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  • 學位論文

二維層狀半導體及有機-無機鈣鈦礦之新型光電元件製備研究

Investigation of Novel Optoelectronic Device Fabrication based on 2-D Layered Semiconductors and Organic-Inorganic Perovskites

指導教授 : 陳永芳
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摘要


二維(2D)層狀半導體之技術如過渡金屬二硫族化合物(TMDs)已經引起了奈米級半導體器件之極大興趣,因為此技術在學術和工業界的興趣都很有吸引力。本論文設計了以SnS2、SnSe2、SnSSe、MoS2、GaSe等二維材料為基礎的新型光電子器件及其異質結構。另外,由於具有良好的發光性能,本論文設計了低維有機-無機(O-I)半導體架構中用於極具前景之光電子器件。經過我們的不懈努力,我們不僅發現了許多富有成效和有趣的光電性質,而且還研究和探討了未來多元化應用的潛力。我們將結果歸類為4個主要議題,總結如下。 1. 藉由能帶工程技術的超薄層狀三元單晶[Sn(SxSe1-x)2]於多功能基底上之高性能光電晶體 二維(2D)三元半導體單晶是新興的一類新材料,由於其在學術興趣和實際應用上的巨大潛力,近來引起了極大興趣。除了其他類型的金屬二硫族化合物之外,二錫二硫族化合物也是具有相似能力的重要的層狀化合物。然而,多元單晶體能夠通過比率改變來幫助多個自由度以獲得主要的物理性質。在這裡,我們報告了單晶硒摻雜SnS2或SnSSe合金的生長,並展示了其高性能光電晶體管基礎製造的能力。基於塊狀高質量單晶的剝離,我們建立了具有結構,光學和電學特性的低分層SnSSe的特性。研究證明,剛性基板(SiO2/Si)和多功能聚對苯二甲酸乙二醇酯(PET)基板及其光電晶體管的光電導SnSSe具有高達約6000 AW-1的超高光信噪比(η)~8.8×105,快速響應時間 ~9 ms,特定探測靈敏度(D*)~8.2×1012 J。這些獨特的特性遠遠高於最近發表的配置有其他幾層二維單晶的光電晶體管,使得超薄SnS Se作為高品質的下一代光電應用候選人。 2. 從自組裝之六方鈣鈦礦單晶和多孔介質之球形諧振器修飾多孔薄膜用於回音廊模態之雷射激發 在自組裝雜化有機-無機鹵化鉛鈣鈦礦半導體中的激光由於其固有出色的光學響應而對低成本和高性能光電子器件進行了深入的研究。然而,要實現小型單晶的可控激光作用仍然是一個具有挑戰性的問題。在這裡,我們提出了一種新穎的技術來製造自組裝高品質的六方鈣鈦礦單晶實現室溫近紅外耳語廊模式(WGM)激光行動。非常有趣的是,單個CH3NH3PbI3六方單晶的激光譜分別包括高質量因子(Q)和低閾值WGM激光在1200和26.8 μJ/cm2附近的方面。此外,我們證明,當多孔鈣鈦礦薄膜用介質球裝飾時,激光振盪可以通過WGM與鈣鈦礦增益材料的耦合來實現。我們發現,激光譜可以很好地控制六角形單晶和SiO2球體的尺寸。此外,所發現的六方單晶鈣鈦礦的激光作用和化學穩定性不僅使其在用於激光光子學,固態照明和顯示應用的高效近紅外發射器件中具有重要的實際應用,而且還提供了對各種光電器件。 3. 垂直疊層石墨烯/單層n-MoS2/SiO2/p-GaN異質結構之多功能探討 在垂直堆疊的p-n異質結上集成不同的尺寸材料已經具有相當的細節,並且可以在光電子器件中具有各種功能開啟極好的可行性。在這裡,我們展示垂直堆疊p-GaN/SiO2/n-MoS2/石墨烯異質結構能夠展現出色的雙光電特性,包括高效的光電探測和光發射,代表了一類新器件的出現。發現光響應性達到 ~10.4 AW-1,檢測靈敏度和外部量子效率估計分別為1.1×1010瓊斯及 ~30%,這些值比大多數報導成果更為優越。此外,該器件還具有自供電的光電探測器,響應速度快,響應速度快。此外,器件還展示了低導通電壓(~1.0 V)的發光,可以通過石墨烯電極的電子注入和從GaN薄膜到單層MoS2層的空穴實現。這些結果表明,通過合適的帶對準選擇,具有不同尺寸的材料的垂直堆疊對於高效異質結構的整合具有顯著的潛力,並且開闢了用於各種應用的集成納米級多功能光電子器件的可行途徑。 4. 用於高性能光電子器件的垂直堆疊的幾層GaSe-SnS2之凡得瓦爾p-n異質結構的第二型能帶排列 原子層薄的垂直堆疊的二維(2D)凡得瓦爾(vdW)異質結構近來已經出現,作為一種新興的設備,具有學術和工業興趣的新奇現象。然而,缺乏p型材料仍然是一個挑戰問題,為實現實際應用創造有用的設備。有趣的是,GaSe是一種具有寬透光性的固有2D 之p型層狀化合物,與厚度無關,且具有直接能帶。在這裡,我們展示了第一個垂直堆疊的幾層p型硒化鎵(GaSe)及n型二硫化錫(SnS2)vdW異質結構,用於高性能光電應用。 p-n接面的電特性表現出良好的整流行為。發現基於GaSe/SnS2 pn結層的光電晶體管的響應度,外部量子效率和比檢測靈敏度分別高達35 AW-1,62%及8.2×1013 J。此外,GaSe/SnS2 p-n接面還可以用作具有大約 ~2.84%的高功率轉換效率的光伏電池。此外,少量層狀GaSe/SnS2 p-n異質結構可製備在具有優異性能的通用基底上,如可撓曲的聚對苯二甲酸乙二醇酯(PET)。通過詳細的研究,少層的GaSe/SnS2之光電器件高性能的潛在機制可以歸因於獨特的第二型能帶排列和良好的接面品量。這裡所示的幾層p-GaSe/n-SnS2 vdW之異質接面結構乃新2D材料堆疊之例證,這對於下一代新型光電器件的發展是非常有用的。

並列摘要


Atomically thin two-dimensional (2D) layered semiconductors, such as transition metal dichalcogenides (TMDs) have attracted tremendous interest in nanoscale semiconductor devices owing to their attractive scrutiny both in academic and industrial interest. In this dissertation, we have designed novel optoelectronic devices based on 2D materials such as SnS2, SnSe2, SnSSe, MoS2, GaSe, and their heterostructures. In addition, low-dimensional organic-inorganic (O-I) semiconductors frameworks have been designed for highly-promising optoelectronic devices owing to the excellent light emission. Through our great efforts, we not only discovered many fruitful and interesting optoelectronic properties, but also studied and discussed the potentials for the diversified applications in the future. Our results are classified as 4 main topics and summarized as followings. 1. Ultra-thin layered ternary single crystals [Sn(SxSe1-x)2] with bandgap engineering for high performance photo transistors on versatile substrates Two-dimensional (2D) ternary semiconductor single crystals, an emerging class of new materials, have attracted significant interest recently owing to their great potential for academic interest and practical applications. In addition to other types of metal dichalcogenides, 2D tin dichalcogenide are also important layered compounds with similar capabilities. Yet, multi-elemental single crystals enable to assist multiple degrees of freedom for dominant physical properties via ratio alteration. Herein, we report the growth of single crystals Se-doped SnS2 or SnSSe alloys, and demonstrate their capability for the fabrication of photo-transistors with high performance. Based on exfoliation from bulk high quality single crystals, we establish the characteristics of few-layered SnSSe in structural, optical, and electrical properties. Moreover, few-layered SnSSe photo-transistors were fabricated on both rigid (SiO2/Si) and versatile polyethylene terephthalate (PET) substrates and their optoelectronic properties were examined. SnSSe as a photo-transistor was demonstrated to exhibit a high photoresponsivity of about 6000 AW-1 with ultra-high photogain (η) ∼8.8×105, fast response time ∼9 ms, and specific detectivity (D*) ∼8.2×1012 J. These unique features are much higher than those of recently published photo-transistors configured with other few-layered 2D single crystals, making ultrathin SnSSe as a highly qualified candidate for next-generation optoelectronic applications. 2. Whispering Gallery Mode Lasing from Self-Assembled Hexagonal Perovskite Single Crystals and Porous Thin Films Decorated by Dielectric Spherical Resonators Lasing in self-assembled hybrid organic-inorganic lead halide perovskites semiconductors has attained intensive research for low cost and high performance optoelectronic devices due to their inherent outstanding optical response. However, to achieve the controllable laser action from a small single crystal remains as a challenging issue. Here, we present a novel technique to fabricate self-assembled high-quality hexagonal perovskite single crystals for realizing room-temperature near-infrared whispering-gallery-mode (WGM) laser action. Quite interestingly, the lasing spectrum for an individual CH3NH3PbI3 hexagonal single crystals encompasses the aspects of high quality factor (Q) and low threshold WGM lasing around 1200 and 26.8 μJ/cm2, respectively. In addition, we demonstrate that when the porous perovskite thin films were decorated with dielectric spheres, the laser oscillation can be achieved through the coupling of WGM with perovskite gain material. We found that the lasing spectra can be well manipulated by the size of hexagonal single crystals and SiO2 spheres. Moreover, the discovered laser action and chemical stability of hexagonal single crystal perovskites not only render them significant practical use in highly efficient near infrared emitting devices for laser photonics, solid-state lighting and display applications, but also provide a potential extension towards various optoelectronic devices. 3. Diverse Functionalities of Vertically Stacked Graphene/Single layer n-MoS2/SiO2/p-GaN Heterostructures Integrating different dimentional materials on vertically stacked p-n hetero-junctions have facinated a considerable scrunity and can open up excellent feasibility with various functionalities in opto-electronic devices. Here, we demonstrate that vertically stacked p-GaN/SiO2/n-MoS2/Graphene heterostructures enable to exhibit prominent dual opto-electronic characteristics, including efficient photo-detection and light emission, which represents the emergence of a new class of devices. The photoresponsivity was found to achieve as high as ~10.4 AW-1 and the detectivity and external quantum efficiency were estimated to be 1.1×1010 Jones and ~ 30%, respectively. These values are superier than most reported hererojunction devices. In addition, this device exhibits as a self-powered photodetector, showing a high responsivity and fast response speed. Moreover, the device demonstrates the light emission with low turn-on voltage (~ 1.0 V) which can be realized by electron injection from graphene electrode and holes from GaN film into monolayer MoS2 layer. These results indicate that with a suitable choice of band alignment, the vertical stacking of materials with different dimentionalities could be significant potential for integration of highly efficient heterostructures and open up feasible pathways towards integrated nanoscale multi-functional optoelectronic devices for a variety of applications. 4. Type II Band Alignment of Vertically Stacked Few-Layered GaSe-SnS2 van-der Walls p-n Heterostructures for High Performance Opto-electronic Devices Atomically thin vertically stacked two dimentional (2D) van der Walls (vdW) heterostructures have recently emerged as a new kind of devices with intriguing novel phenomena for both academic and industrial interests. However, the lack of p-type materials remains as a challenge issue to create useful devices for the realization of practical applications. Interestingly, GaSe is an intrinsic 2D p-type layered compound with a wide optical transparency, and it has a direct band gap with regardless of the thickness. Here, we demonstrate the first vertically stacked few-layered p-type gallium selenide (GaSe) and n-type tin disulphide (SnS2) vdW heterostructure for high performance opto-electronic applications. The electrical characteristic of the p-n junction reveals an excellent current rectification behaviour. It is found that the phototransistors based on few-layered GaSe/SnS2 p-n junction show superior performance with the responsivity, external quantum efficiency and specific detectivity as high as ~ 35 AW-1, 62% and 8.2×1013 J, respectively, which exceed all the reported values derived from 2D materials. In addition, the GaSe/SnS2 p-n junction can also serve as a photovoltaic cell with an high power conversion efficiency of about ~ 2.84%. Moreover, the few-layered GaSe/SnS2 p-n heterostructures can be deposited on versatile substrates with excellent performance, such as flexible polyethylene terephthalate (PET). Through a detailed study, the underlying mechanism responsible for the high performance of opto-electronic devices on few-layered GaSe/SnS2 can be attributed to the unique type II band alignment and excellent quality of interface. The few-layered p-GaSe/n-SnS2 vdW heterojunctions shown here demonstrate a new illustration for the stacking of 2D materials, which is very useful for the development of next generation novel opto-electronic devices.

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