ${\pi}-{\pi}$ stacking

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Synthesis and Design of Electroactive Polymers for Improving Efficiency and Thermal Stability in Organic Photovoltaics

  • Kim, Beom-Jun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.05a
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    • pp.11.2-11.2
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    • 2011
  • Polymer based organic photovoltaics have attracted a great deal of attention due to the potential cost-effectiveness of light-weight and flexible solar cells. However, most BHJ polymer solar cells are not thermally stable as subsequent exposure to heat drives further development of the morphology towards a state of macrophase separation in the micrometer scale. Here we would like to show three different approaches for developing new electroactive polymers to improve the thermal stability of the BHJ solar cells, which is a critical problem for the commercialization of these solar cells. For one of the examples, we report a new series of functionalized polythiophene (PT-x) copolymers for use in solution processed organic photovoltaics (OPVs). PT-x copolymers were synthesized from two different monomers, where the ratio of the monomers was carefully controlled to achieve a UV photo-crosslinkable layer while leaving the ${\pi}-{\pi}$ stacking feature of conjugated polymers unchanged. The crosslinking stabilizes PT-x/PCBM blend morphology preventing the macro phase separation between two components, which lead to OPVs with remarkably enhanced thermal stability. The drastic improvement in thermal stabilities is further characterized by microscopy as well as grazing incidence X-ray scattering (GIXS). In the second part of talk, we will discuss the use of block copolymers as active materials for WOLEDs in which phosphorescent emitter isolation can be achieved. We have exploited the use of triarylamine (TPA) oxadiazole (OXA) diblock copolymers (TPA-b-OXA), which have been used as host materials due to their high triplet energy and charge-transport properties enabling a balance of holes and electrons. Organization of phosphorescent domains in TPA-b-OXA block copolymers is demonstrated to yield dual emission for white electroluminescence. Our approach minimizes energy transfer between two colored species by site isolation through morphology control, allowing higher loading concentration of red emitters with improved device performance. Furthermore, by varying the molecular weight of TPA-b-OXA and the ratio of blue to red emitters, we have investigated the effect of domain spacing on the electroluminescence spectrum and device performance.

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Electrical transport characteristics of deoxyribonucleic acid conjugated graphene field-effect transistors

  • Hwang, J.S.;Kim, H.T.;Lee, J.H.;Whang, D.;Hwang, S.W.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.482-483
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    • 2011
  • Graphene is a good candidate for the future nano-electronic materials because it has excellent conductivity, mobility, transparency, flexibility and others. Until now, most graphene researches are focused on the nano electronic device applications, however, biological application of graphene has been relatively less reported. We have fabricated a deoxyribonucleic acid (DNA) conjugated graphene field-effect transistor (FET) and measured the electrical transport characteristics. We have used graphene sheets grown on Ni substrates by chemical vapour deposition. The Raman spectra of graphene sheets indicate high quality and only a few number of layers. The synthesized graphene is transferred on top of the substrate with pre-patterned electrodes by the floating-and-scooping method [1]. Then we applied adhesive tapes on the surface of the graphene to define graphene flakes of a few micron sizes near the electrodes. The current-voltage characteristic of the graphene layer before stripping shows linear zero gate bias conductance and no gate operation. After stripping, the zero gate bias conductance of the device is reduced and clear gate operation is observed. The change of FET characteristics before and after stripping is due to the formation of a micron size graphene flake. After combined with 30 base pairs single-stranded poly(dT) DNA molecules, the conductance and gate operation of the graphene flake FETs become slightly smaller than that of the pristine ones. It is considered that DNA is to be stably binding to the graphene layer due to the ${\pi}-{\pi}$ stacking interaction between nucleic bases and the surface of graphene. And this binding can modulate the electrical transport properties of graphene FETs. We also calculate the field-effect mobility of pristine and DNA conjugated graphene FET devices.

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A Series of Transition-metal Coordination Complexes Assembled from 3-Nitrophthalic Acid and Thiabendazole: Synthesis, Structure and Properties

  • Xu, Wen-Jia;Xue, Qi-Jun;Liang, Peng;Zhang, Ling-Yu;Huang, Yan-Feng;Feng, Yu
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.218-224
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    • 2014
  • In order to explore new coordination frameworks with novel designed 3-nitrophthalic acid and the same N-donor ancillary ligand, a series of novel coordination complexes, namely, $[Cd_2(3-NPA)_2(TBZ)_2(H_2O)_2]{\cdot}2H_2O$(1), $[Zn_2(3-NPA)_2(TBZ)_2]$(2), $[Zn_2O(3-NPA)(TBZ)(H_2O)]_n$(3), $[Co(3-NPA)(TBZ)(H_2O)]_n$(4) (3-$NPAH_2$ = 3-nitrophthalic acid), have been hydrothermally synthesized through the reaction of 3-nitrophthalic acid with divalent transition-metal salts in the presence of N-donor ancillary coligand (TBZ = thiabendazole). As a result of various coordination modes of the versatile 3-$NPAH_2$ and the coligand TBZ, these complexes exhibit structural diversity. X-ray structure analysis reveals that 1 and 2 are 0D molecular rings, while 3 and 4 are one-dimensional (1D) infinite chain polymers. And the weak O-H${\cdots}$O hydrogen bonds and C-H${\cdots}$O nonclassical hydrogen bonds as well as ${\pi}-{\pi}$ stacking also play important roles in affecting the final structure where complexes 1, 3 and 4 have 3D supramolecular architectures, while complex 2 has a 2D supramolecular network. Also, IR spectra, fluorescence properties and thermal decomposition process of complexes 1-4 were investigated.

Effect of the Length of Side Group Substitution on Optical and Electroluminescene Properties

  • Shin, Hwangyu;Kang, Hyeonmi;Kim, Beomjin;Park, Youngil;Yu, Young-Jun;Park, Jongwook
    • Bulletin of the Korean Chemical Society
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    • v.35 no.10
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    • pp.3041-3046
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    • 2014
  • Blue emitting materials, 9,10-bis-biphenyl-4-yl-anthracene (AC-P), 9,10-bis-[1,1';4',1"]terphenyl-4-yl-anthracene (AC-DP), and 9,10-bis[3",5"-deiphenyltriphenyl-4'-yl]anthracene (AC-TP) were synthesized through boration and Suzuki aryl-aryl coupling reaction. EL performance of blue light-emitters was optimized and improved by varying the chemical structures of the side groups. In the thin film state, the three materials exhibit $PL_{max}$ values in the range of 442-456 nm. EL device with the synthesized compounds in the following configuration was fabricated: ITO/4,4',4"-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine (2-TNATA) 60nm/N,N'-bis (naphthalene-1-yl)-N,N'-bis(phenyl)benzidine (NPB) 15nm/synthesized blue emitting materials (30nm)/1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) 20nm/LiF 1nm/Al 200nm. The current efficiency and C.I.E. value of AC-TP were 3.87 cd/A and (0.15, 0.12). A bulky and non-planar side group helps to prevent ${\pi}-{\pi}^*$ stacking interaction, which should lead to the formation of more reliable amorphous film. This is expected to have a positive effect on the high efficiency of the operating OLED device.

Synthesis and Photovoltaic Properties of Polymers Based on Cyclopentadithiophene and Benzimidazole Units

  • Song, Su-Hee;Park, Sei-Jung;Kwon, Soon-Cheol;Shim, Joo-Young;Jin, Young-Eup;Park, Sung-Heum;Kim, Il;Lee, Kwang-Hee;Suh, Hong-Suk
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1861-1866
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    • 2012
  • The new semiconducting copolymers with 4,4-dialkyl-$4H$-cyclopenta[2,1-$b$:3,4-$b^{\prime}$]dithiophene and 2,2-dimethyl-$2H$-benzimidazole units were synthesized. The fused aromatic rings, such as cyclopentadithiophene (CPDT) unit, can make the polymer backbone more rigid and coplanar, which induces long conjugation length, narrow band gap, and strong intermolecular ${\pi}-{\pi}$ interaction. The stacking ability was controlled through attaching of linear or branched alkyl side chains. The spectra of PEHCPDTMBI and PHCPDTMBI in the solid films show absorption bands with maximum peaks at 401, 759 and 407, 768 nm, and the absorption onsets at 925 and 954 nm, corresponding to band gaps of 1.34 and 1.30 eV, respectively. The devices comprising PHCPDTMBI with $TiO_X$ showed a $V_{OC}$ of 0.39 V, a $J_{SC}$ of 1.14 $mA/cm^2$, and a $FF$ of 0.34, giving a power conversion efficiency of 0.15%. The PHCPDTMBI with linear alkyl chain on CPDT shows good solubility in organic solvent with higher PCE value than that of PEHCPDTMBI.

Lightweight Convolution Module based Detection Model for Small Embedded Devices (소형 임베디드 장치를 위한 경량 컨볼루션 모듈 기반의 검출 모델)

  • Park, Chan-Soo;Lee, Sang-Hun;Han, Hyun-Ho
    • Journal of Convergence for Information Technology
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    • v.11 no.9
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    • pp.28-34
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    • 2021
  • In the case of object detection using deep learning, both accuracy and real-time are required. However, it is difficult to use a deep learning model that processes a large amount of data in a limited resource environment. To solve this problem, this paper proposes an object detection model for small embedded devices. Unlike the general detection model, the model size was minimized by using a structure in which the pre-trained feature extractor was removed. The structure of the model was designed by repeatedly stacking lightweight convolution blocks. In addition, the number of region proposals is greatly reduced to reduce detection overhead. The proposed model was trained and evaluated using the public dataset PASCAL VOC. For quantitative evaluation of the model, detection performance was measured with average precision used in the detection field. And the detection speed was measured in a Raspberry Pi similar to an actual embedded device. Through the experiment, we achieved improved accuracy and faster reasoning speed compared to the existing detection method.

A Single-crystal PMN-29PT Stack Actuator: Fabrication and Performance (단결정 PMN-29PT 적층형 작동기: 제작과 성능)

  • Park, Hoon Cheol;Adyatama, Panji;Lee, Ho-Yong
    • Journal of the Korean Ceramic Society
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    • v.50 no.6
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    • pp.545-550
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    • 2013
  • Piezoelectric PMN-29PT single crystal multilayer actuators [100 $mm^2$ in cross section and 22 mm in length] are designed and fabricated by stacking square plates [$10{\times}10{\times}0.5(t)\;mm^3$] of PMN-29PT single crystals having a $d_{33}$ of about 1,500 pC/N. The characteristics of PMN-29PT multilayer actuators are compared with those of P-025.40P multilayer PZT ceramic actuators [490 $mm^2$ in cross section and 60 mm in length] produced by PI in Germany. Even though the total volume of the PMN-29PT single crystal multilayer actuator is only about 7.5% of that of the P-025.40P ceramic multilayer actuator, PMN-29PT single crystal multilayer actuators are expected to show very similar properties to P-025.40P ceramic actuators in terms of static stroke and blocking force. Therefore, on the basis of their smaller mass and volume compared to the conventional PZT ceramic multilayer actuators, piezoelectric PMN-29PT single crystal multilayer actuators have significant potential regarding the development of various high performance actuators for aerospace subsystems.

Synthesis and Characterization of Power Conversion Efficiency of D/A Structure Conjugated Polymer Based on Benzothiadiazole-Benzodithiophene (Benzothiadiazole-benzodithiophene을 기반으로 한 D/A구조의 공액 고분자 합성 및 광전변환 효율 특성 개선 연구)

  • Seong, Ki-Ho;Yun, Dae-Hee;Woo, Je-Wan
    • Applied Chemistry for Engineering
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    • v.24 no.5
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    • pp.537-543
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    • 2013
  • In this study, the push-pull structure polymer for organic photo voHaics (OPVs) was synthesized and characterized. The poly{4,8-didodecyloxybenzo[1,2-b;3,4-b]dithiophene-alt-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)benzo[c][1,2,5]-thiadiazole} (PDBDT-TBTD) was synthesized by Stille coupling reaction using the benzothiadiazole (BTD) derivative as an electron acceptor and benzodithiophene (BDT) derivative as an electron donor. The structure of monomers and polymers was identified by $^1H-NMR$ and GC-MS. The optical, physical and electrochemical properties of the conjugated polymer were identified by GPC, TGA, UV-Vis and cyclic voltammetry. The number average molecular weight ($M_n$) and initial decomposition temperature (5% weight loss temperature, $T_d$) of PDBDT-TBTD were 6200 and $323^{\circ}C$, respectively. The absorption maxima on the film was about 599 nm and the optical band gap was about 1.70 eV. The structure of device was ITO/PEDOT : PSS/PDBDT-TBTD : $PC_{71}BM/BaF_2/Ba/Al$. PDBDT-TBTD and $PC_{71}BM$ were blended with the weight ratio of 1:2 which were then used as an optical active layer. The power conversion efficiency (PCE) of fabricated device was measured by solar simulator and the best PCE was 2.1%.

Layer-by-Layer Self-Assembled Multilayer Film Composed of Polyaniline, Graphene Oxide, and Phytic Acid for Supercapacitor Application (슈퍼커패시터 활용성 자가조립된 폴리아닐린, 그래핀 옥사이드 그리고 피트산으로 구성된 다층 초박막)

  • Lee, Myungsup;Hong, Jong-Dal
    • Journal of the Korean Chemical Society
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    • v.59 no.1
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    • pp.36-44
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    • 2015
  • This article describes synthesis and electrochemical properties of layer-by-layer self-assembled multilayer film composed of polyaniline (PANi), graphene oxide (GO) and phytic acid (PA), whereby the GO was electrochemically reduced to ERGO, resulting in $(PANi/ERGO/PANi/PA)_{10}$ film electrode. Especially, we examined the possibility to improve the volumetric capacitive property of $(PANi/ERGO)_{20}$ film electrode via combining a spherical hexakisphosphate PA nanoparticle into the multilayer film that would dope PANi properly and also increase the porosity and surface area of the electrode. The electrochemical performances of the multilayer film electrodes were investigated using a three-electrode configuration in 1 M $H_2SO_4$ electrolyte. As a result, the $(PANi/ERGO)_{20}$ electrode showed the volumetric capacitance of $666F/cm^3$ at a current density of $1A/cm^3$, which was improved to the volumetric capacitance of $769F/cm^3$ for the $(PANi/ERGO/PANi/PA)_{10}$ electrode, in addition to the cycling stability maintained to 79.3% of initial capacitance after 1000 cycles. Thus, the electrochemical characteristics of the $(PANi/ERGO)_{20}$ electrode, which was densely packed by ${\pi}-{\pi}$ stacking between the electron-rich conjugate components, could have been improved through structural modification of the multilayer film via combining a spherical hexakisphosphate PA nanoparticle into the multilayer film.

Sensor Applications of Microporous Conjugated Polymers

  • Gwak, Gi-Seop
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.125-125
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    • 2014
  • In 1991, Prof. Toshio Masuda of Kyoto University for the first time synthesized a representative of diphenylacetylene polymer derivatives, poly[1-phenyl-2-(p-trimethylsilyl)phenylacetylene] [PTMSDPA]. This polymer is highly soluble nevertheless a ultra-high molecular weight (Mw) of > $1.0{\times}10^6$ which showed excellent chemical, physical, mechanical properties [1]. As one of the most interesting features of PTMSDPA, Prof. Katsumi Yoshino of Osaka Univ. reported that this polymer emits an intense fluorescence (FL) in a visible region because of the effective exciton confinement within the resonant structure between the polyene pi-conjugated chain and side phenyl full-aromatic bulky groups [2]. Very recently, Prof. Ben-Zhong Tang of Hong-Kong Institute of Science and Technology clarified the idea that the FL emission of disubstituted acetylene polymer derivatives originates from intramolecular excimer due to the face-to-face stacking of the side phenyl groups [3]. Thus, to know what influence to intramolecular excimer emission in the film as well as to further understand how the intramolecular excimer forms in the film became more crucial in order to further precisely design the optimized molecular structure for highly emissive, substituted acetylene polymers in the solid state. In recent studies, we have focused our interests on the origin of the FL emission in order to expand our knowledge to developments of novel sensor applications. It was found that the intramolecular phenyl-pheyl stack structure of PTMSDPA in film was variable in response to various external chemical stimuli. Using PTMSDPA and its derivatives, we have developed various potential applications such as latent fingerprint identification, viscosity sensor, chemical-responsive actuator, gum-like soft conjugated polymer, and bioimaging. The details will be presented in the 49th KVS Symposium held in Pyong Chang city.

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