基板偏壓對磁控濺鍍備製氮化鈦鋯薄膜結構與性質之影響

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研究生：	陳璽安 Chen, Hsi-An
論文名稱：	基板偏壓對磁控濺鍍備製氮化鈦鋯薄膜結構與性質之影響 Effect of Bias on the Structure and Properties of TiZrN Thin Films Deposited by Unbalanced Magnetron Sputtering
指導教授：	喻冀平 Yu, Ge-Ping 黃嘉宏 Huang, Jia-Hong
口試委員:	李志偉 Jyh-Wei Lee 薛富盛 F.S.Shieu
學位類別：	碩士 Master
系所名稱：	原子科學院 - 工程與系統科學系 Department of Engineering and System Science
論文出版年：	2014
畢業學年度：	102
語文別：	英文
論文頁數：	86
中文關鍵詞：	氮化鈦鋯、基板偏壓、硬度、殘餘應力
外文關鍵詞：	TiZrN, Substrate bias, Hardness, Residual stress
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研究目的為探討基板偏壓對於氮化鈦鋯薄膜結構與性質之影響，本實驗是利用非平衡磁控濺鍍法將奈米晶氮化鈦鋯 (TiZrN) 薄膜鍍著於(100)矽晶片上，並且應用不同的基板偏壓，範圍由－35V至－150V，實驗結果指出，所有的試片都存在高強度的(111)織構。在本研究中，我們發現當基板偏壓超過－35V以上，氮化鈦鋯薄膜的性質會顯著的改善，在－40V至－120V之間，氮化鈦鋯薄膜保持著優良的性質，包含：高硬度、高輝度、低電組及平坦的表面。在此區間，氮化鈦鋯薄膜的平均硬度為35.5 GPa，平均電阻為33.5μΩ-cm、輝度達到80以上而且薄膜粗糙度介於0.5nm至0.6nm之間。在大範圍的應用偏壓中，氮化鈦鋯薄膜保持優良的性質，這指出製程參數範圍非常廣。然而當基板偏壓達到－150V，有結構損傷以及薄膜剝落的現象發生，透過拉塞福背向散射分析儀(RBS)的結果與掃描式電子顯微鏡(SEM)也可以驗證此結構損傷現象。對於保護鍍附層，必須要有低的殘餘應力來防止薄膜剝落，藉由控制基板偏壓可以將殘餘應力控制在較低的值。在此研究中隨著基板偏壓由－65V下降至－35V，殘餘應力逐漸下降，在低偏壓－40V和－45V時，氮化鈦鋯薄膜可以同時獲得高硬度以及較低的殘餘應力，硬度與殘餘應力分別為33.4～34.5GPa和－2.7～－3.7GPa。

The objective is to investigate the substrate bias effect on the structure and properties of the TiZrN thin films. The TiZrN thin films were deposited by DC unbalanced magnetron sputtering system (UBMS) with dual guns (Ti,Zr) targets onto Si (100) substrates at different substrate bias ranging from －35V to －150V. Experimental results indicated that all the specimens have strong (111) texture in XRD patterns. In this study, we discovered a transition bias of －35 V, above which a significant improvement of properties was found, including high hardness, excellent brilliance, low resistivity and fine surface morphology. Within the bias range of －40 to －120 V, the hardness of TiZrN films is around 35.5 GPa, the resistivity is about 33.5μΩ-cm, and the brilliance is larger than 80. The roughness is between 0.5 nm and 0.6 nm. The TiZrN films maintain excellent properties through a large range of applying bias, indicating that the process window is considerable wide. However, structure damage and thin film delamination were found when substrate bias reached －150V. The RBS result and SEM image further support the structure damage at －150 V. For protective coatings, low residual stress is required to avoid delamination. By adjusting substrate bias, residual stress can be controlled to lower value. In this study, the residual stress of TiZrN films gradually decreases with decreasing the substrate bias ranging from －65V to －35V. The TiZrN thin films with high hardness, lower residual stress could be obtained simultaneously at low substrate bias of －40V and －45V, the hardness and residual stress are 33.4～34.5GPa and －2.7 ～－3.7GPa, respectively.

Contents
摘要    i
Abstract    ii
致謝    iii
Contents    v
List of Figures    viii
List of Tables……………………………………………………………............................................. v
Chapter 1 Introduction    1
Chapter 2 Literature Review    2
2.1 Unbalance magnetron sputtering system (UBMS)    2
2.2 Characteristics of transition metal nitride (TiN and ZrN)    3
2.3 Characteristics of TiZrN    6
2.4 Effect of substrate bias on thin films    9
2.5 Low substrate bias voltage applied in hard coating    12
Chapter 3 Experimental Details    13
3.1 Experimental Apparatus and Specimen Preparation    13
3.2 Characterization Methods    17
3.2.1X-ray photoelectron spectroscopy (XPS)    17
3.2.2 X-ray diffraction (XRD)    17
3.2.3 Glancing Incidence X-ray diffraction (GIXRD)    18
3.2.4 Field emission gun scanning electron microscopy (FEG-SEM)    19
3.2.5 Atomic Force Microscopy (AFM)    19
3.2.6 Rutherford backscattering spectroscopy (RBS)    19
3.3 Characterization Methods for Properties of TiZrN films    20
3.3.1Resistivity (Four-point probe)    20
3.3.2Hardness (Nanoidentation)    22
3.3.3 Laser Curvature Method (Residual Stress)    22
3.3.4 Coloration    24
Chapter 4 Results    25
4.1 Structure    25
4.1.1 Chemical Compositions (XPS)    25
4.1.2 N/(Ti+Zr) ratio and Packing Factor (RBS)    25
4.1.3 XRD    30
4.1.4 GIXRD    35
4.1.5 SEM    38
4.1.6 AFM    43
4.2 Properties    44
4.2.1 Hardness    44
4.2.2 Residual stress    45
4.2.2 Resistivity    46
4.2.2 Coloration    47
Chapter 5 Discussion    49
5.1 Nanostructure of TiZrN    49
5.2 Properties of TiZrN    52
5.2.1 Residual stress    52
5.2.2 Hardness    53
5.2.4 Coloration    58
5.3 Summary of effect bias    60
Chapter 6 Conclusions    61
References    62
Appendix A The XPS deconvolution spectra    70
Appendix B The GIXRD patterns    79
Appendix C AFM-3D images    83
Appendix D RBS results    85

List of Figures
Fig. 2.1 The structure diagram of TiN and ZrN    4
Fig. 2.2 The binary phase diagram of Ti-N system    5
Fig. 2.3 The binary phase diagram of Zr-N system    5
Fig. 2.4 Result of the XRD pattern for the TiZrN(200), TiN(200) and ZrN(200).    7
Fig. 2.5 The XRD patterns of TiZrN films with different gun power of Zr target    8
Fig. 2.6 The XRD patterns for all samples with the nitrogen flow rate ranging from 0 to 2.5 sccm    8
Fig. 2.7 The surface structures of TiN films with different substrate bias.    10
Fig. 2.8 Schematic diagram of <220> channeling direction    11
Fig. 2.9 Potentiodynamic polarization curves of TiN coated and uncoated samples were carried out in 3.5% NaCl    11
Fig.2.10 The variation of residual stress and hardness of TiAlN films with different bias    12
Fig. 3.1 Schematic diagram of the UBMS system    14
Fig. 3.2 The experimental flow chart    16
Fig. 3.3 Schematic diagram of four-point probe.    21
Fig. 3.4 Schematic diagram of the laser curvature system.    23
Fig. 3.5 Schematic diagram of the L*a*b* color space    24
Fig. 4.1 The XPS deconvolution spectra of (a) Ti-2p peak (b) Zr-3d peak of B75 sample    26
Fig. 4.2The XPS deconvolution spectra of (c) N-1s peak (d) O-1s peak of B75 sample    27
Fig. 4.3 The RBS spectrums of TiZrN films (a) B35 (b) B75    28
Fig. 4.4 The packing factor of the TiZrN films with respect to substrate negative bias.    29
Fig. 4.5 The X-ray diffraction patterns of samples B35~B150    33
Fig. 4.6 The grain size of the TiZrN films with respect to substrate negative bias.    34
Fig. 4.7 The FWHM with respect to substrate negative bias.    34
Fig. 4.8 The GIXRD patterns of (a) B35 (b) B75 (c) B150 specimens    37
Fig. 4.9 The cross-sectional images of the TiZrN films for all samples    40
Fig. 4.10 The SEM surface image of TiZrN films deposition with different substrate bias：B35, B40, B85 and B150    41
Fig. 4.11 The SEM surface image of B150 specimen：partial region delamination    42
Fig. 4.12 The deposition rate of TiZrN films with respect to substrate negative bias.    42
Fig. 4.13 The 3D surface images of B35, B40, B85 and B150 by AFM    43
Fig. 4.14 Hardness of TiZrN films with respect to substrate negative bias.    44
Fig. 4.15 The residual stress of TiZrN films with respect to substrate negative bias.    45
Fig. 4.16 The electrical resistivity of TiZrN films with respect to substrate negative bias    46
Fig. 4.17 The variation of color with different substrate bias    48
Fig. 5.1 The residual stress and hardness with respect to substrate bias    53
Fig. 5.2 The variation surface area of contact with different grain size.    56
Fig. 5.3 The resistivity of the TiZrN films with respect to packing factor.    58
Fig. 5.4 The relationship between incident light and roughness of thin films    59
Fig. A.1 The XPS deconvolution spectra of B35 specimen    70
Fig. A.2 The XPS deconvolution spectra of B40 specimen    71
Fig. A.3 The XPS deconvolution spectra of B45 specimen    72
Fig. A.4 The XPS deconvolution spectra of B55 specimen    73
Fig. A.5 The XPS deconvolution spectra of B65 specimen    74
Fig. A.6 The XPS deconvolution spectra of B85 specimen    75
Fig. A.7 The XPS deconvolution spectra of B95 specimen    76
Fig. A.8 The XPS deconvolution spectra of B120 specimen    77
Fig. A.9 The XPS deconvolution spectra of B150 specimen    78
Fig. B.1 The GIXRD patterns of B35, B40 and B45 samples    79
Fig. B.2 The GIXRD patterns of B55-B75 samples    80
Fig. B.4 The GIXRD patterns of B85-B120 samples    81
Fig. B.5The GIXRD patterns of B150 sample    82
Fig. C.1 The AFM 3D images of sample B35-B65    83
Fig. C.2 The AFM 3D images of sample B75-B150    84
Fig. D.1 The RBS results of B35-B65 samples    85
Fig. D.2 The RBS results of B75-B150 samples    86

List of Tables
Table 2.1 Summary of characteristics of TiN and ZrN    3
Table 3.1 The deposition condition of TiZrN with various substrate bias    15
Table 3.2 The deposition condition of TiZrN thin films    15
Table 3.3 The correction factor at different ds    21
Table 4.1 Summary of the experimental results.    31
Table 5.1 The residual stress, grain size and hardness at different substrate bias.    56
Table 5.2 The roughness and brilliance at different substrate bias    59
Table 5.3 Effect of substrate bias for TiZrN thin films in different regions    60


                                

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