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研究生：	周家民 Chou, Chia-Min
論文名稱：	以射頻濺鍍法製備高介電高熵(Al,Ti,Zr,Ta,Hf)Ox薄膜作為先進閘極堆疊結構 High-K High Entropy (Al,Ti,Zr,Ta,Hf)Ox Films Fabricated Using RF Sputtering For Advanced Gate Stacks
指導教授：	張高碩 Chang, Kao-Shuo
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2020
畢業學年度：	108
語文別：	英文
論文頁數：	67
中文關鍵詞：	濺鍍法、高介電常數介電層、高熵(Al, Ti, Zr, Ta, Hf)Ox薄膜、中熵(Ti, Zr, Ta, Hf)Ox薄膜、熱穩定性
外文關鍵詞：	sputtering, high-k dielectrics, high entropy (Al, Ti, Zr, Ta, Hf)Ox film, medium entropy (Ti, Zr, Ta, Hf)Ox film, thermal stability
相關次數：	點閱：101 下載：2
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以反應式濺鍍法製備的高熵及中熵高介電(Al, Ti, Zr, Ta, Hf)Ox及(Ti, Zr, Ta, Hf)Ox薄膜被沉積在n-型(100)的矽上作為先進閘極堆疊結構中的介電層。經過最佳化的合成氣體熱處理後，兩者都展現了良好的CV 及 IV特性；其中又以(Ti, Zr, Ta, Hf)Ox的漏電流較高。藉由高解析度電子顯微鏡觀察 (Al, Ti, Zr, Ta, Hf)Ox 閘極堆疊結構可以計算出此薄膜的介電常數約為15。EDS的結果可以證明各元素皆均勻分布，而XPS的結果可以證明 (Al, Ti, Zr, Ta, Hf)Ox是由Al2O3, TiO2, ZrO2, Ta2O5和HfO2五種氧化物混合而成的。結合EDS和XPS的結果可以證明高熵(Al, Ti, Zr, Ta, Hf)Ox的形成。為評估(Al, Ti, Zr, Ta, Hf)Ox及(Ti, Zr, Ta, Hf)Ox薄膜的熱穩定性，兩薄膜皆以快速升降溫製程(在900 C的氮氣中持溫5秒)作處理。從XRD及HRTEM的結果可以看出受過快速升降溫製程的(Al, Ti, Zr, Ta, Hf)Ox薄膜大致可以維持非晶結構，而(Ti, Zr, Ta, Hf)Ox薄膜則是明顯地結晶了。這個結果說明了(Al, Ti, Zr, Ta, Hf)Ox有作為先進閘極堆疊結構以及次世代電晶體的潛力。

High-entropy and medium-entropy high-k (Al, Ti, Zr, Ta, Hf)Ox and (Ti, Zr, Ta, Hf)Ox films were deposited on n-type (100) Si using reactive sputtering as dieletrics for advanced gate stacks. After optimal forming gas annealing, both films exhibited robust CV and IV characteristics; however, (Ti, Zr, Ta, Hf)Ox exhibited a higher gate leakage current than (Al, Ti, Zr, Ta, Hf)Ox did. The microstructure of (Al, Ti, Zr, Ta, Hf)Ox-based MOS gate stack was studied through HRTEM, and a dielectric constant of 15 was extracted. A uniform distribution of each constituent element was determined through EDS, and the XPS result showed that a mixing of Al2O3, TiO2, ZrO2, Ta2O5 and HfO2 in the (Al, Ti, Zr, Ta, Hf)Ox films. Thus, the formation of high-entropy (Al, Ti, Zr, Ta, Hf)Ox films was verified. Thermal stabilities of (Al, Ti, Zr, Ta, Hf)Ox and (Ti, Zr, Ta, Hf)Ox films were evaluated through a rapid thermal process (900 C for 5 s) in N2. The XRD results showed that (Al, Ti, Zr, Ta, Hf)Ox retained mostly amorphous, which was further verified through HRTEM, whereas obvious crystallization was observed for (Ti, Zr, Ta, Hf)Ox. These results indicated great promise of (Al, Ti, Zr, Ta, Hf)Ox for advanced gate stacks and next-generation transistors.

摘要	I
Abstract	II
致謝	III
Contents	IV
Figure Contents	VII
Table contents	XI
Chapter 1	Introduction	1
1	High-k dielectric materials	1
1.1	Scaling and enhanced performance	1
1.2	Traditional gate dielectric—SiO2	3
1.3	Metal–oxide–semiconductor (MOS) structure	5
1.4	Capacitance–voltage (C–V) behavior of a MOS structure	8
1.4.1	Ideal C–V characteristic	8
1.4.2	The effect of defects in a MOS gate stack structure	11
1.5	Properties of high-K materials	14
1.5.1	Dielectric constant and band offset	14
1.5.2	Thermodynamic stability on Si	16
1.5.3	Interface quality	17
1.5.4	Kinetic stability	19
1.6	Alternative gate dielectric—HfO2	20
2	High entropy materials	21
2.1	High entropy alloys	21
2.2	High entropy oxides (HEOs)	25
2.2.1	Dielectric properties	27
2.2.2	Reversible energy storage	29
2.2.3	CO oxidation catalyst	30
2.2.4	Thermal barrier coating	31
2.2.5	Magnetic properties	32
3	Motivation and objective of this study	33
Chapter 2	Experimental methods	34
1	Materials	34
1.1	Sputtering targets, gas, and substrate	34
1.2	Annealing gas	35
1.3	Sputtering targets for Al deposition	35
2	Equipment	36
2.1	Ultrasonic cleaner	36
2.2	Magnetron reactive sputtering	36
2.3	Tube furnace	37
2.4	Rapid thermal process (RTP) system	38
3	Experimental procedure	39
3.1	Substrate cleaning	39
3.2	High entropy oxide and medium entropy oxide deposition	40
3.3	Electrode (Al) deposition	41
3.4	Forming gas annealing (FGA)	42
3.5	Rapid thermal process (RTP)	43
4	Characterization	44
4.1	CapacitanceVoltage (CV) measurement	44
4.2	CurrentVoltage (IV) measurement	45
4.3	Transmission Electron Microscopy (TEM)	45
4.4	X-ray Photoelectron Spectroscopy (XPS)	46
4.5	X-Ray Diffraction (XRD)	47
Chapter 3	Results and discussion	48
1	Optimization of the fabrication of HEOs	48
1.1	Composition tuning	48
1.2	Optimizing film quality	49
2	Electrical properties of (Al, Ti, Zr, Ta, Hf)Ox- and (Ti, Zr, Ta, Hf)Ox-based MOS gate stacks	52
3	TEM results after FGA	54
4	EDS results	55
5	XPS results	56
6	Thermal stability (RTP)	58
Chapter 4	Conclusions and future work	61
References	62
                                    

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