臺灣博碩士論文加值系統

氮化鋁(AlN)具有高熱傳導率、高絕緣電阻係數、優越之機械強度以及低介電係數等特性，因此廣泛地被用於散熱體、電子陶瓷基板與電子元件封裝材料。
本研究使用台鹽實業、Dow Chemical及Tokuyama等公司的氮化鋁粉末，添加2 wt%的氧化釔，置於石墨坩鍋使用高溫石墨爐在1650℃常壓燒結，持溫6小時。燒結後以SEM觀察試片的顯微結構，並分析碳、氮、氧之含量，以及量測試片之熱傳導係數與介電常數。
比較三家公司氮化鋁燒結後的顯微結構，台鹽實業試片所形成的二次相比例較高。台鹽實業試片的熱傳導係數與其它兩家公司相近，約在150W/m．K左右。
氧化釔的添加量提高燒結後密度，是因二次相Y3Al5O12其密度較氮化鋁密度高，燒結後過多的液相於晶界處所形成的二次相所佔的面積較大，因而提高燒結後的密度，熱傳導係數的降低是晶界中二次相面積增加，使得熱傳經過二次相化合物造成障礙，因此降低氮化鋁材料的導熱性質。
而燒結過程中石墨的污染使介電常數增加，在使用氮化硼坩鍋後即可降低石墨污染之問題。在碳含量超過0.013 wt%後則會使介電常數(K)提高，在氮化硼坩鍋燒結後其介電常數(K)值約在8.9，與基板特性相同。燒結後碳污染降低了試片氧含量，而在球磨過程中氧化鋯球污染嚴重，而燒結後鋯元素分散於晶粒因而降低熱傳導率，所以未來球磨過程需克服球磨污染的問題。

Aluminum nitride (AlN) is an attractive material because it has high thermal conductivity combined with good electrical insulation, excellent mechanical strength and low dielectric constant. These properties make AlN a leading candidate as a substrate for power circuits and multichip modules, and as a packaging materials for integrated circuits.
In the work, three different aluminum nitride powders(Taiwan salt、Dow Chemical、Tokuyama) were added 2 wt% yttria, respectively. After mixing well, samples were placed in a graphite crucible and sintered in a graphite resistance furnace at 1650℃ for 6 hours under nitrogen gas atmosphere. Sintered specimens cross-section structures was observed by scanning electrical microscope (SEM).and measured the material content of specimens, such as carbon、nitrogen、oxygen, and thermal and electric properties such as, thermal conductivity and dielectric constant.
Compared the microstructure of all sintered specimens, specimen made by Taiwan Salt’s powder has more secondary phase, but the thermal conductivity is about 150 W/m‧K, which is close to others specimens made by other brand’s powders.
To increase amount of yttria would increase sintered specimen density. The secondary phase (Y3Al5O12) density is higher than alumina nitride. After sintering, the secondary phase formed in grain boundary area is larger than added lower yttria specimen. Therefore, the specimen density is increased, and the increased of secondary phase area will reduce the thermal conductivity.
During sintering, the carbon would contaminate the sample, and cause the increase in its dielectric constant. Moreover, the carbon contamination can be reduced by adding boron nitride (BN) crucible. When the carbon content of specimen outstripped 0.013 wt%, the dielectric constant will increase.
The specimen sintered in BN crucible, its dielectric constant is 8.9 as low as commercial available alumina nitride substrates.
The specimens which sintered in graphite crucible, the carbon contamination reduced the oxygen content. During the grinding process, the zirconium (Zr) contamination is significant. The Zirconium element is dispersed in grains; therefore, reduced the thermal conductivity. So the grinding process is required to overcome the grinding contamination in future.

目錄
摘要 I
Abstract III
誌謝 V
目錄 VII
圖目錄 VIII
表目錄 VI
第一章 緒論 1
第二章 理論基礎 4
2-1 氮化鋁合成方法 4
2-2直接氮化法(Direct Nitridation)簡介 5
2-3 液相燒結理論 7
2-4不純物對氮化鋁性能之影響 9
2-5 氧化釔對燒結影響 11
第三章 實驗方法 16
3-1實驗粉末成份 16
3-2 粉體分析 16
3-3 乾壓粉體製備(Uniaxial die pressing) 18
3-4 成型(Forming) 19
3-5 燒結(Sintering) 19
3-6 結構分析和性質試驗(structure analysis and property tests) 20
第四章 實驗結果與討論 23
4-1 四種不同粉末添加2 wt%氧化釔燒結分析 23
4-1-1 SEI影像 23
4-1-2 BEI影像 28
4-1-3 EDX元素分佈分析 32
4-1-4 X-光繞射分析 34
4-2 不同氧化釔添加量對燒結影響 36
4-2-1 SEI與BEI影像 36
4-2-2 X-光繞射分析 38
4-3 氮化硼坩鍋與石墨坩鍋對燒結的影響 39
第五章 建議 45
第六章 結論 47
參考文獻 49
附錄一 氮化鋁產物型態 52
附錄二 表面鍍層對降低氮化鋁粉末水解的效能 55
附錄三 粉體粒徑分析 60
圖目錄
圖1-1 氮化鋁結構 2
圖2-1 燃燒合成法反應示意圖 6
圖2-2氮化物分解的氮分壓與標準溫度關係 7
圖2-2 傳統液相燒結 9
圖2-4 金屬鐵、矽污染對熱傳導率的影響 10
圖2-5氧含量對熱傳導率的影響 10
圖2-6 液相燒結助劑對熱傳導影響 12
圖2-7 氧從晶格中擴散至晶界示意圖 13
圖2-8Al2O3-Y2O3相圖 15
圖2-9 氧化釔添加量與二次相型態關係 15
圖3-1 燒結升溫曲線 20
圖4-1 AlN添加2 wt%氧化釔顯微結構 (a)T.S.S.G(b)T.S.Y (c)Tokuyama (d) Dow Chemical 25
圖4-2 AlN添加2 wt%氧化釔顯微結構 (a)T.S.S.G(b)T.S.Y (c)Tokuyama (d) Dow Chemical 26
圖4-3 AlN添加2 wt%氧化釔顯微結構 (a)T.S.S.G(b)T.S.Y (c)Tokuyama (d) Dow Chemical 27
圖4-4 (a) T.S.S.G (b) T.S.Y (c)Tokuyama(d) Dow Chemical添加2 wt%氧化釔 BEI 29
圖4-5 (a) T.S.S.G (b) T.S.Y (c)Tokuyama(d) Dow Chemical添加2 wt%氧化釔 30
圖4-6 (a) T.S.S.G (b) T.S.Y (c)Tokuyama(d) Dow Chemical添加2 wt%氧化釔 31
圖4-7 T.S.S.G氮化鋁元素半定量分析 33
圖4-8 T.S.S.G晶界二次相元素半定量分析 33
圖4-9 燒結後X-光繞射分析二次相特性峰比較(a)T.S.Y(b)T.S.S.G(c)Dow Chemical(d)Tokuyama 35
圖4-10 T.S.Y (a)(c)添加5wt%氧化釔 (b)(d) 添加2wt%氧化釔SEI Imagine與 BEI 37
圖4-11 X-光繞射分析T.S.Y(a)添加2 wt%(b)氧化釔添加5 wt%氧化釔二次相比較 38
圖4-12 T.S.Y添加5 wt%氧化釔(a)使用石墨坩鍋燒結(b)使用氮化硼坩鍋燒結 39
圖附錄1-1 氮化鋁合成示意圖(a)上方區(b)中間部分(c)腔體外圍(d)腔體底部 53
圖附錄1-2 產物繞射分析(a)上層(b)中間層(c)底層 54
圖附錄2-1 型號 G32粉末(a)未浸於水中與(b)浸於水中24小時後X-光繞射比較 55
圖附錄2-2 有鍍層與未鍍層粉末浸泡於水中的時間對pH的影響 56
圖附錄2-3 型號G32粉末之不同硬脂酸鍍膜量對水溶液pH值的影響 58
圖附錄2-4 兩種粉末在FTIR表面鍵結的分析(a)型號G32 (b)T.S.S.G 59
圖附錄3-1氮化鋁粉末粒徑大小與分佈情形(a) T.S.S.G(b) T.S.Y(c) Dow Chemical (d) Tokuyama 61
圖附錄3-2 (a)T.S.S.G (b) T.S.Y (c) Dow Chemical(d) Tokuyama 62
圖附錄3-3 (a)T.S.S.G (b) T.S.Y (c) Dow Chemical(d) Tokuyama 63
圖附錄3-4 (a)T.S.S.G(b)T.S.Y(c) Dow Chemical (d)Tokuyama粉體 X-光繞射分析 64
表目錄
表1-1 氮化鋁之物理與化學特性 2
表1-2 目前氮化鋁市場基板特性比較 3
表3-1 初始粉末特性 18
表4-1 燒結前與燒結後晶粒尺寸比較 24
表4-2 四種不同粉體添加2 wt%燒結後二次相量比例 28
表4- 3 T.S.S.G微結微EDX線性元性分析 33
表4- 4 T.S.S.G二次相微結微EDX線性元性分析 33
表4-5 氧化釔添加量與二次相量對應關係 37
表4-6 石墨與氮化硼坩鍋對其含碳量/含氧量影響 40
表4-8 燒結後試片碳/氮/氧分析 40
表4-8 氮化鋁性質量測結果 42

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