https://ir.lib.ncu.edu.tw/handle/987654321/47 Search the Channel s https://ir.lib.ncu.edu.tw/simple-search https://ir.lib.ncu.edu.tw/handle/987654321/110103 title: 合成用於染料敏化太陽能電池之含Naphthopyran光致變色有機染料;Synthesis of Naphthopyran-Based Photochromic Organic Dyes for Dye-Sensitized Solar Cells abstract: 染料敏化太陽能電池(Dye-Sensitized Solar Cells， DSC)因具備透光性、可撓曲性及色彩多樣化等優點，極具應用潛力，但DSC元件在組裝完成後顏色無法再度調整，限制了其在建築上的應用。因此本研究的目標是合成具光致變色的有機染料並將其應用於DSC。目前以光致變色染料NPI作為敏化劑之DSC元件具有最高光電轉換效率，NPI結構為典型的D-π-A (Donor–π-bridge–Accepter)結構，以二苯胺為推電子基經由Naphthopyran變色單元(作為π-bridge)連接氰乙酸拉電子基而成。然而，其吸收範圍窄(半高寬約130 nm)，為擴展其吸收範圍以提高DSC之效率，因此本研究提出兩種方案。第一個方案是於NPI結構中引入Benzothiadiazole (BT) 單元作為輔助拉電子基(Auxiliary acceptor， Aa)形成D-Aa-π-A (Donor–Auxiliary acceptor–π-bridge–Accepter)結構，合成出有機染料DBT-NP；第二個方案是將NPI錨定基團前的苯環替換為Benzothiadiazole (BT) ，使染料的LUMO分布集中於拉電子區，合成出有機染料DNP-BT。兩染料於甲苯中在未照光時的吸收光譜，皆表現π→π*與分子內電荷轉移(ICT)兩個主要吸收峰，DBT-NP 溶液呈亮橘色(兩吸收峰的λmax分別位於377 nm與487 nm)；DNP-BT 溶液呈淺黃色(兩吸收峰的λmax則位於312 nm與395 nm)。在AM 1.5G模擬太陽光(強度100 mW/cm2)照射 20 分鐘後，DBT-NP 轉為暗橘色，原始吸收峰強度隨照光時間遞增且半高寬增加(144 nm→154 nm)，並於602 nm產生微弱吸收峰；DNP-BT 則轉為深綠色，且原始吸收峰強度隨照光時間遞減，並於 617 nm 產生明顯新峰，半高寬約148 nm。將兩染料停止照光再置於暗處20~25分鐘後皆可回復初始狀態，再經過5次循環測試，確認了DBT-NP、DNP-BT於溶液中的光致變色具有不錯的可逆性。由光致變色動力學與能隙分析證實，因DNP-BT相較於DBT-NP能產生更強 ICT 效應，使其褪色速度較慢，表示其開環結構較穩定；此外，前置軌域分佈圖顯示，DBT-NP的LUMO軌域被侷限於輔助拉電子基(BT)上，限制了電子傳遞，而DNP-BT的LUMO更多貢獻在拉電子基上，有效促進電子傳遞至拉電子基再注入至TiO2電極。最後，DNP-BT敏化之DSC元件的最高光電轉換效率為1.33%，優於DBT-NP所敏化元件的1.21%。;Dye-Sensitized Solar Cells (DSCs) have great application potential due to advantages such as transparency， flexibility， and color diversity. However， the color of DSC devices cannot be adjusted once they are assembled， which limits their applications in architecture. Therefore， the goal of this study is to synthesize photochromic organic dyes and apply them to DSCs. Currently， DSC devices using NPI as a sensitizer exhibit the highest power conversion efficiency amongst the photochromic dyes used. NPI features a typical D-π-A (Donor–π-bridge–Acceptor) structure， consisting of a diphenylamine electron donor connected to a cyanoacetic acid electron acceptor via a naphthopyran photochromic unit (acting as the π-bridge). However， its absorption band is narrow (with a full width at half maximum， FWHM， of ca. 130 nm). To broaden its absorption range and improve DSC efficiency， this study proposes two approaches. The first approach introduces a benzothiadiazole (BT) unit into the NPI structure as an auxiliary acceptor (Aa) to form a D-Aa-π-A (Donor–Auxiliary acceptor–π-bridge–Acceptor) configuration， resulting in the synthesis of DBT-NP. The second approach replaces the benzene ring in front of the anchoring group of NPI with a BT unit， allowing the dye′s LUMO to mainly distribute on the anchoring group， resulting in the synthesis of DNP-BT. In toluene solutions， the absorption spectra of both as-prepared dyes exhibit two main absorption peaks corresponding to π→π* and intramolecular charge transfer (ICT) transitions. The DBT-NP solution appears bright orange (the λmax of the two peaks are located at 377 nm and 487 nm， respectively); the DNP-BT solution is light yellow (the λmax of the two peaks are at 312 nm and 395 nm). After 20 minutes of irradiation under AM 1.5G simulated sunlight (intensity of 100 mW/cm²)， DBT-NP turns dark orange; the intensity of its original absorption peak increases with irradiation time， its FWHM broadens (144 nm to 154 nm)， and a weak absorption peak emerges at 602 nm. Conversely， DNP-BT turns dark green; the intensity of its original absorption peak decreases with irradiation time， and a distinct new peak appears at 617 nm with an FWHM of about 148 nm. When the irradiation is stopped and both dyes are placed in the dark for 20 to 25 minutes， they can both return to their initial states. After 5 cycle tests， it was confirmed that both DBT-NP and DNP-BT exhibit good photochromic reversibility in solution. DNP-BT exhibits a slower fading speed than DBT-NP， indicating that its ring-opened structure is more stable. Frontier orbital distribution maps show that the LUMO of DBT-NP is localized on the auxiliary acceptor (BT)， restricting electron transfer. In contrast， the LUMO of DNP-BT exhibits more contribution from the electron acceptor， which effectively promotes electron transfer to the acceptor and subsequent injection into the TiO₂ electrode. Finally， the maximum power conversion efficiency of the DSC device sensitized by DNP-BT is 1.33%， outperforming the 1.21% efficiency of the device sensitized by DBT-NP. <br> Tue, 20 Oct 2026 07:15:02 GMT https://ir.lib.ncu.edu.tw/handle/987654321/110099 title: 不同胺基取代位置的2-methylpyridine對錫鉛鈣鈦礦膜光伏性質的影響;Effects of 2-Methylpyridine with Different Amino Substitution Positions on the Photovoltaic Properties of Tin-Lead Perovskite Films abstract: 錫鉛混合鈣鈦礦(TLPSK)因其能隙(~1.2eV)小於純錫鈣鈦礦和純鉛鈣鈦礦，能夠作為全鈣鈦礦堆疊型太陽能電池的下層電池的吸收層而受到關注。在製備錫鉛混合鈣鈦礦膜時，由於錫鈣鈦礦的結晶速度比鉛鈣鈦礦快，導致膜的品質不佳且膜中的錫與鉛離子分布不均勻，影響鈣鈦礦膜的吸光。另外，二價錫容易被氧化成四價錫而導致所組裝的太陽能電池的光電轉換效率低。為了解決上述缺點，本研究選用了不同胺基取代位置的2-甲基吡啶(amino-2-methylpyridine)的異構物(以下稱xA2M，其中x是amino group位置)作為鈣鈦礦的添加劑，利用上述分子上的胺基或吡啶上氮原子的孤對電子和鈣鈦礦組成中的錫、鉛鈣鈦礦的前驅物產生交互作用，藉此使二者的結晶速度趨於一致，以製備高品質錫鉛混合鈣鈦礦膜。FT-IR光譜中顯示，這些xA2M和錫離子的作用力皆比和鉛離子的作用力大，且與錫的作用力由大至小依序為4A2M > 6A2M > 5A2M > 3A2M，而DLS結果顯示，添加xA2M的錫鉛鈣鈦礦前驅溶液的膠體大小皆有得到不同程度的控制，其中以添加5A2M的錫鉛鈣鈦礦前驅溶液的膠體大小的分佈最為集中。首先，藉由Top view SEM圖比較未添加和添加了這四種分子的鈣鈦礦膜的晶粒大小的分布情況，發現添加5A2M的鈣鈦礦膜的晶粒幾乎集中分布於200 nm到500 nm之間，而未添加與添加了另外三種分子的鈣鈦礦膜的晶粒雖然也有大量分布在200 nm到500 nm之間，但是有較多小於200 nm和大於500 nm的晶粒產生，此結果說明了5A2M與錫、鉛離子之間的交互作用能夠最有效地調控錫、鉛鈣鈦礦的結晶速度，使晶粒的成長速度較一致，晶粒尺寸較相近，而其餘三者與金屬離子之間作用力的大小無法有效調控錫鉛鈣鈦礦的結晶速度，尺寸差異較大。XRD圖中也顯示出添加5A2M的鈣鈦礦膜其(100)晶面的繞射峰強度最高，意味著鈣鈦礦的晶格的排列最為規整，綜合以上數據可知，xA2M與錫、鉛離子的作用力要適中才能有效地去平衡錫鈣鈦礦和鉛鈣鈦礦的結晶速度並調控結晶過程，才能製備出高光伏性能的鈣鈦礦膜。未添加的鈣鈦礦膜作為吸光層所組裝的太陽能電池的光電轉換效率為19.33%，添加3A2M、4A2M、5A2M或6A2M的鈣鈦礦膜作為吸光層所組裝的太陽能電池的光電轉換效率分別為20.82%、19.89%、21.23%和19.37%。將未封裝的元件放置於室溫的氮氣環境中1080小時後，未添加和分別添加3A2M、4A2M、5A2M或6A2M的鈣鈦礦膜作為吸光層所組裝的元件光電轉換效率分別維持原本的77%、81%、80%、86%和77%。;Tin–lead mixed perovskites (TLPSKs) have emerged as highly promising low-bandgap (~1.2 eV) absorbers for all-perovskite tandem solar cells. However， the development is inherently hampered by the mismatched crystallization rates between tin and lead perovskites， which typically induces severe compositional heterogeneity， poor film morphology， and detrimental oxidation of Sn²⁺ to Sn⁴⁺.Herein， this study overcomes these problems by introducing amino-2-methylpyridine isomers (xA2M) as multifunctional additives. By leveraging the lone-pair electrons from either the amino groups or the pyridine nitrogen atoms， these molecular variants strategically coordinate with both tin and lead precursors to synchronizing their distinct crystallization pathways. FT-IR spectroscopy reveals that the xA2M isomers possess a fundamentally stronger affinity toward Sn than Pb， with the Sn-coordination strength decreasing in the order of 4A2M > 6A2M > 5A2M > 3A2M. Top-view SEM images unveils that this interaction hierarchy directly dictates film morphology. Specifically， 5A2M yields an exceptionally uniform film with grain sizes tightly confined within 200 to 500 nm. In contrast， both the pristine films and films modified with the other three isomers exhibit a disordered， bimodal grain distribution with abundant sub-200 nm and oversized (>500 nm) clusters. This stark disparity underscores that 5A2M offers a precisely tailored chemical environment to balance crystal growth. Concurrently， XRD analysis shows that the 5A2M-engineered perovskite exhibits the highest diffraction intensity along the (100) lattice plane， implying a superior， highly oriented crystalline order. Collectively， our findings establish a fundamental design rule for perovskite additives: the coordination strength between organic ligands and metal cations must be finely optimized—rather than maximized—to effectively homogenize the crystallization kinetics. Driven by this structural refinement， the solar cells leveraging the 5A2M-modified absorber deliver a superior power conversion efficiency (PCE) of 21.23%， substantially outperforming the control device (19.33%) and those with 3A2M (20.82%)， 4A2M (19.89%)， and 6A2M (19.37%). Furthermore， unencapsulated 5A2M devices exhibit exceptional long-term durability， retaining 86% of their initial efficiency after 1080 hours of aging in a room-temperature nitrogen environment， markedly surpassing the 77% retention of the pristine control cell. <br> Tue, 20 Oct 2026 07:14:40 GMT https://ir.lib.ncu.edu.tw/handle/987654321/110095 title: D-A單元強弱調控高分子能階並應用於鈣鈦礦太陽能電池載子傳遞層;D-A單元強弱調控高分子能階並應用於鈣鈦礦太陽能電池載子傳遞層 abstract: 鈣鈦礦太陽能電池(Perovskite Solar Cells， PSCs)中載子傳遞層的功能是將鈣鈦礦層吸收光後激發出的載子萃取並傳遞至外部電路。其中，有機高分子材料因具備好的成膜性、高載子遷移率和可調控能階的性質，在PSCs載子傳輸層的應用上備受關注。先前本實驗室已合成D-A type高分子PIDT-BTCN，其雖具備載子萃取能力，但因結構中的Donor單元IDT具強推電子能力，導致高分子的HOMO能階(-5.44 eV)無法與鈣鈦礦層的價帶(-5.44 eV)形成能障阻擋電洞流向。為了改善高分子與鈣鈦礦層間的能階搭配，本研究透過調整D-A結構中推拉電子的強弱來調整D-A高分子的前置軌域能階，將原先的IDT結構替換成強拉電子能力的benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)作為Acceptor單元，並分別以含兩個拉電子氰基的benzo[c]thiophene-5，6-dicarbonitrile (BTCN)及3，4-dicyanothiophene (TCN)作為弱Donor單元，合成出高分子PBDOPV-BTCN和PBDOPV-TCN。PBDOPV-BTCN和PBDOPV-TCN的熱裂解溫度分別為245 ℃及256 ℃，高於元件組裝及運作時的溫度(約小於150 ℃)。在鈣鈦礦膜上沉積兩個高分子的水接觸角由原先的45.9度分別提高至80.8度和82.7度。PBDOPV-BTCN、PBDOPV-TCN與鉛鈣鈦礦層間的前置軌域能階顯示，兩個高分子的HOMO能階(-5.06 eV和-5.16 eV)均高於鈣鈦礦層的價帶，而其LUMO能階(-3.46 eV和-3.49 eV)也高於鈣鈦礦層的導帶，此能階排列有助於鈣鈦礦層中的電洞被萃取出並傳遞至電極，同時可對電子形成阻擋效果，因此高分子PBDOPV-BTCN和PBDOPV-TCN較適合作為鈣鈦礦太陽能電池之電洞傳遞層。將兩個高分子作為電洞傳遞層組裝成一般式鉛鈣鈦礦太陽能電池的效率分別為1.36%及1.70%。;In Perovskite Solar Cells (PSCs)， the function of the charge transport layer is to extract the charge carriers generated by the perovskite layer after light absorption and transport them to the external circuit. Among various materials， organic polymers have attracted significant attention for applications in PSC charge transport layers due to their excellent film-forming properties， high carrier mobility， and tunable energy levels. Previously， our laboratory synthesized a D-A type polymer， PIDT-BTCN. Although it possesses charge extraction capabilities， the strong electron-donating ability of the IDT donor unit results in a HOMO energy level (-5.44 eV) that cannot form an energy barrier with the valence band of the perovskite layer (-5.44 eV) to block the flow of holes. To improve the energy level alignment between the polymer and the perovskite layer， this study modulates the frontier orbital energy levels of the D-A polymers by tuning the electron push-pull strength within the D-A structure. The original IDT structure was replaced with benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)， which exhibits strong electron-withdrawing ability， as the acceptor unit. Additionally， benzo[c]thiophene-5，6-dicarbonitrile (BTCN) and 3，4-dicyanothiophene (TCN)， both containing two electron-withdrawing cyano groups， were used as weak donor units to synthesize the polymers PBDOPV-BTCN and PBDOPV-TCN.The thermal decomposition temperatures of PBDOPV-BTCN and PBDOPV-TCN are 245 °C and 256 °C， respectively， which are higher than the temperatures required for device assembly and operation (approximately below 150 °C). After depositing the two polymers on the perovskite film， the water contact angles increased from the original 45.9° to 80.8° and 82.7°， respectively. The frontier orbital energy level alignments between PBDOPV-BTCN， PBDOPV-TCN， and the lead perovskite layer show that the HOMO energy levels of both polymers (-5.06 eV and -5.16 eV) are higher than the valence band of the perovskite layer， and their LUMO energy levels (-3.46 eV and -3.49 eV) are also higher than the conduction band of the perovskite layer. This energy level arrangement facilitates the extraction and transport of holes from the perovskite layer to the electrode while simultaneously providing an electron-blocking effect. Therefore， the polymers PBDOPV-BTCN and PBDOPV-TCN are more suitable as hole transport layers for perovskite solar cells. When these two polymers were applied as hole transport layers in regular lead perovskite solar cells， the power conversion efficiencies were 1.36% and 1.70%， respectively. <br> Tue, 20 Oct 2026 07:14:10 GMT https://ir.lib.ncu.edu.tw/handle/987654321/110092 title: 同碳雙碳烯與鈀、銥金屬錯合物之合成、鑑定與反應選擇性探討;Synthesis， Characterization， and Reaction Selectivities of Carbodicarbene Palladium and Iridium Complexes abstract: 同碳雙碳烯具有形式上的碳(0)中心，並借助兩側碳烯提供電子達成八隅體穩定。其碳(0)中心上存在兩對相互正交的孤對電子，能作為給電子配位基，展現出雙重配位能力。本論文接續周凱文學長的研究，將咪唑並[1，5-a]吡啶的分子片段引入同碳雙碳烯前驅物的結構設計，與鈀和銥金屬前驅物合成同碳雙碳烯和鈀、銥金屬錯合物。隨後與不同金屬試劑反應形成一系列雙金屬錯合物。 將 6a-Pd、6b-Pd 和 6c-Ir 與第二金屬進行配位反應，三種單核金屬錯合物皆能展現出同碳雙碳烯的典型的偕位配位模式，並形成偕位雙金屬錯合物 (7a-PdCu， 7a-PdIr， 7b-PdIr， 7c-IrCu， 7c-IrAu)。特別的是，6a-Pd、6b-Pd 和 PPh3AuCl；PPh3AgOTf；SMe2AuCl 表現出不同的選擇性反應。首先，發現在 6a-Pd、6b-Pd 系列中可獲得同碳雙碳烯暨異常碳烯鈀金雙金屬錯合物 (8a-PdAu， 8b-PdAu)；與銀金屬反應可獲得碳碳鍵偶聯的單鍵產物 (9a-Pd2， 9b-Pd2)。更令人意外的是，與 SMe2AuCl 反應可獲得碳碳鍵偶聯的雙鍵產物 (10b-Pd2)。我們針對偶聯產物的反應進行了 EPR 的追蹤，在反應的過程中偵測到 EPR 的訊號峰，證實反應過程中生成了順磁性的物質。但在 6c-Ir 的錯合物 (9c-Ir)，卻無法獲得相同的結果，經由實驗結果，我們推論咪唑並[1，5-a]吡啶的結構使得整體配位基的電子共振能力提升，而配位第一個金屬錯合物的氧化性質，會影響反應選擇性。 本研究發現同碳雙碳烯與鈀、銥金屬錯合物兩套系統之反應性差異，探討同碳雙碳烯碳第二對孤對電子在不同配位環境下的電子結構變化，以及其對配位模式與反應選擇性的影響。;Carbodicarbenes (CDC) possess a formal carbon(0) center stabilized by electron donation from two flanking carbene to achieve an octet configuration. The carbon(0) center contains two orthogonal lone pairs， allowing it to act as an electron-donating ligand and exhibit dual coordination ability. Building on the previous work of Kai-Wen Chou， this thesis introduces imidazo[1，5-a]pyridine carbenes into the CDC precursors. These ligands were then reacted with Pd and Ir precursors to synthesize CDC–Pd and CDC–Ir complexes， which were subsequently treated with different metal reagents to afford a series of bimetallic complexes. The reactions of the three mononuclear metal complexes 6a-Pd， 6b-Pd， and 6c-Ir with second metal reagents demonstrate the typical geminal coordination mode of CDC， affording geminal bimetallic complexes (7a-PdCu， 7a-PdIr， 7b-PdIr， 7c-IrCu， and 7c-IrAu). Notably， 6a-Pd and 6b-Pd displayed selective reactivity toward PPh₃AuCl， PPh₃AgOTf， and SMe₂AuCl， affording CDC–aNHC bimetallic complexes (8a-PdAu and 8b-PdAu)， C–C single-bond-coupled complexes (9a-Pd₂ and 9b-Pd₂)， and， unexpectedly， a C–C double-bond-coupled complexe (10b-Pd₂)， respectively. EPR signals were detected during the coupling reaction， suggesting the formation of paramagnetic species. However， 6c-Ir showed different reactivity， affording 9c-Ir instead. Based on these experimental results， we propose that the imidazo[1，5-a]pyridine framework enhances the electronic delocalization ability of the ligand， while the redox properties of the initially coordinated metal center can influence reaction selectivity. This study reveals the reactivity differences between CDC–Pd and CDC–Ir complexes， and investigates how different coordination environments affect the electronic structure of the second lone pair at the carbon (0) center， as well as its influence on coordination modes and reaction selectivity. <br> Tue, 20 Oct 2026 07:13:39 GMT