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研究生： 莊詠嵐
Chuang, Yung Lan
論文名稱： 二維層狀金屬磷硒化合物之寬頻光電元件研究
Two-Dimensional Layered Metal Phosphorus Selenides for Broadband Photonics Devices
指導教授： 許進恭
Sheu, Jinn Kong
學位類別： 博士
Doctor
系所名稱： 理學院 - 光電科學與工程學系
Department of Photonics
論文出版年： 2026
畢業學年度： 114
語文別： 中文
論文頁數： 187
中文關鍵詞： 金屬磷硫族化合物 、寬頻光偵測 、金半金光偵測器 、拉曼光譜 、厚度相依能隙 、場效電晶體
外文關鍵詞： Metal phosphorus trichalcogenides, Broadband photodetection, MSM photodetector, Raman spectroscopy, Thickness-dependent bandgap, Field-effect transistor
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    • 從可見光到近紅外的寬頻光偵測，是成像、感測、光通訊乃至環境監測等眾多技術的共同基礎。長久以來，這類偵測多半倚賴塊材半導體；然而任何單一塊材材料的能隙是固定的，能涵蓋的光譜窗口往往很窄，想做到寬頻就得把多種材料拼在一起，或設計複雜的異質結構堆疊，製程因而變得繁瑣而難以整合。自石墨烯問世以來，二維層狀材料開啟了另一條路：它們以凡得瓦力鬆散堆疊、可剝離至原子層級，性質又能隨厚度與組成連續調控，為元件設計提供了塊材所沒有的自由度。而且這類材料的重要性並不僅止於光學：當矽電晶體被推進到越來越短的通道、關態漏電逐漸成為關鍵限制時，二維半導體那原子級的薄體—恰好能補回塊材矽逐漸失去的閘極靜電控制—使整個家族成為延續元件微縮的有力候選。然而即便是研究已相當深入的過渡金屬二硫族化物，單一材料能涵蓋的能隙範圍仍然有限。於是一個自然的問題浮現：有沒有可能在單一化學家族裡，僅靠組成調控，就把整個可見光到近紅外的窗口補滿？本論文正是以此為出發點。
    層狀金屬磷硒化合物 MnPSe3、HgPSe3 與 SnP2Se6 同屬 MPX3 硒化物家族。本研究並不把它們當成三種各自獨立的材料，而是視為單一、組成可調的材料平台。為了讓三者之間的比較是公平的，所有材料都刻意走同一套流程：以機械剝離與乾式轉印製備，並在相同條件下做成 MSM 光偵測器與底閘極電晶體。
    本論文的重心放在拉曼光譜（第三、四章）。拉曼是一種非破壞性、具空間解析、又對層數與相純度敏感的工具，因此本研究先以它建立三種材料的振動指紋，並進一步從晶體結構的角度理解每個峰的來源：高頻段來自 [P2Se6]4 – 團簇的內部 P–Se 伸縮，由於團簇幾何在整個家族中幾乎不變，這些峰恰好成為跨材料的內部參考；中、低頻段則混入金屬陽離子對其硒籠的振動，會隨陽離子質量與配位幾何規律地移動，因而帶有金屬位置的化學指紋。在這個架構下，本研究首次完整記錄了 HgPSe3 從塊材一路到五層的厚度相依拉曼序列，並發現三種材料中只有 HgPSe3 的拉曼模式圖樣會隨層數改變、可作為層數的判讀依據。
    其餘章節則把這個平台延伸到元件層面。第五章以光響應的截止波長估計光學能隙，SnP2Se6 的九個獨立元件給出清楚的厚度相依趨勢，三種材料合起來涵蓋約 455 到745 nm 的連續範圍。第六章把三者做成相同幾何的 MSM 光偵測器並列比較。第七章首次對少層 SnP2Se6 量測底閘極電晶體，並指出場效遷移率的瓶頸主要落在金屬與材料的界面，而非材料本身的能帶結構。
    總結來說，本研究以實驗證實了 MPX3 硒化物家族確實可以當成一個寬頻光偵測的單一平台，其光譜涵蓋範圍能藉由金屬取代與材料厚度共同調控；更重要的是，這套以共同製程、共同拉曼判讀為基礎的比較框架，讓往後的改良能夠有系統地進行，而不再是針對單一材料各做各的。

    Broadband photodetection spanning the visible and near-infrared underpins a wide range of modern technologies, from imaging and sensing to optical communication and environmental monitoring. For decades this task has rested on bulk semiconductors; but the fixed bandgap of any single bulk material covers only a narrow spectral window, so broadband operation has typically demanded that several materials be combined, or that elaborate heterostructure stacks be engineered—an approach that quickly becomes cumbersome to integrate. The emergence of two-dimensional layered materials since the isolation of graphene has opened a different route: held together by weak van der Waals forces, these crystals can be exfoliated down to the atomic limit and their properties tuned continuously with thickness and composition, offering a design freedom that bulk crystals do not. Their importance, moreover, reaches beyond optics: as silicon transistors are scaled to ever-shorter channels and off-state leakage becomes a defining constraint, the atomically thin body of a 2D semiconductor—which restores the gate control that bulk silicon progressively loses—has made the family a leading candidate for continued device scaling. Yet even the most thoroughly studied 2D semiconductors, such as the transition-metal dichalcogenides, span only a limited bandgap range on their own. This raises a natural question: could a single chemical family, tuned by composition alone, cover the entire visible-to-near-infrared window? It is this question that motivates the present work.
    The layered metal phosphorus selenides MnPSe3, HgPSe3, and SnP2Se6 all belong to the MPX3 selenide family. Rather than treating them as three separate materials, this work approaches them as a single, compositionally tunable platform. To keep the comparison between the three a fair one, every material was deliberately put through the same process: prepared by mechanical exfoliation and dry transfer, and built into metal–semiconductor–metal (MSM) photodetectors and back-gated transistors under identical conditions.
    The core of the dissertation is its Raman study (Chapters 3 and 4). Raman spectroscopy is non-destructive, spatially resolved, and sensitive to layer number and phase purity, and it is used here first to establish the vibrational fingerprints of the three compounds and then to interpret each peak in terms of the crystal structure: the high-frequency bands originate within the [P2Se6]4 – cluster, whose geometry is almost unchanged across the family and which therefore serves as a material-independent internal reference, while the mid- and low-frequency modes involve the metal cation moving against its selenium cage and shift systematically with cation mass and coordination, carrying a genuine chemical fingerprint of the metal site. Within this framework, the first complete thickness-resolved Raman series for HgPSe3, from bulk down to five layers, was recorded; of the three compounds, only HgPSe3 shows a Raman mode pattern that changes with layer number and can thus act as a layer counter.
    The remaining chapters extend this platform to the device level. Chapter 5 uses the photoresponsivity cut-off wavelength to estimate the optical bandgap; nine SnP2Se6 devices show a clear thickness-dependent trend, and the three compounds together cover a continuous window from roughly 455 to 745 nm. Chapter 6 compares all three as MSM photodetectors of identical geometry. Chapter 7 reports the first back-gated transistor measurement of few-layer SnP2Se6 and identifies the metal–flake interface, rather than the band structure of the material itself, as the bottleneck limiting field-effect mobility. Taken together, the work experimentally confirms that the MPX3 selenide family can serve as a single platform for broadband photodetection, with its spectral coverage tunable through both metal substitution and flake thickness. More importantly, the common-process, common-Raman-protocol framework established here means that future improvements can be pursued systematically, rather than one material at a time.

    摘要 i Abstract iii 誌謝 v Table of Contents vi List of Tables ix List of Figures x Chapter 1 Introduction and Motivation 1 Section 1.1 The Two-Dimensional Materials Landscape 1 Section 1.2 The Emerging MPX3 Family: Structure, Chemistry, and Promise 8 Section 1.3 Research Gap: Lack of Systematic Intra-Family Comparative Studies 12 Section 1.4 Scope and Organisation of This Dissertation 14 Chapter 2 Literature Review: Metal Phosphorus Trichalcogenides 17 Section 2.1 Crystal Structure, Bonding, and Polytypism 17 Section 2.2 Electronic Band Structure and Bandgap Trends 21 Section 2.3 Vibrational Properties and Raman Fingerprints 28 Section 2.4 Distinguishing Physical Properties of the Three Selenides 34 Section 2.5 Prior Work on MPX3-Based Devices 40 Section 2.6 Open Questions and Motivation for This Work 44 Chapter 3 Experimental Methods 46 Section 3.1 Bulk Crystals and Substrate Preparation 46 3.1.1 Crystal source and morphology 46 3.1.2 Substrate selection and cleaning 49 Section 3.2 Mechanical Exfoliation and Dry Transfer 49 3.2.1 Polymer-stamp transfer protocol 51 3.2.2 Optical-microscope identification of few-layer flakes 53 Section 3.3 Photolithography and Metal Deposition 53 3.3.1 Step-by-step lithography sequence 53 3.3.2 Electron-beam evaporator 55 3.3.3 Quality control 57 Section 3.4 Raman Spectroscopy 57 3.4.1 Excitation-wavelength selection 59 3.4.2 Power calibration and damage protocol 61 Section 3.5 Atomic Force Microscopy 61 3.5.1 Conversion to layer number 63 Section 3.6 Photoresponse Characterisation 63 3.6.1 Light sources and spectral conditioning 65 3.6.2 Gaussian spot profile correction 65 3.6.3 Bias-voltage and timing protocols 67 Section 3.7 Field-Effect Transistor Measurement 67 Section 3.8 Statistical Treatment and Reproducibility 69 Chapter 4 Raman Spectroscopy of MPX3 Selenides 70 Section 4.1 Motivation and Open Questions 70 Section 4.2 Bulk Raman Fingerprints 70 4.2.1 MnPSe3 70 4.2.2 HgPSe3 73 4.2.3 SnP2Se6 75 4.2.4 Cross-material comparison 77 Section 4.3 Excitation-Wavelength Dependence and Laser Damage 77 4.3.1 Penetration depth and resonance considerations 77 4.3.2 Damage-threshold mapping 77 4.3.3 Power-dependent spectral evolution 80 Section 4.4 Thickness Evolution of the Raman Spectrum 83 4.4.1 HgPSe3: a complete series from bulk to 5 L 83 4.4.2 SnP2Se6: peak positions invariant 85 4.4.3 MnPSe3: intensity scaling 87 Section 4.5 Comparative Discussion 87 Section 4.6 Summary 87 Chapter 5 Thickness-Dependent Bandgap Engineering 89 Section 5.1 Methodology: Cut-off Wavelength as a Bandgap Probe 89 5.1.1 Photoresponsivity spectrum and cut-off definition 89 5.1.2 Sources of systematic uncertainty 92 Section 5.2 SnP2Se6: A Systematic Thickness--Bandgap Map 92 5.2.1 Single-device example 92 5.2.2 Nine-device statistical regression 95 5.2.3 Interpretation 97 Section 5.3 HgPSe3: Few-Layer Bandgap Shift 97 Section 5.4 MnPSe3: A Wide-Gap Reference 100 Section 5.5 Cross-Material Synthesis: Spectral Coverage and Confinement Scaling 103 Section 5.6 Limitations of the Cut-off Methodology 105 Section 5.7 Summary 105 Chapter 6 MSM Photodetector Benchmarking 106 Section 6.1 Device Architecture and Process Variants 106 6.1.1 Unified MSM geometry 106 6.1.2 Pre-exfoliation versus post-exfoliation processing 108 Section 6.2 Photoresponse of SnP2Se6 108 6.2.1 Pre-exfoliation device 108 6.2.2 Post-exfoliation device 112 6.2.3 Transient response 115 Section 6.3 Photoresponse of HgPSe3 117 6.3.1 Device A: sapphire substrate 117 6.3.2 Device B: SiO2/Si substrate, post-exfoliation 122 Section 6.4 Photoresponse of MnPSe3 126 6.4.1 Sapphire-based MSM device 126 6.4.2 Reference control: bare-sapphire device 132 Section 6.5 Cross-Material Synthesis of Figures of Merit 132 Section 6.6 Summary 135 Chapter 7 Field-Effect Transport in SnP2Se6 136 Section 7.1 Motivation and Literature Context 136 Section 7.2 Device Architecture 137 Section 7.3 Output Characteristics 139 7.3.1 Pre-exfoliation device 139 7.3.2 Post-exfoliation device 141 Section 7.4 Transfer Characteristics and Mobility 143 7.4.1 Transfer curves and hysteresis 143 7.4.2 Field-effect mobility extraction 146 7.4.3 Interpretation of the mobility values 149 Section 7.5 Gate-Sweep Hysteresis and Interface Trap Density 149 Section 7.6 Comparison with the Broader MPX3 FET Literature 150 Section 7.7 Summary 152 Chapter 8 Conclusions and Future Work 155 Section 8.1 Conclusions 155 Section 8.2 Future Work 156 References 157 Appendix A Tamm-Plasmon-Mediated Sub-gap Extension of MnPSe3 Photoresponse 162 A.1 Motivation and Context 162 A.2 Physical Basis 163 A.3 Device Design and Optical Characterisation 167 A.4 Photoresponse Measurement and Preliminary Result 169 A.5 Analysis of the Present Sensitivity Ceiling 171 A.6 Design Refinements and Outlook 172

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