射頻磁控濺鍍鋯酸鉛鋇鐵電薄膜變容器之特性研究

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研究生：	吳林榮 Wu Lin-Jung
論文名稱：	射頻磁控濺鍍鋯酸鉛鋇鐵電薄膜變容器之特性研究 Characteristics of (Pb,Ba)ZrO3 Thin Film Varactors Deposited by RF-Magnetron Sputtering
指導教授：	吳振名 Wu Jenn-Ming
口試委員:
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2007
畢業學年度：	96
語文別：	中文
論文頁數：	190
中文關鍵詞：	微波、變容器、鋯酸鉛鋇
外文關鍵詞：	microwave, varactor, (Pb,Ba)ZrO3
相關次數：	點閱：3 下載：0
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鋯酸鉛鋇(Pb,Ba)ZrO3鐵電薄膜材料擁有隨不同外加直流偏壓而改變介電常數的特性，稱之為調變性(Tunability)。運用此特性可製作變容器、調變濾波器(Tunable Filters)與相位移器(Phase Shifter Devices)等元件。由磁控濺鍍法鍍製的鋯酸鉛鋇薄膜的基本介電性質在本研究中被詳細探討。濺鍍法鍍製的薄膜與同樣成分的溶凝膠法鍍製的薄膜相比，擁有相當高的調變性以及相差無幾的介電損。藉由鉛酸鋇電極當作緩衝層，我們可在400度以上結晶並得到（111）優選取向的鋯酸鉛鋇薄膜。然而，在PBZ/BPO介面附近會形成一富含鉛的介面層產生，其厚度約為40 nm，而藉由不同厚度的介電性質量測，可以推斷介電常數隨著厚度而大幅減少的可能原因包括：(1) PBZ/BPO介面層; (2) Pt/PBZ介面處的低介電層; 和(3) 晶界造成的影響。
藉由適當的參雜元素以及適當的參雜含量，鋯酸鉛鋇的許多介電性質都可獲得改善，如降低漏電流，降低介電損，以及降低電容溫度係數(temperature coefficient of capacitance)等，最佳值分別為J=1.32×10-8 A/cm2 (外加電場為1 MV/cm)、tanδ=0.003和TCC=1.13×10-4。此外，材料的高頻微波性質可利用環形電容(circular-patch capacitor)和網路分析儀(network analyzer)來量測，結果顯示藉由適當的參雜量以及參雜元素得到的濺鍍鋯酸鉛鋇薄膜很適合作為微波元件的應用材料。

The dielectric constant of ferroelectric material, (Pb,Ba)ZrO3, (PBZ) depends on dc voltages. Because of this tunable characteristic, it is applied to fabricate the varactors, tunable filters and phase shifter devices. The dielectric properties of the PBZ films deposited by RF- magnetron sputtering were investigated in this thesis. The sputtered PBZ film exhibits much higher tunability (60% at 200kV/cm) and only a little higher loss tangent (0.015) than the corresponding sol-gel PBZ films. (111) prefer-oriented PBZ thin film was successfully grown on BaPbO3 (BPO) buffer layer at temperatures once 400oC. Non-stoichiometry of Pb near the BPO interface was observed. The interface consisted of a Pb-rich interfacial layer of ~40nm. The thickness-dependent dielectric properties of Pt/PBZ/BPO capacitors can be attributed to (1) the interfacial layer at PBZ/BPO interface, (2) dead layer at Pt/PBZ interface, and (3) the grain boundary dead layers
With doping of Pt or Al2O3, the dielectric properties of PBZ films are greatly improved. The doped PBZ films possess low leakage current, low dissipation factor, and low temperature coefficient of capacitance. The best dielectric properties are J=1.32×10-8 A/cm2 (applied field : 1 MV/cm), tanδ=0.003, and TCC=1.13×10-4, respectively. The microwave dielectric properties were measured with a circular-patch capacitor geometry and a network analyzer (HP8753ES, Agilent). The results demonstrate that the sputtered PBZ films are promising materials for microwave device applications by optimum doping content and doping element.

Contents
Abstract (Chinese)…………………………………………………….    I
Abstract (English)……………………………………………..    II
Acknowledgement………………………………………………..    IV
Contents………………………………..……………………….    VI
List of Tables……………………………...…………….….    XIII
List of Figures………………………………………………...    XIV


Chapter 1 Introduction…………………………………................    1
1 Introduction to the Ferroelectric Materials………    1
2 Varactors made with ferroelectric materials………    2
2.1 Varactors used in personal communication systems (PCS)  …4
2.2 Varactors used in wireless and satellite communications systems.    6
3 Motivation and objectives of research.....…….    8

Chapter 2 Background Study………………………………….    15
1 Varactors…………………………………………………….    15
1.1 Varactors in parallel structure (MIM structure)…….....................    17
1.2 Varactors in coplanar structure (MOS structure)……...................    19
2 Typical tunable ferroelectric materials………….    21
2.1 SrTiO3 (STO)…………………………………….……..    23
2.2 (Ba,Sr)TiO3 (BST)……………………………………...    24
2.3 (Ba,Zr)TiO3 (BZT)………………………………………    25
2.4 (Pb,Sr)TiO3 (PST)………………………………………    26
2.5 (Pb, Ba)ZrO3 (PBZ)………………………………………28
3 Basic concepts of microwave measurement...…………    29
3.1 Resonant Methods………………………………………..    31
3.2 Waveguide and Transmission Line Methods…………    33
3.3 Capacitor Methods...............................    35

Chapter 3 Experimental procedures………………………..    51
1 Substrate preparation………………………………………………......    51
2 Fabrication of bottom and top electrodes……………    52
2.1 Deposition of BaPbO3 (BPO) thin films……………    52
2.2 Deposition of Pt thin films…………………………    52
2.3 Deposition of Ag thin films…………………………    52
3 Fabrication of ferroelectric thin films……………    53
3.1 Deposition of (Pb,Ba)ZrO3 thin films………………    53
3.2 Deposition of doped (Pb,Ba)ZrO3 thin films………    53
4 Characteristic measurements……………………………    54
4.1 Structure analysis………………………………………    54
4.1.1 X-ray Diffraction (XRD) and Grazing Incident X-ray Diffraction (GIXD)………………………………………...…    54
4.1.2 Field Emission Scanning Electron Microscopy (FESEM)……    55
4.1.3 Raman spectroscopy……………………………………    55
4.2 Compositional depth profile and chemical bonding    56
4.2.1 Secondary Ion Mass Spectroscopy (SIMS)…………    56
4.2.2 X-ray Photoelectron Spectroscopy (XPS)…………    56
4.3 Electrical properties…………………………………    56
4.3.1 Dielectric measurements……………………………    56
4.3.2 Microwave frequency measurements…………………    57
4.3.3 Leakage current measurements………………………    57

Chapter 4 Electric tunable behavior of sputtered lead barium zirconate thin films…………………    63
1 Introduction…………………………………………………    63
2 Experimental Details……………………………………………………    64
3 Results and discussion…………………………………………………    64
3.1 Structure and surface morphology……………………    65
3.2 Polarization-electric field curves (P-E)…………    66
3.3 Capacitance-voltage curve at high frequency……    67
3.4 Electrical properties at microwave frequency……    69
4 Conclusions…………………………………………………    72

Chapter 5 Effect of conductive BaPbO3 electrode on the structural and dielectric properties of (Pb,Ba)ZrO3 films    81
1 Introduction…………………………………………………    81
2 Experiments…………………………………………………    82
3 Results and Discussion…………………………………    84
3.1 Structure and surface morphology……………………    84
3.2 Capacitance-voltage curves……………………………    85
3.3 Current-voltage characteristics……………………    87
3.4 Current transients………………………………………    89
3.5 AC conductivity…………………………………………    93
3.6 Chemical analysis………………………………………    95
4 Conclusions…………………………………………………    96

Chapter 6 Thickness-dependent dielectric properties of nanoscale Pt/(Pb,Ba)ZrO3/BaPbO3 capacitors……………    107
1 Introduction…………………………………………………    107
2 Experiments…………………………………………………    108
3 Results and discussion…………………………………… 110
3.1 Crystal structure and surface morphology…………    110
3.2 Electrical properties…………………………………    112
3.3 Thickness dependent dielectric properties………    113
4 Conclusions…………………………………………………    117

Chapter 7 Reduced leakage current and conduction mechanisms of sputtered platinum-doped lead barium zirconate thin films………………    127
1 Introduction…………………………………………………    127
2 Experiments…………………………………………………    129
3 Results and discussion…………………………………    130
3.1 Crystal structure and surface morphology…………    130
3.2 Capacitance-voltage curves……………………………    131
3.3 Leakage currents…………………………………………    132
3.4 Chemical analysis………………………………………    134
3.5 Raman scattering spectra………………………………    137
4 Conclusions…………………………………………………    138

Chapter 8 Improved dielectric properties of Al2O3-doped Pb0.6Ba0.4ZrO3 thin films for tunable microwave applications……    149
1 Introduction…………………………………………………    149
2 Experiments…………………………………………………    150
3 Results and discussion…………………………………    152
3.1 Structure and surface morphology……………………    152
3.2 Polarization-electric field curves (P-E)…………    152
3.3 Dielectric properties as a function of frequency    153
3.4 Dielectric properties as a function of temperature    155
3.5 Dielectric loss mechanisms……………………………    157
4 Conclusions…………………………………………………    158

Chapter 9 Conclusions…………………………………………    167

References………………………………………………………    169

Publications………………………………………………………    189

                                

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