聚苯胺(PANI)被認為與奈米碳管有相似的物理化學性質，均具有導電度與光學性質可調控的特性，因此吸引對聚苯胺與奈米碳管組合的複材其特殊電、熱、光學性質的探討。本論文以各類官能基化的多層奈米碳管為模板，採用直接聚合聚苯胺方式，將苯胺聚合於多層奈米碳管(MWNTs)表面，以進行其熱電性質，光學性質與微結構和聚苯胺參雜量對導電度的關係。
aromatic amine (AA)官能基化的MWNTs/PANI，其熱電性質可有效的被提升，PANI/AA-MWNTs的TEP約是PANI的1.5~3.5倍，且PANI/AA-MWNTs的熱電轉換操作溫差範圍可達32 oC，高於PANI操作溫差範圍~12 oC。aromatic amine化學鍵結與物理吸附於MWNTs導致奈米碳管光學性質的差異，系列的探討認為奈米碳管可直接經由化學鍵結位置將電子傳至修飾基且奈米碳管表面修飾基也被認為易捉住excitation energy因而增強其放光性質。反之，修飾基與奈米碳管的靜電吸引力等相互作用現象會導致減弱光學性質。以不同聚合條件製備兩種對溫度變化因素有不同導電度呈現的PANI/MWNTs，一為導電度隨溫度上升而減低，另一則相反。複材微結構和聚苯胺參雜量影響PANI/MWNTs電性質，低溫時高參雜量且PANI、MWNT成長方向接近平行時，較有利於導電度。
Tetar-aniline可光學調控並穩定CdS奈米粒子，經材料結構分析與光學性質比對，因有效Tetar-aniline與CdS間的電子轉移，導致CdS的bad gap降低，發光性質提高。同時自組裝薄層的樣品製備法，實現二次離子質譜術應用於奈米粒子其元素分佈的偵測。

Carbon nanotubes (CNTs) were firstly discovered by Iijima, S in 1991. Conductivity polymer was discovered by Heeger, MacDiarmid and Shirakawa in 1970’s. Polyaniline (PANI) possesses physicochemical characteristics similar to CNTs. Their conductive and optical properties could be modulated. PANI has widely been regarded as quasi-one-dimensional semiconductor; whereas CNT can be considered as quantum wires. The novel electronic, photonic and optical properties obtained by coupling these two components are potentially attractive.
In this thesis, in-situ polymerization was applied to produce PANI/MWNTs composites and various functional groups were used as template for aniline polymerization. To study the thermoelectric properties of multi-walled carbon nanotubes-polyaniline (MWNTs/PANI), we applied “PGEC” model of thermoelectric materials to an organic hybrid system, which was consisted of an aromatic amine functionalized MWNTs (AA-MWNTs) and PANI. The obtained TEP was up to 31 □V/K, which was 1.5~3.5 times to that of neat PANI. The voltage generated by PANI/AA-MWNTs was in the 32 oC temperature gradient, indicating PANI/AA-MWNTs possessing wider operating temperature than PANI (□T<12 oC). The improvement was attributed to the aromatic amine on MWNTs surface and enhanced interface adhesion between PANI and MWNT.
To study the optical properties of MWNTs/PANI composite, two functional MWNTs, AA-MWNTs and AC-MWNTs (aniline contacted MWNTs), were prepared by chemical bonding and physical absorption with aniline, respectively. For AA-MWNTs, decreasing band gap for π-π* transition is obtained. The electrons generated in MWNTs could transfer directly to aromatic amine group when MWNTs absorb UV or visible light. The aromatic amine was suggested to trap quickly excitation energy and to enhance luminescence behavior. For AC-MWNTs, the interaction between MWNTs acceptor and aniline donor or acid-base/electrostatic reactions between carboxyl group and aniline anion quenched the luminescence. The PANI/AC-MWNTs made of short-chain PANI led band gap increase and red shift luminescence behavior was observed. Directly charge transfer from CNT to modifier on CNT surface and modifier trapped excitation energy from CNT was proposed as two key factors responsible for optical behavior of CNT-base material.
To study the morphology and dopant effect on conductivity of MWNTs/PANI composite, MWNTs wrapped with polyanaline (MWPs) and aligned with polyanaline (MAPs) composites were prepared by using different addition sequence of oxidant. Systematic study demonstrated the orientation of polyanaline (PANI) long chains and the direction of electron transport in MWNTs and PANI played an important role in conductivity. At RT, the conductivity of MWPs was higher as PANI and MWNTs aligning parallel. However, at higher temperature de-doping resulted in decreasing conductivity. For MAPs, the perpendicular alignment between PANI and MWNTs resulted in lower conductivity at RT. At higher temperature, PANI short chains would switchover and got adsorbed on MWNTs to form a near parallel orientation. More aromatic amine of PANI would directly graft to MWNTs, resulting in increasing conductivity of MAPs. Similar morphology and dopant caused MWPs and MAPs to possess similar conductivity. The results indicate that morphology and dopant are critical for governing the conductivity of MWNTs/PANI composites at RT. At temperature above 150 oC, morphology becomes the dominant influencing factor.
To study the photoluminescence tuning and stabilization of CdS nanoparticles by surface modification of tetra-aniline, 11-Mercaptoundecanoic acid (11-MUA) capped CdS and 11-MUA/ tetra-aniline capped CdS were prepared. The modification of the CdS surface with 11-MUA and tetra-aniline organic compounds increases the solubility and stability of CdS/11-MUA/TA particles. Decreasing band gap and enhancing spectroscopic properties by efficient charge-transfer between CdS and tetra-aniline was observed.
To study atomic distribution in CdS nanoparticles by ToF-SIMS, the atomic distribution in the monolayer of two different Mn-doped CdS quantum dots (QDs) was studied for the first time with ToF-SIMS. The model Cd:Mn QDs were immobilized on Au substrate by use of a self-assembly-monolayer via 1,10-decanedithiol. Morphological analysis by SPM and TEM indicate larger particle size of in-situ synthesizing CdS:Mn. ToF-SIMS depth profile and 3D-images revel that Mn atoms reside on the surface of in-situ synthesizing CdS:Mn and are uniformly embedded in capped CdS:Mn. Comparable results obtained by SPM, TEM, XPS and ToF-SIMS are obtained, indicating that ToF-SIMS might find potential applications in surface and interface study of semiconductor nanocrystals.

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Chapter 2
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Chapter 3
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Chapter 4
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Chapter 6
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