本研究目的在於了解N型鑽石薄膜的氮摻質的摻雜機制和氮原子在鑽石晶種中之型態。利用微波電漿輔助化學氣相沉積（MPCVD）製作摻雜氣體為氮氣(N2)與氨氣(NH3)之N型鑽石薄膜，成長於n-type高阻值的矽基板上，探討氮氣與氨氣兩種摻雜氣體之N型鑽石薄膜的成長機制與摻雜特性。本研究改變微波功率、基板溫度、壓力、摻雜氣體的流量和成長時間等參數條件，沉積N型鑽石薄膜。利用掃描式電子顯微鏡、X光繞射儀、霍爾量測、X射線光電子能譜分析N型鑽石薄膜的表面結構、鑽石薄膜厚度、結晶構造、元素化學態、電阻、載子遷移率和載子濃度。
實驗結果發現，氮氣與氨氣的氮摻雜質有不同的摻雜特性，氮氣的氮摻質於晶粒界面之sp2結構中，氨氣的氮摻質摻雜進鑽石晶粒中。摻雜源為氮氣在正偏壓下長時間的成長，鑽石晶粒變大，而sp2界面物減少，導致阻值變大，結晶性變好。摻雜源為氨氣在正偏壓下長時間成長，同時存在成長機制與蝕刻機制，故薄膜厚度變薄，且表面粗糙度大。摻雜源為氨氣在負偏壓下長時間成長，鑽石晶粒變大，薄膜變厚，阻值變小，成功製作出氮摻雜進鑽石晶粒中的低阻值N型鑽石薄膜。

The n-type diamond has been shown to be very difficultly synthesized by CVD method. Nitrogen as a donor impurity shows a similar atom size of carbon for diamond lattice. However, nitrogen doped diamond reveals deep level and large carrier activation energy with much defects in diamond. The application of n-type diamond has less reported and the characteristic of nitrogen doped diamond seems varied due to different fabrication process. Our previous study of nitrogen doped diamond using mixture of N2 and argon gas synthesized by microwave CVD indicated that nitrogen atoms were precipitated in the grain boundaries of diamond crystallites. In this paper, it compared the synthesis of nitrogen doped diamond using the mixed gas of nitrogen/CH4/Ar and ammonia/CH4/Ar gases by microwave CVD method for different temperature, gas flow rate, pressure, and microwave power. The conductivities, carrier concentrations and mobility of the n-type doped diamond have been analyzed and discussed. The Hall measurement shows that the mixture of gas with Ar reveals different growth mechanism and carrier transportation properties in diamond. Nitrogen atoms of N2 were located in the grain boundaries and interfaces among diamond crystallites with the sp2 structure. Nitrogen atoms of NH3 are doped into the diamond crystallites.

中文摘要 ....................................................................................... i
Abstract ......................................................................................... ii
Contents ....................................................................................... iii
Table Captions .............................................................................. v
Figure Captions ............................................................................ vi
Chapter 1 Introduction .............................................................. 1
Chapter 2 Experimental Details ................................................ 2
2.1 Microwave plasma CVD system .............................................. 2
2.2 Substrate preparation................................................................. 4
2.3 Diamond deposition process ..................................................... 4
2.4 Analysis of N-type diamond thin film analysis methods ........ 10
2.4.1 Van der Pauw ................................................................................. 10
2.4.2 Hall measurements ......................................................................... 12
2.4.3 Scanning electron microscope ........................................................ 15
2.4.4 X-ray diffraction measurements ..................................................... 15
2.4.5 X-ray photoelectron spectroscopy .................................................. 16
Chapter 3 Results and Discussions ......................................... 17
3.1 N2 doping effect of diamond films growth.............................. 17
3.1.1 Effect of microwave power on deposition growth of diamond ...... 17
3.1.2 Effect of temperature on deposition growth of diamond ................ 23
3.1.3 Effect of pressure and flow rate on deposition growth of diamond 29
3.1.4 Effect of growth time on deposition growth of diamond ............... 33
3.2 NH3 doping effect of diamond films growth with positive DC
bias ......................................................................................... 41
3.2.1 Effect of microwave power on deposition growth ......................... 41
3.2.2 Effect of temperature on deposition growth ................................... 46
iv
3.2.3 Effect of pressure and flow rate on deposition growth ................... 52
3.2.4 Effect of growth time on deposition growth ................................... 55
3.3 NH3 doping effect of diamond films growth in dependence of
growth time with negative DC bias ....................................... 62
3.4 Growth mechanism of nitrogen doped diamond thin film ...... 70
Chapter 4 Conclusion ............................................................. 72
Reference .................................................................................... 74

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