近年來，由於半導體產業的急遽發展及元件尺寸的微縮下，傳統使用的微影製程技術已達到臨界點，而需採用高昂的深紫外光來進行圖形轉移，這使得傳統的微影製程已不再具備低成本且快速的優點。為了解決尺寸微縮下所造成的技術障礙，選擇性沉積逐漸地受到重視，因為其可達到奈米尺寸的選擇性，且具備著較低成本的優勢，例如單層自組裝分子已經被相當多的文獻證實可以在化學氣相沉積中達到選擇性沉積，透過單層自組裝分子鈍化特定的區域，可以延長化學氣相沉積前驅物的成核時間，藉此來達成選擇性的效果，最常見的方法就是使有機矽烷類分子功能化在矽基板上面，藉此鈍化矽基板，達成金屬對金屬間的沉積。然而，相當多的文獻指出有機烷類在高溫的狀態下容易降解，並且會在基板表面進行聚集，產生高達30奈米的團簇，種種的跡象顯示有機矽烷類分子在需要一定溫度的化學氣相沉積下會在表面進產生許多不利的影響。在此篇研究中，我們研究了新穎的磷酸鹽類作為在矽基板上取代有機烷類的可能性，在與化學氣相沉積相同的壓力環境下，我們分析其表面形貌以及斷鍵的行為，藉此來研究兩種材料的熱穩定性。為了解決在雙鑲嵌結構中，有機磷酸會與底部的基板產生反應，我們使用正交功能化方法來克服，其使用硫醇鹽類來當作阻擋層，並且在不損害矽上磷酸單層膜的情況下來去除此阻擋層。最終研究成果表明，我們成功的證明有機磷酸鹽類是相對熱穩定性的材料，並且也成功地用正交功能化方法來使有機磷酸選擇性沉積在矽基板上。

The thermal stability of butylphosphonic acid (BPA) and 3-aminopropyltriethoxysilane (APTES) SAM on silicon substrate was investigated under a reduced pressure condition. The thermal desorption and surface morphology of the BPA and APTES SAM on silicon is determined from high-resolution X-ray photoelectron spectroscopy (HRXPS) and atomic force microscopy (AFM) upon thermal annealing from 50 °C to 550 °C. XPS and AFM results revealed that the anchoring group of APTES SAM on silicon first detached under a thermal treatment at 150 °C for 60min. The detached APTES further aggregate to a thermally stable cluster at 150 °C to 400 °C. Upon the 400 °C annealing, the APTES SAM completely decompose and desorbed from the substrate. On the other hand, the BPA SAM first cleavage at the C2—C3 bond, leaving the ethylphosphonate SAM on silicon. However, the surface morphology of BPA SAM on silicon remained smooth upon thermal annealing. The BPA SAM on silicon can remain stable up to 350 °C annealing. Upon 400 °C annealing, the P—O—Si bonding decomposed, and the molecular detached from the silicon surface. Compared to the organosilane SAM on silicon, organophosphonate SAM on silicon can remain stable and smooth surface on the silicon substrate up to 350 °C. Herein, we demonstrate the advantage of utilizing organophosphonate as an alternative SAM to be applied in the process requiring thermal annealing. We also demonstrate an orthogonal functionalization approach to overcome the spontaneous reaction between organophosphonate and metal. With the orthogonal functionalization approach, the functionalization of organophosphonate SAM on silicon can be further applied in the structure with both metal and silicon surfaces.

摘要 1
Abstract 2
Acknowledgment 4
Table of Contents 5
Figure and table 7
Chapter 1 Introduction 13
1.1 Executive summary 13
Chapter 2 Literature Review 16
2.1 Introduction of self-assembled monolayers (SAM) 16
2.2 Introduction of area selective deposition (ASD) in microelectronics 25
2.3 Application of SAM towards ASD in microelectronics 29
2.4 Thermal stability of SAM on Si 37
2.5 Orthogonal functionalization of SAM on Si and Cu. 39
Chapter 3 Preparation and Design of Experiment 43
3.1 Substrate pretreatment and SAMs functionalize on silicon 46
3.2 Thermal stability analysis 49
3.3 Orthogonal selective functionalization 51
3.4 Instrument 52
Chapter 4 Result and Discussion 54
4.1 Characterization of aminopropyltriethoxysilane (APTES)-functionalized Si 54
4.2 Characterization of butylphosphonic acid (BPA)-functionalized Si 61
4.3 Thermal stability of APTES and BPA SAMs functionalized on Si 67
4.4 Selective functionalization of BPA on silicon and copper substrate 78
Chapter 5 Conclusion 85
Chapter 6 Prospective 87
Method 1 Thermal stability enhancement with the terminal hydrogen bond induced by –NH2 87
Method 2 Thermal stability enhancement with the crosslinking system 90
Reference 95

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