第一部分: 在超大積體電路中的金屬化製程
本部分主要研究金屬阻障層(Ta，TaN)與多孔隙低介電材料(多孔的HSQ，PPSZ)在超大積體電路製程中金屬化的應用。尤其探討關於這些材料的物理和電子特性。
用不同比例氮氣/氬氣所成長出的Ta-N 薄膜可用拉賽福回向散射分析，電子顯微鏡，X射線繞射和片電阻測量分析其性質。
用純氬氣，10%，20%，30%，40%，50%，60% 氮氣/氬氣 所分別成長出的Ta和Ta-N薄膜微結構分別是□-Ta和bcc-Ta，bcc-Ta，bcc-TaNx，晶格擴張的bcc-TaNx，hcp-Ta2N，fcc-TaN 和fcc-TaN(接近無結晶型)。而且隨著氮濃度的增加我們發現薄膜的電阻率也隨之增加。並且成長在這些TaN上的銅膜，其中銅(111)/(200)比率隨Ta-N薄膜中的氮濃度增加而減少。
我們已經利用傅立葉轉換紅外線分析儀，電子顯微鏡，歐傑電子分析儀，以及電流電壓分析器和電容電壓分析器來測量多孔隙HSQ的材料與電子特性。其中的孔洞大小約2 nm而且形狀約為球狀並隨機均勻分佈在XLK薄膜內。在500度退火30分鐘之後，在銅與XLK薄膜之間發現一層光滑的無結晶性的物質其中含有銅與氧的成分。而在600度退火30分鐘之後，銅被發現擴散進入XLK薄膜內部。
由於內部孔洞的高密集度，所以同樣多孔隙的polysilazane(PPSZ)薄膜的介電常數可以低到2.2。在550度30分鐘退火之後，由於來自PPSZ的SiO解離出來，並且與銅產生反應因而產生在銅和PPSZ薄膜之間形成銅矽化物。銅矽化物與氧起反應在室溫形成銅和SiO2。在550度退火30分鐘之後的PPSZ薄膜，發現其漏電流在室溫時隨著暴露在空氣中的日子增加而減少。

第二部分 奈米材料
有關銅的奈米材料微結構和成長機制(銅奈米管，銅奈米球棒)已經被深入研究中。
銅奈米管可使用矽氧化物奈米線作為模板來合成。矽氧化物奈米線可利用有機金屬化學氣相沉積方法成長上一層銅膜。而空的銅奈米管可藉由利用稀薄的HF溶液蝕刻內部的矽氧化物模板而產生。
有機金屬氣相沈積方法已經用來成長銅奈米棒但不需要金屬催化劑。已經可成功利用有機金屬氣相沉積系統成長出五角形的銅奈米球棒且不需要特別的化學覆蓋試劑。銅奈米棒具有球棒形狀且粗端的平均直徑以及尾端分別是100 nm和50 nm。關於此種特殊五角型結構的產生主要跟双晶的側向生長與延伸生長機制有很重要的關係。最後發現銅奈米球棒具有強大的場發射特性。
為了研究ZnS奈米管的熱穩定性，我們使用現場即時觀測的TEM系統用來觀察單一個奈米管在加熱過程中的形態變化。在ZnS-C奈米管的表面上發現接連形成4層分別具有無結晶性和具結晶的碳層。在加熱過程中發現沒有照射電子束的情況下，ZnS-C奈米管將會解離出碳和氮。並且發現電子束可使碳蒸汽穩定成長在ZnS-C(N)奈米管上並進而形成無結晶性的碳膜。

PART Ⅰ Cu Metallization in ULSI
Barrier layer (Ta, TaN) and porous low-k materials (porous HSQ, PPSZ) for ULSI metallization applications have been investigated. The physical and electrical characteristics of these materials have been investigated.
The microstructures and phases of Ta-N films deposited with various N2/Ar gas mixtures have been investigated by Rutherford backscattering spectrometry, transmission electron microscope, X-ray diffraction, and sheet resistance measurement.
Ta and Ta-N films sputtered with pure Ar, 10%, 20%, 30%, 40%, 50%, and 60% N2/Ar gas ratios were found to be a mixture of □-Ta and bcc-Ta, bcc-Ta, bcc-TaNx, expanded bcc-TaNx, hcp-Ta2N, fcc-TaN, and fcc-TaN (nearly amorphous) phases, respectively. The resistivity was found to increase with nitrogen content in samples deposited with 10 to 60% N2/Ar. For Cu layers deposited on these films, Cu (111)/(200) ratio was decreased with the nitrogen content of Ta-N films.
The structural and electrical properties of porous hydrogen silsesquioxane (XLK) have been characterized using a combination of Fourier transform infrared spectroscopy, transmission electron microscope, Auger electron spectroscopy, current-voltage analyzer and capacitance-voltage analyzer. The pores, about 2 nm in size and of spherical shape, were distributed randomly and uniformly in the XLK film. A smooth amorphous-like layer including Cu-O-Si was found to form between Cu and the XLK film after annealing at 500 □C for 30 min. Cu was found to diffuse into XLK film after annealing at 600 □C for 30 min.
The dielectric constant of porous polysilazane (PPSZ) film was as low as 2.2 owing to the high porosity and uniformity of the film. The copper silicide was found to form between Cu and the PPSZ film after annealing at 550 □C for 30 min due to the SiO desorption from PPSZ. The copper silicide reacts with oxygen to form Cu and SiO2 at room temperature. The leakage current of the broken PPSZ film after annealing at 550 □C for 30 min was found to decrease with exposure in air for a few days at room temperature.

PART Ⅱ Nanostructures
Synthesis and growth mechanism of Cu nanostructures (Cu nanotubes, Cu nanobats) have been investigated.
. Cu nanotubes have been synthesized using silicon oxide nanowires as templates. The silicon oxide nanowires were coated with a thin and uniform copper layer by metalorganic chemical vapor deposition (MOCVD) method. Hollow Cu nanotubes were then produced by etching away the inner silicon oxide templates with dilute HF solution.
Metal-organic chemical vapor deposition method has been used to grow Cu nanorod without metal catalysts. Pentagonal Cu nanobats with five-fold symmetry were successfully synthesized without capping reagents by MOCVD. Cu nanorods are of bat shape and the average diameters of the head and tail of the Cu nanobats are 100 nm and 50 nm, respectively. Both elongation along the five-fold symmetry axis and lateral growth of exterior twins were found to be important in the growth of pentagonal Cu nanobats. The Cu nanobats possess strong field emission characteristics.
In order to investigate the stability of ZnS nanotubes, in-situ TEM was used to observe the morphological changes in a heating process. Four amorphous and crystalline C layers were found to form consecutively on the surface of ZnS-C nanotubes. C and N species would decompose and evaporate from ZnS-C nanotubes. The electron beam stabilized the C vapor and promoted the formation of amorphous C layer on the ZnS-C(N) nanotubes.

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Chapter 5
[5.1] The National Technology Roadmap for Semiconductors; Semiconductor Industry Association: San Jose, CA, 2004.
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Chapter 6
[6.1] The National Technology Roadmap for Semiconductors; semiconductor Industry Association: San Jose, CA, 2004.
[6.2] M. Morgen, E. T. Ryan, J. H. Zhao, C. Hu, T. Cho, and P. S. Ho, “Low dielectric constant materials for ulsi interconnects,” Annu. Rev. Mater. Sci., 30, 645-680 (2000).
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[6.4] S. Yang, P. A. Mirau, C. S. Pai, O. Nalamasu, E. Reichmanis, J. C. Pai, Y. S. Obeng, J. Seputro, E. K. Lin, H. J. Lee, J. Sun, and D. W. Gidley, “Nanoporous ultralow dielectric constant organosilicates templated by triblock copolymers,” Chem. Mater., 14, 369-374 (2002).
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Chapter 7
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Chapter 8
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Chapter 9
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