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研究生：	許宗賢 Hsu, Tsung-Hsien
論文名稱：	低損耗超低溫共燒陶瓷材料微波介電特性應用於5G/6G 先進高頻通訊元件系統 Microwave Dielectric Properties of Low-Loss and ULTCC Materials for Advanced High-Frequency Communication Components in 5G/6G Systems
指導教授：	黃正亮 Huang, Cheng-Liang
學位類別：	博士 Doctor
系所名稱：	電機資訊學院 - 電機工程學系 Department of Electrical Engineering
論文出版年：	2024
畢業學年度：	112
語文別：	英文
論文頁數：	167
中文關鍵詞：	超低溫共燒陶瓷、低損耗、微波介電特性、天線、濾波器、5G/6G通訊系統
外文關鍵詞：	Ultra-Low-Temperature Co-fired Ceramics, Low Loss, Microwave Dielectric Properties, Antennas, Filters, 5G/6G Communication Systems
相關次數：	點閱：83 下載：0
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隨著5G時代的來臨，基站和天線的研究已成為當今最重要的課題之一。這些研究主要涵蓋了兩個頻段：Sub-6GHz（0.45–6GHz）和毫米波（24–52GHz）。在這項研究中，我們成功地開發了一種超低溫共燒陶瓷材料，稱為AMO（A=Li、Co、Ag；M=V、Mo、W）。通過微量取代Mg和Zn，本研究精心優化了其介電特性，同時大幅降低了燒結溫度。這一突破性的成就彰顯了微量取代對燒結劑的深遠影響，可實現顯著的成本降低，同時保持材料性能的完整性。此外，還針對影響材料性能的內在和外在因素進行了全面的研究，確保了研究的系統性和可靠性。最後，我們還開展了基於這些材料的濾波器和陣列天線的研發和全面研究。本論文將系統性地探討四個部分：
A. 釩酸鹽陶瓷研究：
釩-基陶瓷與Li+元素結合，表現出極低的燒結溫度和生產成本。透過微量的Mg2+或Zn2+取代Li+，特別是在520°C下，明顯提高了微波介電性能，Li0.98Mg0.01VO3表現出優秀的特性，包括εr為9.78，Q×f為45,600 GHz，τf為–45 ppm/°C；同時，Li0.98Zn0.01VO3的εr為9.25，Q×f為33,100 GHz，τf為-53.6 ppm/°C。值得注意的是，Li0.98Mg0.01VO3與鋁電極具有相當優異的化學相容性，並且在520°C下添加2 mol%的TiO2後，其特性進一步提升，εr為9.2，Q×f為30,000 GHz，τf為–2.8 ppm/°C。

B. 含銀的釩酸鹽陶瓷研究：
本研究成功利用Ag的添加促使新型AgMgVO4陶瓷的形成，其具有優異的微波介電性能。在630 °C下燒結的陶瓷達到高相對密度（96.2%），展現出優秀的微波介電性能，包括εr約為14.89，Q×f約為19,400 GHz，τf約為–2.71 ppm/°C。此外，這些陶瓷與鋁電極表現出良好的化學相容性。
C. 鎢酸鹽陶瓷研究：
鎢酸鹽陶瓷的燒結溫度相對較高，但透過添加熔點較低的Li元素，可以實現較低的燒結溫度。此外，通過使用0.05 mol%的Mg2+或0.07 mol%的Zn2+取代Li+，Li2WO4陶瓷的燒結溫度從660 °C降至540 °C。總結陶瓷的綜合介電性能εr為6.2和5.8，Q×f為76,000和68,000 GHz，τf分別為–94和–86 ppm/°C。
D. 鉬酸鹽陶瓷研究：
鉬酸鹽陶瓷具有超低的燒結溫度、低吸濕性和具成本效益的優勢。在690°C下燒結的純CoMoO4陶瓷表現出εr = 8.27，Q×f = 64,000 GHz和τf = –96 ppm/°C的介電性能。部分Mg2+取代Co2+有效地提高了陶瓷的緻密度，降低了介電損耗並降低了燒結溫度。在630 °C下燒結的Co0.95Mg0.05MoO4陶瓷表現出卓越的介電性能，包含εr為8.42，Q×f為71,000 GHz，τf為–62.27 ppm/°C，同時保持與鋁電極的相容性。
最後，我們成功地使用HFSS軟體模擬並應用這些陶瓷材料於5G/6G高頻通訊元件，如介質濾波器和天線。這些材料以其低損耗的微波介電性能而著稱，展現出卓越的潛力，有望成為ULTCC陶瓷的首選選項之一。

The onset of the 5G era has elevated research on base stations and antennas to a paramount domain. This research primarily spans across two frequency bands: Sub-6GHz (0.45–6GHz) and millimeter-wave (24–52GHz). Within this study, we have achieved the successful development of ULTCC material, denominated as AMO (A=Li, Co, Ag; M=V, Mo, W). By incorporating minor substitutions of Mg and Zn, we meticulously optimized its dielectric properties, concurrently effecting a significant reduction in sintering temperature. This groundbreaking accomplishment underscores the profound influence of minor substitutions on sintering agents, leading to substantial cost reduction while preserving material performance integrity. Moreover, we conducted an exhaustive examination of both intrinsic and extrinsic factors that impact material performance, ensuring the systematic and dependable nature of this research. Furthermore, we embarked on the development and comprehensive study of filters and array antennas based on these materials. This thesis systematically dissects and investigates four components:
A. Vanadium-Based Ceramics:
Vanadium-based ceramics, in conjunction with Li elements, manifest exceedingly low sintering temperatures and production costs. The substitution of minute quantities of Mg or Zn for Li has yielded remarkable enhancements in microwave dielectric properties, particularly at 520 °C. Li0.98Mg0.01VO3 demonstrated exemplary characteristics, featuring εr of 9.78, Q×f of 45,600 GHz, and τf of –45 ppm/°C. Meanwhile, Li0.98Zn0.01VO3 exhibited εr of 9.25, Q×f of 33,100 GHz, and τf of –53.6 ppm/°C. Notably, Li0.98Mg0.01VO3 exhibited compatibility with aluminum electrodes, and the introduction of 2 mol% TiO2 further amplified its properties at 520 °C, with εr of 9.2, Q×f of 30,000 GHz, and τf of –2.8 ppm/°C.
B. Silver-Containing Vanadium-Based Ceramics:
In this study, the introduction of Ag has successfully facilitated the formation of novel AgMgVO4 ceramics, characterized by remarkable microwave dielectric properties. Ceramics sintered at 630 °C have achieved high relative density (96.2%) and exhibited outstanding microwave dielectric properties, including εr ~14.89, Q×f ~19,400 GHz, and τf ~–2.71 ppm/°C. Furthermore, these ceramics have demonstrated excellent chemical compatibility with aluminum electrodes.
C. Tungsten-Based Ceramics:
Tungsten-based ceramics, despite their inherently higher sintering temperatures compared to vanadium-based ceramics, can achieve lower sintering temperatures through the incorporation of Li elements with lower melting points. In addition, the substitution of 0.05 mol% of Mg2+ or 0.07 mol% of Zn2+ for Li+ has led to a reduction in the sintering temperature of Li2WO4 ceramic from 660 °C to 540 °C. The comprehensive dielectric properties of the resulting ceramics encompass εr of 6.2 and 5.8, Q×f of 76,000 and 68,000 GHz, and τf of –94 and –86 ppm/°C, respectively.

D. Molybdenum-Based Ceramics:
Molybdenum-based ceramics boast the advantages of ultra-low sintering temperatures, low moisture absorption, and cost-effectiveness. Pure CoMoO4 ceramics sintered at 690 °C have exhibited dielectric properties including εr = 8.27, Q×f = 64,000 GHz, and τf = –96 ppm/°C. The strategic substitution of Mg2+ for Co2+ has effectively augmented ceramic densification, reduced dielectric loss, and decreased the sintering temperature. Co0.95Mg0.05MoO4 ceramics sintered at 630 °C have showcased outstanding dielectric properties with εr = 8.42, Q×f = 71,000 GHz, and τf = –62.27 ppm/°C, all while maintaining compatibility with aluminum electrodes.
Finally, these ceramic materials have been successfully simulated and employed in 5G/6G high-frequency communication components such as dielectric filters and antennas using HFSS software. These materials, distinguished by their low-loss microwave dielectric properties, exhibit significant potential as the favored options for ULTCC.

摘要 I
SUMMARY III
致謝 VI
Contents VII
Table Captions X
Figure Captions XII
Chapter 1. Introduction 1
1	Development and Application of Low-Temperature Ceramic Materials (LTCC) 3
2	Review of Ultra-Low Temperature Co-Fire Ceramic Materials.  5
Chapter 2. Theory 11
1	Sintering of Ceramic Materials 11
1.1 Types of Material Sintering 11
1.2 The Process of Material Sintering 15
1.3 Diffusion Mechanisms in Material Sintering 17
2	Dielectric Resonator 18
3 Characteristics of Microwave Dielectric Materials 22
3.1 Dielectric constant (εr ) 22
3.2 Quality factor (Q) 28
3.3 Temperature coefficient of resonant frequency (τf) 30
3.4 Factors Affecting Dielectric Properties 31
4 The Principles of Raman Spectroscopy and Molecular Vibrational Modes 37
4.1 Raman spectra 37
4.2 Vibrational Modes 37
5 Theory of Filter 39
5.1 Introduction to Filters 39
2-5-2 Types of filters and their frequency responses. 41
6 Theory of Antenna 45
6.1 Introduction to Antennas 45
6.2 Types and Applications of Antennas 47
7 Theory of Microstrip 49
7.1 Introduction to Microstrip Transmission 49
7.2 Transmission Modes of Microstrip- TEM Wave 50
7.3 The calculation of various parameters of microstrip 51
7.4 Microstrip Line Discontinuities 53
7.5 Losses in Microstrip Lines 59
Chapter 3. Experimental and Measurement Methods 61
1 Fabrication of Microwave Dielectric Materials 61
1.1 Powder Preparation and Ball Milling 62
1.2 Powder Drying and Phase Calcination 62
1.3 Addition of Binder and Sieving 62
1.4 Green Body Formation, Binder Removal, and Sintering 63
2 Measurement and Analysis of Microwave Dielectric Materials 64
2.1 X-ray Analysis 64
2.2 SEM Analysis 64
2.3 Raman Spectroscopy Analysis 65
2.4 Density Measurement 66
2.5 Measurement and Methodology for Microwave Dielectric Properties 66
Chapter 4. Development of Microwave Dielectric Materials for ULTCC Applications. 69
1.	Low-loss microwave dielectric of novel Li1-2xMxVO3 (M = Mg, Zn) (x = 0–0.09) ceramics for ULTCC applications 69
2.	Ultra-low temperature sintering and temperature stable microwave dielectrics of phase pure AgMgVO4 ceramics 86
3.	Low-loss microwave dielectrics of Li2(1–x)MxWO4 (M= Mg, Zn; x= 0.01–0.09) for ULTCC applications 97
4.	Microwave dielectric properties of ultra-low temperature sintered Co1-xMgxMoO4 (x = 0–0.09) ceramics for 5G array antenna applications at millimeter-wave frequency. 111
Chapter 5. Conclusion 132
References 135
                                    

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