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製備矽單晶微奈米結構水滴發電元件及其產電特性之研究;製備矽單晶微奈米結構水滴發電元件及其產電特性之研究

title: 製備矽單晶微奈米結構水滴發電元件及其產電特性之研究;製備矽單晶微奈米結構水滴發電元件及其產電特性之研究 abstract: 本研究成功於N-type (001)之矽單晶基材上，利用鹼性蝕刻法及兩步驟金屬輔助化學蝕刻法分別製備出大面積之隨機排列金字塔結構及準直奈米線結構並以拋光之矽單晶基材作為對照組，利用DI Water初步測試其水衝擊結果並探討其產電原理。接著，為了改善矽晶材料長時間暴露於空氣中容易形成氧化層，導致材料表面從疏水轉變為親水的困境。本研究利用表面改質技術，於具備奈米結構之矽晶材料上噴塗商售之防水噴霧，進而提升材料之疏水性及長時間穩定性。經實驗結果可證實，材料表面維持長久之疏水性，且與未噴塗之結構相比，接觸角顯著提升。此外，該表面改質技術除了提升材料的疏水特性外，同時也提升了輸出電壓及輸出電流。為進一步提升水衝擊元件之電性輸出，本研究首先從材料結構方面切入，同時結合了前述之鹼性蝕刻法與兩步驟金屬輔助化學蝕刻法，先製備出大面積之隨機排列金字塔結構並於其表面製備一維矽晶奈米線以形成矽單晶微奈米結構，此結構不僅具備高比表面積之特性，且結構強度優於準直型矽晶奈米線結構，同時也具備了優異的疏水性。將此結構以前述噴塗技術對其進行表面改質，其接觸角量測結果顯示出經表面改質後的矽單晶微奈米結構具備優異且長時間穩定之疏水特性，且於水衝擊發電量測中顯現出優於前述其他奈米結構之電性輸出。此外，為探究其最佳電性輸出，本研究也透過改變外部條件來探究發電趨勢之變化，如滴水高度、傾斜角度和滴水頻率等，透過實驗結果可評估其元件之最佳量測條件。最後，為符合可撓曲穿戴式裝置及實際應用需求，本研究擬透過一步驟金屬輔助化學蝕刻技術實現均勻且超薄單晶矽基材的製備，並於正面製備前述最佳製程條件之矽單晶微奈米結構，並實施表面改質，期望該結構不僅展現出優異的耐彎折特性，且在彎曲狀態下仍具備穩定的發電性能。最終，本研究預期進行串、並聯水衝擊發電元件模組實驗，成功對多個電容充電並進行串聯後驅動商售之 LED 燈，證明此元件作為微型供電裝置之應用具備了發展潛力。;This study successfully fabricated micro-pyramid structures and vertically aligned nanowire arrays on n-type (001) silicon substrates via alkaline etching and two-step metal-assisted chemical etching (MACE) to systematically investigate water-impact energy harvesting mechanisms. To combat surface degradation from native oxide formation upon atmospheric exposure—which undesirably shifts the surface from hydrophobic to hydrophilic—a commercial hydrophobic coating was spray-deposited onto the textured surfaces. Experimental results confirmed that this surface modification technique not only achieved durable， long-lasting hydrophobicity with a significantly increased contact angle， but also effectively boosted the device′s electrical performance， yielding a simultaneous enhancement in both output voltage and current. To further maximize the electrical output， both etching techniques were integrated to engineer a hierarchical silicon single-crystalline micro-nano structure. Compared to conventional standalone nanowire arrays， this unique architecture offered an exceptionally high specific surface area， superior structural robustness to withstand fluid impact， and outstanding stable hydrophobicity， thereby exhibiting peak power generation performance. Furthermore， the device′s operational efficiency was systematically evaluated and optimized by exploring the shifting trends in electricity generation under varying external parameters， including the dripping height， inclination angle， and dripping frequency. Finally， targeting flexible wearable applications and real-world deployment， uniform and ultra-thin single-crystal silicon substrates were successfully developed via a one-step silver-assisted chemical etching approach. The optimized hierarchical structure engineered onto this flexible platform demonstrated excellent bending endurance and sustained stable power output even under mechanical deformation. Ultimately， module integration experiments involving series and parallel configurations were conducted; the integrated system successfully charged multiple capacitors and illuminated commercial LEDs， validating its immense developmental potential as a micro-scale power supply system.

分岔型陽極氧化鋁水蒸發發電奈米元件之製備及其產電特性研究;Fabrication of Branched Anodic Aluminum Oxide Water Evaporation Electricity Generation Nanodeviced and Investigation of Their Power Generation Characteristics

title: 分岔型陽極氧化鋁水蒸發發電奈米元件之製備及其產電特性研究;Fabrication of Branched Anodic Aluminum Oxide Water Evaporation Electricity Generation Nanodeviced and Investigation of Their Power Generation Characteristics abstract: 本研究以水蒸發驅動之摩擦奈米發電技術為核心，設計並製備一種結合陽極氧化鋁（Anodic Aluminum Oxide， AAO）奈米通道的高效能能量轉換元件。首先，藉由電解拋光與陽極氧化製程，製備具有高孔隙率、良好準直性及規則排列特性的多孔 AAO 奈米通道結構，以增加材料與水分子的接觸面積，進而強化毛細輸水能力與水分蒸發效率，達到提升元件電性輸出的目的。其中，採用草酸電解液進行單次陽極氧化，可形成孔徑約 50 nm 的準直型奈米通道；採用磷酸電解液進行單次陽極氧化，則可形成孔徑約 100–200 nm 的準直型奈米通道。此外，透過磷酸與草酸電解液進行二次陽極氧化處理，可製備具有不同孔徑的分岔型奈米通道，其中由磷酸電解液形成的上層孔徑約為 150 nm，而由草酸電解液形成的下層孔徑約為 50 nm。後續利用噴塗法將金屬奈米粒子均勻披覆於大孔徑 AAO 奈米通道表面，形成兼具導電性與光熱轉換能力的功能性電極層。由於金屬奈米結構具有表面電漿共振（Surface Plasmon Resonance， SPR）效應，可有效吸收入射光並將光能轉換為熱能，進而提高材料局部溫度與水分蒸發速率，同時增強電荷收集能力。相較於連續式金屬薄膜電極，奈米粒子電極可保留較多孔道開口與水氣傳輸路徑，降低電極披覆所造成的孔道阻塞及蒸發效率下降等問題。此外，針對 AAO 奈米通道底部阻障層限制液體滲透與離子傳輸的問題，本研究採用濕式蝕刻技術移除阻障層，以改善孔道連通性並提升離子傳輸效率。同時，選用導電碳布作為下電極材料，不僅可簡化元件整體結構，亦能提升其導電性與機械穩定性。為提升元件長時間操作的穩定性，本研究進一步利用軟性基板固定元件，使其漂浮於水面，並藉由毛細作用持續將水分輸送至奈米通道內部，實現自供水與穩定蒸發發電功能，進而提高元件的耐久性及實際應用潛力。本研究亦透過材料結構分析與電性量測，驗證所提出製程與元件設計的可行性及操作穩定性，並進一步探討不同電極材料、環境溫度及電解質濃度對元件發電效能的影響。藉由本研究成果，可建立一套兼具穩定性、實用性及可擴展性的水蒸發摩擦奈米發電元件設計方法，未來可望應用於微型自供能感測器、物聯網裝置及環境能量收集系統等領域，展現其於新世代綠色能源技術中的發展潛力。;This study focuses on evaporation-driven triboelectric nanogenerator technology and proposes a high-performance energy conversion device integrated with anodic aluminum oxide (AAO) nanochannels. First， porous AAO nanochannel structures with high porosity， excellent channel alignment， and highly ordered arrangements were fabricated through electropolishing and anodization processes. These structural characteristics effectively increase the contact area between the material and water molecules， thereby enhancing capillary-driven water transport and water evaporation efficiency to improve the electrical output performance of the device. When oxalic acid electrolyte was employed in a one-step anodization process， vertically aligned nanochannels with pore diameters of approximately 50 nm were obtained. In contrast， the use of phosphoric acid electrolyte in one-step anodization produced aligned nanochannels with pore sizes ranging from approximately 100 to 200 nm. Furthermore， by applying a two-step anodization process using both phosphoric acid and oxalic acid electrolytes， branched nanochannel structures with different pore diameters were successfully fabricated， in which the phosphoric-acid-derived pores were approximately 150 nm and the oxalic-acid-derived pores were approximately 50 nm in diameter. Subsequently， metal nanoparticles were uniformly deposited onto the surfaces of the large-pore channels via a spray-coating method to form a functional electrode layer possessing both electrical conductivity and photothermal properties. Owing to the surface plasmon resonance (SPR) effect of metallic nanostructures， the deposited nanoparticles can effectively absorb light energy and convert it into thermal energy， thereby increasing the local temperature and accelerating the water evaporation rate. Meanwhile， the metallic conductive layer also enhances charge collection capability and alleviates the common issue of pore blockage and reduced evaporation efficiency caused by conventional electrode coatings. To improve liquid and ion transport， wet etching was used to remove the AAO barrier layer. Conductive carbon cloth served as the bottom electrode， simplifying the structure while maintaining conductivity and mechanical stability. For long-term operation， the device was fixed on a flexible substrate and floated on water， allowing capillary action to continuously supply the nanochannels and sustain evaporation-induced power generation. Structural and electrical analyses verified device feasibility and stability， while the effects of electrode materials， ambient temperature， and electrolyte concentration on output were evaluated. The resulting design is stable， practical， and scalable， with potential applications in self-powered sensors， Internet of Things devices， and environmental energy harvesting.

電刺激誘導之肌管分泌物增強吉西他濱對乳癌模型抗腫瘤效應之研究;Enhanced Gemcitabine Efficiency and Infiltration Promoted by Secretions from Myoblast in Breast Cancer within a 3D Tissue Model

title: 電刺激誘導之肌管分泌物增強吉西他濱對乳癌模型抗腫瘤效應之研究;Enhanced Gemcitabine Efficiency and Infiltration Promoted by Secretions from Myoblast in Breast Cancer within a 3D Tissue Model abstract: 本研究旨在探討受體外電脈衝刺激（EPS）活化之骨骼肌條件培養基（CM），是否能作為強效化療增敏劑，協同臨床一線化療藥物 Gemcitabine 抑制人類乳癌細胞（MDA-MB-231）之生長。實驗平台從常規二維（2D）單層細胞型態，橫跨至貼近真實病理之三維（3D）仿生骨轉移微組織模型。二維平台之結果確立了骨骼肌分泌物之條件培養基（CM）作為化療增敏劑的分子可行性，乳癌細胞之半抑制濃度（IC50）隨電刺激電壓提升而呈現明確的電壓依賴性調降趨勢。然而，當研究推進至高度複雜的三維仿生骨支架環境時，乳癌微組織因立體空間幾何障壁與細胞間交互作用，展現出頑強的多細胞抗藥性（MCR）。在此組織層級環境下，相對低強度（15V）的電刺激 CM 已不再具備任何化療增敏有用性。相較之下，高強度（60V）的電刺激 CM 則展現出優秀的增敏效果，不僅能克服 3D 空間屏障引導藥物穿透至深層（250μm），更可促使中大型腫瘤團塊（>500μm）結構瓦解與小型化，成功逆轉三維組織之耐藥性並恢復 Gemcitabine 之化療毒殺效益。綜上所述，本研究定性地證實了電刺激骨骼肌分泌物能協同化療藥物產生加成之組織毒殺效益，並揭示了環境維度與電刺激強度在抗癌療效上的關鍵交互作用。此成果為未來臨床上整合「電刺激運動處方」與「傳統腫瘤化療」之聯合抗癌策略提供了堅實的理論依據。;This study aims to investigate whether electrical pulse stimulation (EPS)-activated skeletal muscle conditioned medium (CM) can serve as a potent chemosensitizer to synergistically enhance the therapeutic efficacy of the frontline chemotherapeutic drug， Gemcitabine， against human breast cancer cells (MDA-MB-231). The experimental platform spans from conventional two-dimensional (2D) monolayers to a highly biomimetic three-dimensional (3D) scaffold model that recapitulates the breast cancer bone metastasis microenvironment at a tissue level. Results from the 2D platform established the molecular feasibility of secretions from myoblast as chemosensitizers， where the half-maximal inhibitory concentration (IC50) of breast cancer cells exhibited a distinct voltage-dependent decrease with increasing electrical stimulation intensity. However， when transitioned to the highly complex 3D biomimetic bone scaffold， the breast cancer micro-tissues displayed robust multicellular resistance (MCR) due to spatial geometric barriers and intricate cell-matrix interactions. Within this tissue-level microenvironment， conditioned medium generated from relatively low-intensity electrical stimulation (15V) lost its chemosensitizing utility completely. In contrast， high-intensity (60V) CM demonstrated superior spatial penetration capability， which not only overcomes the 3D spatial barrier to guide deep drug penetration (up to 250μm)， but also induces the structural disintegration and shrinkage of medium-to-large tumor aggregates (over 500μm). This successfully reverses the chemoresistance of 3D microtissues and restores the cytotoxic efficacy of Gemcitabine. In conclusion， this study qualitatively demonstrates that electrical stimulation-modulated skeletal muscle secretome can synergistically enhance chemotherapeutic tissue cytotoxicity， revealing a critical interaction between environmental dimensionality and electrical stimulation intensity in anticancer efficacy. These findings provide a solid theoretical foundation for future clinical translations combining "electrical stimulation exercise prescriptions" with "conventional oncological chemotherapy" as an innovative joint therapeutic strategy.

用COSMO-SAC估計PC-SAFT分散力參數預測汽液相平衡;Estimation of the PC-SAFT Dispersion Energy Parameter Using COSMO-SAC for Vapor-Liquid Equilibrium

title: 用COSMO-SAC估計PC-SAFT分散力參數預測汽液相平衡;Estimation of the PC-SAFT Dispersion Energy Parameter Using COSMO-SAC for Vapor-Liquid Equilibrium abstract: 熱力學模型的優勢在於能預測物質的行為，從而節省時間及經濟成本，並降低處理有毒或具爆炸性物質可能潛在的風險。PC-SAFT是以統計力學理論為基礎推導而出的狀態方程式，相較於立方型狀態方程，PC-SAFT在複雜流體與高分子系統之純物質計算與相平衡預測方面有更好的準確性。對於不具有分子間缔合作用之物質，其特徵可由三個參數描述：球體直徑(σ)、球體數量(m)以及分子間分散能量參數(ε)。而對於具有缔合作用之分子，則需多加引入兩項參數：缔合體積(κAB)與缔合能量(εAB)。過去使用PC-SAFT預測溶液相平衡時，需藉由回歸實驗數據而得到二元交互作用參數kij來修正混合物分散能量參數εij，以提升模型的準確性。過去本研究團隊開發了一種結合PC-SAFT與COSMO-SAC的方法，透過調整PC-SAFT二元交互參數，在給定參考壓力下使PC-SAFT與COSMO-SAC所得之過量吉布斯自由能(Gex)相等，即可在無需實驗數據下求得kij。此方法預測流體相平衡雖然有不錯的結果，但參考壓力的選定，是經由我們從大量二元混合物系統的計算經驗，給出一個建議的參考壓力值，才能使此方法在預測多數二元相平衡系統能有較高的準確性。近年來，有研究團隊開發全新的方法結合PC-SAFT與COSMO-SAC，其核心概念在於假定無窮壓力條件下堆積因子(packing fraction)為1，並在此條件下使PC-SAFT與COSMO-SAC之過量吉布斯自由能相等，從而預測εij。此方法相較於我們之前的研究方法，能在更具有理論基礎的公式下推導求得εij，然而其所呈現的預測系統數較少，且結果有非常大的改善空間，尤其是交叉缔合作用系統（cross-associating systems），我們認為問題在於無窮壓力條件下之堆積因子不該為1，亦即在無窮壓力下分子不會堆積得毫無空隙，因此本研究主題旨在探討無窮壓力下堆積因子對流體相平衡預測準確度之影響。此外，針對交叉缔合作用系統預測準確性不足的問題，亦提出改善方法。本研究涵蓋更大量且更多樣之二元混合物汽液相平衡系統，使模型預測具有高度統計代表性，並能充分驗證其對於不同類型分子交互作用下之穩定性與預測能力。在不含氫鍵之系統，壓力平均相對誤差(AARD-P)為4.47%，汽相組成平均絕對誤差(AAD-y)為 1.64%；而在含有氫鍵分子的系統中，AARD-P和AAD-y分別為5.70%和2.32%。相較之下，PC-SAFT在不考慮kij參數的情況下預測相平衡時，在不含氫鍵分子系統的AARD-P為8.97%，AAD-y為3.27%；在含有氫鍵分子的系統中，AARD-P為12.45%，AAD-y為3.95%。從計算結果可知，在缺少實驗數據無法迴歸求得PC-SAFT所需之kij參數時，此次研究提出的方法，相較於PC-SAFT在沒有kij的條件下，能更準確的預測相平衡。而相較於純COSMO-SAC模型，此方法的優勢在於能在高壓系統中準確預測相平衡，而這正是活性係數模型的局限，此方法能夠在高壓系統中維持良好的預測準確性，對於化學工程與工業應用特別重要，因為這代表其能用於預測各種溫壓下的相平衡，即使在嚴苛的操作條件仍能適用。;Thermodynamic models offer the advantage of predicting the behavior of substances， thereby reducing the time and economic costs associated with experiments while minimizing the potential risks involved in handling toxic or explosive materials. PC-SAFT is an equation of state derived based on statistical mechanics. Compared with cubic equations of state， PC-SAFT generally provides better accuracy in pure-component property calculations and phase equilibrium predictions for complex fluids and polymer systems. For non-associating substances， their characteristics can be described by three parameters: segment diameter (σ)， segment number (m)， and dispersion energy parameter (ε). In contrast， for associating molecules， two additional parameters must be introduced: association volume (κAB) and association energy (εAB). In previous studies， the prediction of phase equilibria using PC-SAFT required the regression of experimental data to determine the binary interaction parameter， kij， which was used to correct the mixture dispersion energy parameter， εij， thereby improving the accuracy of the model. Previously， our research group developed a method combining PC-SAFT and COSMO-SAC， in which the binary interaction parameter in PC-SAFT was adjusted such that the excess Gibbs free energy (Gex) calculated by PC-SAFT was equal to that obtained from COSMO-SAC at a given reference pressure. Through this approach， kij could be determined without relying on experimental data. Although this method showed promising performance in predicting fluid phase equilibria， the selection of the reference pressure was based primarily on our computational experience from a large number of binary mixture systems. A recommended reference pressure was therefore proposed to achieve satisfactory accuracy for the prediction of most binary phase equilibrium systems. In recent years， a research group developed a novel approach combining PC-SAFT and COSMO-SAC. The core concept of this method is based on assuming that the packing fraction under infinite-pressure conditions is equal to unity. Under this assumption， the excess Gibbs free energies predicted by PC-SAFT and COSMO-SAC are constrained to be equal， allowing the prediction of εij. Compared with our previous approach， this method provides a more theoretically grounded formulation for deriving εij. However， the number of systems presented in their study was limited， and the predictive results were not entirely satisfactory， particularly for cross-associating systems. We consider that this issue arises from the assumption that the packing fraction under infinite-pressure conditions is equal to 1. In other words， molecules are unlikely to pack without any free volume even under infinite-pressure conditions. Therefore， the objective of this study is to investigate the influence of the packing fraction under infinite-pressure assumptions on the accuracy of fluid phase equilibrium predictions. This study covers a larger and more diverse set of binary VLE systems， providing greater statistical representativeness for model evaluation and enabling a comprehensive assessment of its robustness and predictive capability for different types of molecular interactions. For systems without hydrogen-bonding molecules， the average absolute relative deviation in pressure (AARD-P) and the average absolute deviation in vapor-phase composition (AAD-y) are 4.47% and 1.64%， respectively. For systems containing hydrogen-bonding molecules， the corresponding AARD-P and AAD-y values are 5.70% and 2.32%， respectively. In comparison， when PC-SAFT is used without the binary interaction parameter kij， the AARD-P and AAD-y values are 8.97% and 3.27%， respectively， for systems without hydrogen-bonding molecules， while the corresponding values for systems containing hydrogen-bonding molecules are 12.45% and 3.95%， respectively. These results demonstrate that， when experimental data are unavailable for regressing the kij parameters required by PC-SAFT， the proposed method provides more accurate VLE predictions than PC-SAFT without kij. Compared with the COSMO-SAC model， the advantage of the proposed method is its ability to maintain good predictive accuracy for VLE in high-pressure systems， where activity-coefficient-based models have inherent limitations. The proposed method therefore provides a more reliable framework for predicting phase equilibria over a wide range of temperature and pressure conditions. This capability is particularly important for chemical engineering and industrial applications， as it allows phase equilibrium behavior to be predicted under various operating conditions， including relatively severe conditions where conventional activity-coefficient models may have limited applicability.