林金福臺灣大學:材料科學與工程學系暨研究所周子瑜Chou, Zi-YuZi-YuChou2010-07-142018-06-282010-07-142018-06-282008U0001-0812200817201800http://ntur.lib.ntu.edu.tw//handle/246246/189011在本研究中，我們成功地利用Horner-Wittig Reaction合成出Oligo(2,5-bis(octyloxy)-p-phenylene vinylene) (OHC-Tri-BOPV-CHO)，並與較早之前實驗室合成出來的Oligo(2,5-bis(hexyloxy)-p-phenylene vinylene) (OHC-Tri-BHPV-CHO)共同做一系列的光學性質、自組裝奈米結構與有機/無機掺和實驗的探討和比較。利用UV-vis光譜及PL光譜來研究OHC-Tri-BOPV-CHO、OHC-Tri-BHPV-CHO以chloroform、hexane、decane為指定溶劑時不同濃度之溶液態光學性質，並且進一步研究藉由旋轉塗佈所形成的固態薄膜，其光學特性及與溶液間的差異。經由分析我們發現：UV光譜的高峰強度增加皆與溶液的濃度變化成正比；且當溶劑由極性改為非極性溶劑時，不論是溶液或薄膜固態的UV圖譜皆會有藍位移的現象，薄膜固態的螢光特性則會有紅位移的現象產生；固態的UV光譜與螢光光譜和溶液的UV及PL圖譜相較下皆有紅位移的現象。此外，我們又將OHC-Tri-BOPV-CHO、OHC-Tri-BHPVCHO 溶在不同的溶劑下(hexane、decane、chloroform、THF)，以AFM及TEM觀測其溶劑中不同濃度下的自組裝結構，其自組裝結構出現濃度與PL光譜分析結果一致，我們並利用其分子結構的組成與觀測到的自組裝結構結合起來，提出一個modle來描述OHC-Tri-BOPV-CHO及OHC-Tri-BHPV-CHO系列分子之間堆疊的機制，其驅動力為偶極矩作用力與π-π堆疊交互作用力，OPV系列分子在溶液中由於π-π堆疊交互作用力使π共軛分子彼此平行排列且偶極矩作用力使側邊醛基部分相連而向兩旁延伸排列，由此形成極薄的片狀結構，而OHC-TriBOPV-CHO由於側鏈烷鏈段較長，其空間與能量不足以使片狀結構整個向上捲起為管狀，因此在適當的濃度下僅能在邊緣處稍微捲起( 在hexane中) ，或是藉由排列形成長板型的條狀結構(在THF中) ，甚至有上下堆疊的情形產生(在chloroform中)。相較之下，OHC-Tri-BHPVCHO則由於側鏈烷鏈段較短，片狀結構向上捲起為中空管狀時除了可降低表面能外，也提供側鏈烷鏈段足夠的伸展空間，因此在適當的濃度下可以形成中空管狀結構(在THF中)，或是藉由片狀結構的堆疊而形成條狀結構(在chloroform中)。最後，我們以OHC-Tri-BOPV-CHO、OHC-Tri-BHPV-CHO在THF中形成的管狀自組裝結構為基礎，進行Titania與Silica兩個系列不同濃度比的有機/無機摻合實驗，得出最佳化的濃度比例，兩組系列的主要差異在於：Titania掺和實驗的主要發光波長較為紅移、與Silica掺和之螢光結構呈條狀且長度較長，而與Titania掺和之螢光結構則呈現較粗短且緻密的網狀結構。In this research, oligo(2,5-bis(octyloxy)-p-phenylene vinylene) (OHC-Tri-BOPV-CHO) was successfully synthesized via the Horner-Wittig Reaction. A series of experiments including optical properties, investigation of self-assembly nanostructure and organic/ inorganic hybrid had been done on OHC-Tri-BOPV-CHO and oligo(2,5-bis(hexyloxy)-p-phenylene vinylene) (OHC-Tri-BHPV-CHO). We used UV and PL to study the optical properties of OHC-Tri-BOPV-CHO and OHC-Tri-BHPV-CHO compounds dissolving in the chloroform, hexane, and decane and in solid thin films by spinning coating. From the UV spectroscopy, the intensity of absorption peaks increase with solution’s concentration. And the compounds dissolving in different solvent showed the absorption peaks would be blue-shifted with increasing the solvent polarity while the PL peaks red-shifted. Nevertheless, the solid thin films always showed red-shifted in both UV/vis absorption and PL spectra compared to the compounds in solutions. Moreover, the self-assembly nanostructure of compounds in different solvent (hexane、decane、chloroform、THF) and concentration was also investigated by AFM and TEM. The change of self-assembly nanostructure with the concentration was parallel with the result of PL investigation. It is believed that the driving forces for all above self-assembly processes were the combination of dipole-dipole interaction, π-πinteraction, and Van der Waals force. The compounds of OHC-TriBHPV-CHO in THF self-assembled to form a very thin film, which tended to roll up into a hollow tubular structure to decrease the surface energy. Due to the longer length of side chain, OHC-Tri-BOPV-CHO molecules could only arrange into plank-like long stripes structure in THF and slightly roll up at film edge ( in hexane ), or even stack up with each other ( in chloroform ). At last, we took the tubular self-assembly structures of OHC-Tri-BOPV-CHO and OHC-Tri-BHPV-CHO in THF solvent as a structure base to further study the hybrid nano-strucutures with titania and silica.The result showed that the wavelength of luminescence of the titania hybrid series was red-shifted compared to the silica hybrid series, and the luminescent structure of the silica hybrid series has longer length but less dense than that of the titania hybrid series.致謝……………………………………………………………………..Ⅰ要…………………………………………………………….……….Ⅱbstract…………………………………...……………………………Ⅳ錄……………………………………………………………….…….Ⅵ目錄………………………………………..……………….……. ⅩⅠ目錄………………………………………………………….…….ⅩⅡ一章 緒論............................................................................................1-1超分子化學與自組裝簡介 …………………………………………1-2 π共軛系統的自組裝與超分子結構……………………..……….....4-2-1 π共軛系統的自組裝定律…………………………………….4-2-2 π共軛系統的自組裝文獻回顧……………………………….8-3本實驗室研究成果回顧……………………………………………33-3-1 OHC-Tri-BHPV-CHO共軛分子之合成及自組裝性質探討…………………………………………………………… 33-3-2本篇研究研究構想與重點……………………….………….47二章 實驗設備與方法……………………………………………...49-1化學藥品……………………………………………………………49-2儀器設備………………………………………………………..…..50-3合成步驟……………………………………………………………52-3-1 OHC-Tri-BHPV-CHO之合成……………………….………52-3-1-1 2,5-dibromobenzene-1,4-diol (1) [91-93].-3-1-2 1,4-dibromo-2,5-bis(hexyloxy)benzene (2) [94].-3-1-3 2,5-bis(hexyloxy)benzene-1,4-dialdehyde (3) [95].-3-1-4 1,4-bis(hexyloxy)benzene (4).-3-1-5 1,4-bis(bromomethyl)-2,5-bis(hexyloxy)benzene (5).-3-1-6 2,5-bis(hexyloxy)benzene-1,4-dibutyl phosphate (6).-3-1-7 Oligo(2,5-bis(hexyloxy)-p-phenylene Vinylene) (OHC-Tri-BHPV-CHO) (7).-3-2 OHC-Tri-BOPV-CHO之合成……....………………….……57-3-2-1 1,4-bis(octyloxy)benzene (8).-3-2-2 1,4-dibromo-2,5-bis(octyloxy)benzene (9)-3-2-3 2,5-bis(octyloxy)benzene-1,4-dialdehyde (10)-3-2-4 1,4-bis(bromomethyl)-2,5-bis(octyloxy)benzene (11).-3-2-5 2,5-bis(octyloxy)benzene-1,4-dibutyl phosphate (12).-3-2-6 Oligo(2,5-bis(octyloxy)-p-phenylene Vinylene) (OHC-Tri-BOPV-CHO) (13).-4有機/無機掺和 ……………………………………………………62-4-1 OHC-Tri-BHPV-CHO /Silica掺和…………………..………63-4-2 OHC-Tri-BHPV-CHO /Titania掺和.……………..…………64-4-3 OHC-Tri-BOPV-CHO /Silica掺和.…………………………65-4-4 OHC-Tri-BOPV-CHO /Titania掺和…………………………67-5樣品準備……………………………………………………………68-5-1 測量紫外光/可見光吸收光譜儀、螢光光譜儀之OHC-Tri-OPV-CHO溶液樣品準備……………………….……………68-5-2測量紫外光/可見光吸收光譜儀、螢光光譜儀之OHC-Tri-HPV-CHO固態樣品準備………………………….…………69-5-3測量紫外光/可見光吸收光譜儀、螢光光譜儀之OHC-Tri-OPV-CHO固態樣品準備 ………………………………...…70-5-4 OHC-Tri-BOPV-CHO在不同溶液、濃度下之AFM、TEM、SEM試片準備……………………………………………………71-5-5 OHC-Tri-BHPV-CHO、OHC-Tri-BOPV-CHO與Silica、Titania掺和之AFM、TEM、SEM、SCMS試片準備..………….72三章 結果與討論……………………………………………….…..79-1溶液中的分子構裝…………………………………………………79-1-1溶液中的光學吸收特性……………………………………..79-1-2溶液中的螢光特性…………………………………………..81-1-3 綜和討論…………………………………………………….85-2 固態光學吸收特性與螢光特性……………………….…….……99-2-1固態的光學吸收特性……………………………….……….99-2-2固態的螢光特性……………………………………….…...100-2-3 綜和討論…………………………………………….……..101-3 π共軛分子的固體狀態超分子連結…….………...……………108-3-1 OHC-Tri-BOPV-CHO在hexane溶液中的自組裝結構…..109-3-2 OHC-Tri-BOPV-CHO在decane溶液中的自組裝結構…..110-3-3 OHC-Tri-BOPV-CHO在chloroform溶液中的自組裝結構…………………………………………………………..111-3-4 OHC-Tri-BOPV-CHO在THF溶液中的自組裝結構……..113-3-5 OHC-Tri-BHPV-CHO在THF溶液中的自組裝結構……..115-3-6綜合討論……………………………………………..……..117-4 有機/無機掺和的超分子連結…………………………………..137-4-1 OHC-Tri-BHPV-CHO /Silica掺和，濃度比OHC-Tri-BHPVCHO：Silica＝1：400……………………………………..137-4-2 OHC-Tri-BHPV-CHO /Silica掺和，濃度比OHC-Tri-BHPVCHO：Silica＝1：4000………………………..….………140-4-3 OHC-Tri-BHPV-CHO /Titania掺和，濃度比OHC-Tri-BHPVCHO：Titania＝1：400……………………………………141-4-4 OHC-Tri-BOPV-CHO /Titania/Silica掺和…………………143-4-5 綜合討論……………………………………………..…….144四章 結論……………………………………………….…………162五章 參考資料…………………………………………….………168ist of Tables and Schemesable 1-1 Strength of non-covalent forces ……………………………………..…… 6able 1-2 Lattice parameters of the two-dimensional crystals of oligo(pphenylene vinylene)s formed by physisorption on HOPG, as obtained by STM ………….....…21able 3-1 The total date of UV-vis peaks for OHC-Tri-BOPV-CHO and OHC-TriBHPV-CHO in different solution……………………………………………...……87able 3-2 The total date of PL peaks for OHC-Tri-BOPV-CHO and OHC-Tri-BHPVCHO in different solution……………………………………………………...……87able 3-3 The total date of UV-vis peaks for OHC-Tri-BOPV-CHO and OHC-TriBHPV-CHO in solid state………………………………………………………….104able 3-4 The total date of PL peaks for OHC-Tri-BOPV-CHO and OHC-Tri-BHPVCHO in solid state………………………………………………………………….104able 3-5 The description of structure of OHC-Tri-BOPV-CHO observed by AFM & TEM in hexane、chloroform and THF solution………………..…………………..119able 3-6 The description of structure of OHC-Tri-BHPV-CHO observed by AFM & TEM in hexane、chloroform and THF solution……………………………………120ist of Figuresigure 1-1 Supramolecular nanostructures with well-defined shapes and sizes….…. 2igure 1-2 Self-organization of block copolymers……………………….…….……..3igure 1-3 Basic structures of some semi-conducting polymers ……………………. 4igure 1-4 Representation on how the properties of molecular devices are related to chemical structures and supramolecular architectures………………………….……. 5igure 1-5 Interaction between two idealized a-atoms as a function of orientation: two attractive geometries and the repulsive face-to-face geometry are illustrated…....6igure 1-6 Chemical structure of the rod-coil polymers studied in ref. 74. The structural units of the polyisoprene segments result from 3,4 addition (x) (~ 71%) and 1,2 addition (y) (~29%)……………………………………………………………..... 8igure 1-7 Unfiltered TEM image of rod-coil polymers having rod fraction= 0.35 (upper left), 0.20 (upper right), 0.30 (down)………………………………………..... 9igure 1-8 Chemical structures of the rod-coil polymers studied in ref. 75…….….. 10igure 1-9 Upper: Direct TEM comparison of the nanostructures formed by (a)18 and (b) 19. Down: TEM micrograph of 26 revealing the formation of strips with nanoscale dimensions. The strips are 8 nm in width and approximately 80 nm in length (left). (Right) Molecular graphics model showing the herringbone packing of the phenylene vinylene oligomeric rods………………….………………….…………. 11igure 1-10 Chemical structures of DRCs………………………………………..... 12igure 1-11 (a) TEM micrograph of 4T-DRC ribbons cast on amorphous carbon. (b) Molecular graphics of two DRC molecules measuring to be 10 nm. (Right) Atomic force microscopy image of aligned ribbons of 4T-DRC on Au/Cr patterned mica substrate. The diagram (left) depicts where the edge of the gold electrode begins on the substrate. Ribbons are aligned in the gap………………………………….……. 13igure 1-12 Mosaic birefringence texture of the OPV-12 amphiphile at 130°C, observed between crossed polarizers ……………………………………….…... 14igure 1-13 (a) Small-angle X-ray scattering of OPV amphiphiles. Inset showsnter-layer spacing as a function of PEG length determined from the first order diffraction peak. Dashed line is the fully extended length of one molecule. (b) Wide-angle X-ray diffraction of OPV amphiphiles………………………………… 14igure 1-14 (a) Absorption and (b) photoluminescence of OPV amphiphile solutions and films of varying PEG length. All spectra are normalized to the same intensity to facilitate comparison of peak shape. (c) Bilayer packing model showing alkyl (red), OPV (green), and PEG (blue) layers. Inset arrows show approximate orientation of OPV transition dipole……………………………………………………….………. 15igure 1-15 Atomic force microscopy images of R-DRC (left) and S-DRC (right). The horizontal and vertical scale bars are identical for both images. The white lines indicate handedness………………………………………………………….……… 17igure 1-16 Chemical structures of sexithiophenes with chiral and achiral penta(ethylene glycol) chains………………………………………….…….……… 19igure 1-17 Scanning probe microscopy images of thin deposits cast from toluene solutions of 1. (a) Tapping-mode AFM phase image showing the preferential orientation of large ribbons on graphite. The three-fold symmetry is indicated as a guide; (b) 80 x 80 nm2 STM topographic images showing the internal structure of a large ribbon on graphite. The white arrows indicate the width of a single thin ribbon. The vertical grayscale is 15 nm; (c) 700 x 700 nm2 tapping-mode AFM phase image on silicon, showing left-handed helical aggregates……………………….………… 19igure 1-18 Schematic representation of the molecules studied by STM: the achiral OPV-dimer (OPV2), the chiral OPV-tetramer (OPV4), and the chiralPV-hexamer (OPV6)………………………………………………….…………... 20igure 1-19 STM images of OPV6 monolayers formed by physisorption on graphite. OPV moieties and alkyl chains can both be observed. Image size of (a) is 10.7 x 10.7 nm2 ………………………………………………………………………….……..... 21igure 1-20 STM images of OPV4 at the liquid/graphite interface. The molecules are organized in an end-to-end type fashion, with the alkyl chains residing in between the rows of OPV-units. Some alkyl chains are resolved and can be recognized in the image. Image size of (a) is 25.1 x 25.1 nm2 ……………………………….…….…. 22igure 1-21 STM images of OPV2 at the liquid/graphite interface. The unit cell of the 2D lattice is indicated. The long-dashed line indicates a boundary between an area where the OPV-units are aligned in rows. Image size of (a) is 14.5 x 14.5 nm2….....22igure 1-22 Chemical structures of the studied oligothiophenes in Ref. 86……..… 23igure 1-23 AFM images of 6T island growth at (a) deposition T = 25 °C, h =5 nm; (b) T = 150 °C, h = 3 nm ...………………………………………………..……… 24igure 1-24 AFM height (a) and phase (b) images (2.5 x 2.5 μm2) of a thin deposit of 6c on graphite………………………………………………………………..……… 24igure 1-25 AFM images on silicon oxide of (a) 2b (5.0 x 5.0 μm2) and (b) 3b (2.5 x 2.5 μm2). Only 3b shows left-handed helical aggregates………………….………... 25igure 1-26 Structures of chiral OPV derivatives…………………………..……… 26igure 1-27 Helical morphology of C-OPV1 self-assembly from a solution in dodecane: a) FESEM image of left-handed-helical fibers (9 x10-5 M) and b) FESEM image showing the formation of a coiled-coil rope (5 x10-4M)…………….………. 27igure 1-28 Physical appearance and AFM images of the C-OPV1 gel from a solution in dodecane (6 x10-3 M): a) photograph of the gel; b) dense network of helical fibers; c) single left-handed coiled-coil rope………………………….…….….…… 27igure 1-29 Schematic representation of the hierarchical self-assembly of C-OPV1 into helical coiled-coil gel nanostructures……………………………………...…… 28igure 1-30 Concentration and temperature dependence of the CD spectrum of C-OPV1 in dodecane: CD spectra of C-OPV1 at different a) concentrations (T=293 K, l=1 mm) and b) temperatures (c=5.3 x10-4M, l=1 mm). c) Concentration-dependent transition of the intensity of the CD signal of C-OPV1 monitored at 391 nm; d) melting-transition plot of CD intensity at 470 nm; e) melting-transition curve of the absorbance of C-OPV1 at 405 nm. The inset in (a) shows the CD spectra of C-OPV1 in dodecane and chloroform (c=5.3 x10-4M, l=1 mm); the inset in (b) shows the same CD spectra as in the main plot at different temperatures, but just within the range 24–35oC ...………………………………………………………………....…….. ….28igure 1-31 Chemical structures of fluorene-based diblock and triblock copolymers ……………………………………………………………………........30igure 1-32 AFM image of a thin deposit on mica of (a) 1a from THF; (b) 1b from THF; (c) 1c from THF; (d) 1d from toluene. The scale bar represents 500 nm….…..31igure 1-33 (a) AFM picture (1.5 x 1.5 μm2) of a thin deposit of 1a on a mica substrate. (b) Molecular modeling of the proposed supramolecular organization within the nano-ribbons……………………………………………………….…………. …31igure 1-34 Plot showing the dependence of morphology on both the solution concentration and surface type. Depicted are tapping mode AFM images on glass (repulsive surface), graphite (inert surface) and gold (attractive surface)..……....… 32igure 1-35 Synthesis routes of Oligo(2,5-bis(hexyloxy)-p-phenylene Vinylene) (OHC-Tri-BHPV-CHO) (7)…………………………………………………….…... 34 Figure 1-36 1H NMR spectrum of (OHC-Tri-BHPV-CHO) (7).……………...…... 34igure 1-37 The pictures of OHC-Tri-BHPV-CHO in hexane for the concentration of 1.065 x 10-4 M, 1.065 x 10-5 M, and 1.065 x 10-6 M (from left to right)……….35igure 1-38 The pictures of OHC-Tri-BHPV-CHO in decane for the concentration of 1.065 x 10-4 M, 1.065 x 10-5 M, and 1.065 x 10-6 M (from left to right)……….35igure 1-39 The pictures of OHC-Tri-BHPV-CHO in chloroform for the concentration of 1.023 x 10-4 M, 1.023 x 10-5 M, and 1.023 x 10-6 M (from left to right)………………………………………………………………………………….35igure 1-40 PL spectra of OHC-Tri-BHPV-CHO in hexane for the concentration ranging from 1.065 x 10-6 to 1.065 x 10-4 M (a), and the plot of Ieq versus the concentration (b)…..…………………………………….……………………….…...36igure 1-41 PL spectra of OHC-Tri-BHPV-CHO in decane for the concentration ranging from 1.065 x 10-6 to 1.065 x 10-4 M (a), and the plot of Ieq versus the concentration (b)..…………........................................................................................ 37igure 1-42 PL spectra of OHC-Tri-BHPV-CHO in chloroform at the indicated concentrations (a), and their plot of Ieq versus the concentration (b).…………........ 38igure 1-43 AFM images with section analysis (a, b) of tubular structures formed by OHC-Tri-BHPV-CHO in hexane solution at C =1.065 x 10-4 M; and the scheme to depict the possible formation mechanism (c)..………………………………............ 40igure 1-44 HR-TEM images (a,b) with the FFT pattern (inset, blue arrow indicates Fourier components) of OHC-Tri-BHPV-CHO tubular nanostructure taken by cryo-TEM under 400 kV; molecular simulation graphics of OHC-Tri-BHPV-CHO molecules after performing Cerius 2 energy minimization (side view (c) and top view (d))..………………………………………………………………………….......…...41igure 1-45 AFM images with section analysis (a, b) and TEM image (inset of b) of tubular structures formed by OHC-Tri-BHPV-CHO in decane solution at C = 1.065 x 10-5 M; AFM (c) and TEM (d) images at C = 1.065 x 10-4 M……....………….......42igure 1-46 HR-TEM images (a, b) with the FFT pattern (inset of b, black arrow indicates Fourier components) of OHC-Tri-BHPV-CHO tubular nanostructure taken by cryo-TEM under 400 kV (b is the magnified image of green circle region in a, and FFT pattern is taken from red box region)………………………………...…………43igure 1-47 Scheme to depict the possible formation mechanism for OHC-Tri-BHPVCHO nanotubes………………………………………...………………...…...……..43igure 1-48 AFM and TEM images (inset) of nanostructures of OHC-Tri-BHPVCHO prepared from chloroform solutions at C = 1.023 x 10-5 M (2a); and C = 1.023 x 10-4 M (2b) with its section analysis (2c)………...……………………….……….44igure 1-49 TEM images of nanostructures of OHC-Tri-BHPV-CHO prepared from chloroform solutions at C = 1.023 x 10-5 M (3a); and C = 1.023 x 10-4 M (3b)……...45igure 1-50 HR-TEM image to show the molecular packing of OHC-Tri-BHPVCHO inside the multi-layer strips with the corresponding FFT spots shown in left inset. Right inset is the STM image of molecular packing of OHC-Tri-BHPV-CHO inside the monolayer strip prepared from the chloroform solution at C = 1.023 x 10-5 M ..………………………………………………………………………..…..….…..46igure 1-51 Formation mechanism of monolayer strip (b); and multilayer strip (c). (Orange plane indicates OHC-Tri-BHPV-CHO backbone, red ball indicates ether group, blue ball indicates aldehyde group, black line indicates aliphatic side chain)………………………………………………………………………………... 47igure 2-1 Synthesis routes of Oligo(2,5-bis(hexyloxy)-p-phenylene Vinylene) (OHC-Tri-BHPV-CHO) (7).………………………………………….…..……....…. 57igure 2-2 Synthesis routes of Oligo(2,5-bis(octyloxy)-p-phenylene Vinylene) (OHC-Tri-BOPV-CHO) (13)…………………………………………….……...……62igure 2-3 1H NMR spectrum of the compound 7………………………….….....…73igure 2-4 13C NMR spectrum of the compound 7 ……………………..…..………74igure 2-5 1H /13C 2DNMR spectrum of the compound 7……………….….………74igure 2-6 1H NMR spectrum of the compound 8……………………………..……75igure 2-7 1H NMR spectrum of the compound 9 ………..……….......................... 75igure 2-8 1H NMR spectrum of the compound 10 …………………………..…… 76igure 2-9 1H NMR spectrum of the compound 11 ………………………….……..76igure 2-10 1H NMR spectrum of the compound 12 …..……………………….…..77igure 2-11 1H NMR spectrum of the compound 13 ……………………….............77igure 2-12 13C NMR spectrum of the compound 13 ....………..……..……………78igure 2-13 DEPT NMR spectrum of the compound 13……………………………78igure 3-1 The pictures of OHC-Tri-BOPV-CHO in chloroform for the concentration of 1.266 x 10-4 M, 1.266 x 10-5 M, and 1.266 x 10-6 M (from left to right)….…….88igure 3-2 The pictures of OHC-Tri-BOPV-CHO in hexane for the concentration of 1.175 x 10-4 M, 1.175 x 10-5 M, and 1.175 x 10-6 M (from left to right)…………..88igure 3-3 The pictures of OHC-Tri-BOPV-CHO in decane for the concentration of 1.221 x 10-4 M, 1.221 x 10-5 M, and 1.221 x 10-6 M (from left to right)…………..88igure 3-4 The absorption of OHC-Tri-BOPV-CHO in chloroform for the concentration (c) ranges 1.266 x 10-6 M < c < 1.266 x 10-4 M……………………..89igure 3-5 The intensities (at 358 and 446 nm) of OHC-Tri-BOPV-CHO in chloroform for the concentration (c) ranges 1.266 x 10-6 M < c < 1.266 x 10-4 M……………………………………………………………………………………..89igure 3-6 The absorption of OHC-Tri-BOPV-CHO in hexane for the concentration (c) ranges 1.175 x 10-6 M < c < 1.175 x 10-4 M…………………...………………..90igure 3-7 The intensities (at 344 and 433 nm) of OHC-Tri-BOPV-CHO in hexane for the concentration (c) ranges 1.175 x 10-6 M < c < 1.175 x 10-4 M…………..…90igure 3-8 The absorption of OHC-Tri-BOPV-CHO in decane for the concentration (c) ranges 1.221 x 10-6 M < c < 1.221 x 10-4 M…………………...………………..91igure 3-9 The intensities (at 345 and 437 nm) of OHC-Tri-BOPV-CHO in decane for the concentration (c) ranges 1.221 x 10-6 M < c < 1.221 x 10-4 M……………..91igure 3-10 The PL intensity of OHC-Tri-BOPV-CHO in chloroform for the concentration (c) ranges 1.266 x 10-6 M < c < 1.266 x 10-4 M……………………..92igure 3-11 Normalized PL (at peak1st ) of OHC-Tri-BOPV-CHO in chloroform for the concentration (c) ranges 1.266 x 10-6 M < c < 1.266 x 10-4 M……….………..92igure 3-12 Concentration dependences of Normalized PL (at peak1st ) intensity for OHC-Tri-BOPV-CHO in chloroform for the concentration (c) ranges 1.266 x 10-6 M < c < 1.266 x 10-4 M………….……………………………………………………..93igure 3-13 Ieq of OHC-Tri-BOPV-CHO in chloroform for the concentration (c) ranges 1.266 x 10-6 M < c < 1.266 x 10-4 M…………………………………….….93igure 3-14 The PL intensity of OHC-Tri-BOPV-CHO in hexane for the concentration (c) ranges 1.175 x 10-6 M < c < 1.175 x 10-4 M……………….…….94igure 3-15 Normalized PL (at peak1st ) of OHC-Tri-BOPV-CHO in hexane for the concentration (c) ranges 1.175 x 10-6 M < c < 1.175 x 10-4 M ..……..…….………94igure 3-16 Concentration dependences of Normalized PL (at peak1st ) intensity for OHC-Tri-BOPV-CHO in hexane for the concentration (c) ranges 1.175 x 10-6 M < c < 1.175 x 10-4 M………..……………………………………………….…….……..95igure 3-17 Ieq of OHC-Tri-BOPV-CHO in hexane for the concentration (c) ranges 1.175 x 10-6 M < c < 1.175 x 10-4 M……………………………………….……….95igure 3-18 The PL intensity of OHC-Tri-BOPV-CHO in decane for the concentration (c) ranges 1.221 x 10-6 M < c < 1.221 x 10-4 M……………….…….96igure 3-19 Normalized PL (at peak1st ) of OHC-Tri-BOPV-CHO in decane for the concentration (c) ranges 1.221 x 10-6 M < c < 1.221 x 10-4 M………..……....……96igure 3-20 Concentration dependences of Normalized PL (at peak1st ) intensity for OHC-Tri-BOPV-CHO in decane for the concentration (c) ranges 1.221 x 10-6 M < c < 1.221 x 10-4 M………..……………………………………………………..……..97igure 3-21 Ieq of OHC-Tri-BOPV-CHO in decane for the concentration (c) ranges 1.221 x 10-6 M < c < 1.221 x 10-4 M………………...……………………….……..97igure 3-22 PL intensity of OHC-Tri-BOPV-CHO in hexane, decane, and chloroform at 10-5 M………………………………………………………..…………….……..98igure 3-23 The absorption of OHC-Tri-BHPV-CHO in chloroform、hexane and decane at solid state…………………………………………………………………105igure 3-24 The absorption of OHC-Tri-BOPV-CHO in chloroform、hexane and decane at solid state…………………………………………………………………105igure 3-25 PL intensity of OHC-Tri-BHPV-CHO in hexane, decane, and chloroform at solid state…………………………………………………...…………………….106igure 3-26 Normalized PL (at peak2nd ) of OHC-Tri-BHPV-CHO in hexane, decane, and chloroform at solid state……………………………………………….……….106igure 3-27 PL intensity of OHC-Tri-BOPV-CHO in hexane, decane, and chloroform at solid state…………………………………………………...…………………….107igure 3-28 Normalized PL (at peak2nd ) of OHC-Tri-BOPV-CHO in hexane, decane, and chloroform at solid state……………………………………………….……….107igure 3-29 AFM images and TEM image of OHC-Tri-BOPV-CHO deposited on a mica substrate in hexane solution at C =1.175 x 10-4 M……………………………121igure 3-30 AFM section images of OHC-Tri-BOPV-CHO deposited on a mica substrate in hexane solution at C =1.175 x 10-4 M………………………………….122igure 3-31 AFM section images and TEM image of OHC-Tri-BOPV-CHO deposited on a mica substrate in hexane solution at C =1.175 x 10-5 M……………123igure 3-32 Illustration of OHC-Tri-BOPV-CHO packing mechanism in hexane. [96]………………………………………………………………………………….124igure 3-33 AFM images of OHC-Tri-BOPV-CHO deposited on a mica substrate in chloroform solution at C =1.266 x 10-5 M…………………………………………125igure 3-34 AFM section images of OHC-Tri-BOPV-CHO deposited on a mica substrate in chloroform solution at C =1.266 x 10-5 M………………………….…126igure 3-35 TEM image of OHC-Tri-BOPV-CHO deposited on a mica substrate in chloroform solution at C =1.266 x 10-5 M…………………………………………127igure 3-36 AFM section images of OHC-Tri-BOPV-CHO deposited on a mica substrate in chloroform solution at C =1.266 x 10-6 M…………………………….127igure 3-37 Illustration of OHC-Tri-BOPV-CHO packing mechanism in chloroform…………………………………………………………………………..128igure 3-38 AFM images and 3D image of OHC-Tri-BOPV-CHO deposited on a mica substrate in THF solution at C =1.217 x 10-5 M……………………………..129igure 3-39 AFM section images of OHC-Tri-BOPV-CHO deposited on a mica substrate in THF solution at C =1.217 x 10-5 M………………………………...…130igure 3-40 AFM images and 3D image of OHC-Tri-BOPV-CHO deposited on a mica substrate in THF solution at C =1.217 x 10-4 M……………………………..131igure 3-41 AFM section images of OHC-Tri-BOPV-CHO deposited on a mica substrate in THF solution at C =1.217 x 10-4 M…………………………………...131igure 3-42 Illustration of OHC-Tri-BOPV-CHO packing mechanism in THF. [97]……………………………………………………………………………….…132igure 3-43 AFM images with section analysis of OHC-Tri-BHPV-CHO deposited on a mica substrate in THF solution at C =1.117 x 10-4 M……………………………133igure 3-44 AFM images with section analysis of OHC-Tri-BHPV-CHO deposited on a mica substrate in THF solution at C =1.117 x 10-5 M…………………………....134igure 3-45 AFM images with section analysis of OHC-Tri-BHPV-CHO deposited on a mica substrate in THF solution at C =1.117 x 10-6 M…………………………....135igure 3-46 Illustration of OHC-Tri-BHPV-CHO packing mechanism in THF. [97]……….…………………………………………………………………………136igure 3-47 AFM image and 3D image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 3 hours in dilute state..........................................................146igure 3-48 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 3 hours in dilute state...........................................................................147igure 3-49 AFM image with section analysis of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 6 hours in dilute state..................................................148igure 3-50 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 6 hours in dilute state...........................................................................148igure 3-51 AFM image with section analysis and 3D image of OHC-Tri-BHPVCHO /silica hybrid ratio =1:400 at hybrid time = 12 hours in dilute state………...149igure 3-52 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 12 hours in dilute state.........................................................................150igure 3-53 AFM image with section analysis and 3D image of OHC-Tri-BHPVCHO /silica hybrid ratio =1:400 at hybrid time = 24 hours in dilute state………...150igure 3-54 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 24 hours in dilute state........................................................................151igure 3-55 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 12 hours.(no dilute)………………………………………………….151igure 3-56 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 24 hours.(no dilute).............................................................................151igure 3-57 Florescence images of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 6 hours in dilute state......................................................................152igure 3-58 Florescence images of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 1 week in dilute state.......................................................................152igure 3-59 Photoluminescence spectra (bottom image) tacken from selected florescence image(up image) of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:400 at hybrid time = 6 hours in dilute state..........................................................................153igure 3-60 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:4000 at hybrid time = 3 hours in dilute state. ……………………………………………....154igure 3-61 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:4000 at hybrid time = 6 hours in dilute state..........................................................................154igure 3-62 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:4000 at hybrid time = 12 hours in dilute state........................................................................155igure 3-63 TEM image of OHC-Tri-BHPV-CHO /silica hybrid ratio =1:4000 at hybrid time = 24 hours in dilute state........................................................................155igure 3-64 TEM image of OHC-Tri-BHPV-CHO /Titania hybrid ratio =1:400 at hybrid time = 2 hours(left image) and 3 hours(right image) in no dilute state..........156igure 3-65 TEM image of OHC-Tri-BHPV-CHO /Titania hybrid ratio =1:400 at hybrid time = 6 hours in no dilute state......................................................................157igure 3-66 TEM image of OHC-Tri-BHPV-CHO /Titania hybrid ratio =1:400 at hybrid time = 12 hours in no dilute state....................................................................157igure 3-67 TEM image of OHC-Tri-BHPV-CHO /Titania hybrid ratio =1:400 at hybrid time = 24 hours in no dilute state....................................................................158igure 3-68 TEM image of OHC-Tri-BHPV-CHO /Titania hybrid ratio =1:400 at hybrid time = 3 days in no dilute state.......................................................................158igure 3-69 Florescence images of OHC-Tri-BHPV-CHO / Titania hybrid ratio =1:400 at hybrid time = 6 hours in dilute state..........................................................159igure 3-70 Florescence images of OHC-Tri-BHPV-CHO / Titania hybrid ratio =1:400 at hybrid time = 6 hours in dilute state..........................................................160igure 3-71 Photoluminescence spectra (bottom image) tacken from selected florescence image(up image) of OHC-Tri-BHPV-CHO / Titania hybrid ratio =1:400 at hybrid time = 6 hours in dilute state..........................................................................16121342494 bytesapplication/pdfen-US超分子π-共軛系統OPV3有機/無機掺和self-assemblysupramoleculeπ-conjugated systemhybridthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/189011/1/ntu-97-R94527047-1.pdf