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西湖大學(xué)王睿組Acc. Mater. Res：有機(jī) Amidiniums在鈣鈦礦光伏材料中的作用

發(fā)表時(shí)間：2025-01-02 10:50

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主要內(nèi)容：

清潔能源作為可持續(xù)發(fā)展的基石，在光伏技術(shù)中，尤其是基于有機(jī)-無機(jī)鉛鹵化物鈣鈦礦（OLHPs）材料的太陽能電池，近年來取得了顯著的突破性進(jìn)展。OLHPs的化學(xué)式為ABX3，其中A位陽離子的選擇對于鈣鈦礦結(jié)構(gòu)的穩(wěn)定性和整體光電性能具有至關(guān)重要的影響。隨著研究的不斷深入，超大尺寸Amidiniums（作為一類特殊的A位陽離子）作為添加劑或鈍化劑，在OLHPs中展現(xiàn)出了其獨(dú)特且不可或缺的作用。

在本文中，西湖大學(xué)工學(xué)院王睿教授及其團(tuán)隊(duì)深入探討了Amidiniums在OLHPs研究中的關(guān)鍵進(jìn)展。這些進(jìn)展不僅從熱力學(xué)和動力學(xué)的角度揭示了Amidiniums對成核與結(jié)晶過程的精細(xì)調(diào)控機(jī)制，還深入分析了其對體相和界面電子態(tài)的調(diào)制效應(yīng)。具體而言，Amidiniums通過優(yōu)化OLHPs的成核過程，顯著提升了結(jié)晶質(zhì)量，并深刻影響了電子構(gòu)型。同時(shí)，它們還能通過應(yīng)變誘導(dǎo)效應(yīng)**調(diào)控體相電子態(tài)，并通過誘導(dǎo)形成低維相和多功能基團(tuán)來調(diào)節(jié)表面電子態(tài)，從而有效消除了表面電勢的不均勻性，進(jìn)一步提高了太陽能電池的光電轉(zhuǎn)換效率和長期穩(wěn)定性。

此外，該研究團(tuán)隊(duì)還通過對比分析不同厚度的鈣鈦礦薄膜，揭示了應(yīng)力、電導(dǎo)率、載流子遷移率和濃度之間的復(fù)雜關(guān)系，并提出了一種創(chuàng)新的應(yīng)變釋放策略（SRS）來有效減輕厚膜中的應(yīng)變，進(jìn)而提升器件性能。引入大尺寸Amidiniums不僅通過晶格膨脹顯著改善了熱載流子的弛豫過程，還顯著提升了太陽能電池的光電轉(zhuǎn)換效率。在界面工程方面，Amidiniums鈍化技術(shù)成功形成了特殊的低維相，有效解決了由表面電勢不均勻引起的降解問題，從而進(jìn)一步提升了PSC（鈣鈦礦太陽能電池）的性能。同時(shí)，具有特定功能基的鈍化層還有效抑制了外來離子的注入，為PSC的長期穩(wěn)定性提供了有力保障。

綜上所述，Amidiniums在OLHPs研究中的作用不容忽視。它們在增強(qiáng)鈣鈦礦結(jié)晶動力學(xué)、調(diào)節(jié)電子態(tài)以及提高PSC效率和穩(wěn)定性方面發(fā)揮著至關(guān)重要的作用。隨著鈣鈦礦太陽能電池逐步邁向商業(yè)化應(yīng)用，Amidiniums有望在制備大面積、均勻且高質(zhì)量的鈣鈦礦薄膜方面發(fā)揮關(guān)鍵作用，為解決太陽能電池和組件的長期運(yùn)行不穩(wěn)定性挑戰(zhàn)提供新的解決方案。未來，新Amidiniums發(fā)現(xiàn)或新穎應(yīng)用的出現(xiàn)，將進(jìn)一步推動OLHPs及其相關(guān)光電器件的蓬勃發(fā)展，為清潔能源的廣泛應(yīng)用貢獻(xiàn)力量。

Figure 1. (a) History of record PSCs performance and main A cation compositions that were used. (1,2) (b) Molecular structures of the reported organic ammoniums.

Figure 2. (a) Schematic representation illustrating the thermodynamic driving forces and kinetics underlying the oriented nucleation of perovskite films. (b) In situ GIXRD analysis of perovskite films fabricated without PAD (top) and with PAD (bottom), highlighting the transition through the nucleation and growth stages, where N++0 marks the nucleation initiation, Ns represents the nucleation stage, and G corresponds to the growth stage. The intensity is represented on a black-red color scale (arbitrary units). (c) Azimuthal angle evolution during the nucleation stage, comparing films without PAD (top) and with PAD (bottom), illustrating the differences in crystallographic orientation. (d) Photoluminescence (PL) spectra evolution during nucleation for films without PAD (top) and with PAD (bottom), demonstrating enhanced structural uniformity with PAD. Reproduced with permission from ref +++++(9). Copyright 2023 The Author(s), under exclusive license to Springer Nature Limited.

Figure 3. (a) TRPL and (b) PCEs of the perovskite films with different thicknesses. (c) Conductivity of SRS, 2.0 M, and 1.4 M perovskite films. GIWAXS scattering profiles of 1.4 M (d), 2.0 M (e), and SRS-2.0 M (f) perovskite films with the increasing angle of incident beam. Reproduced with permission from ref (12). Copyright 2024 The Authors.

Figure 4. (a) Schematic illustration of the hot phonon bottleneck effect, highlighting the accumulation of hot phonons and their influence on carrier cooling dynamics. (b) Carrier temperatures for perovskites doped with FA, higher BZM, and PLM concentrations, extracted using the Boltzmann model, revealing variations in carrier cooling efficiency among the compositions. (c) Intrinsic electron–phonon scattering times for these perovskite materials, illustrating differences in electron–phonon coupling strength and its impact on carrier relaxation processes. Reproduced with permission from ref +++(13). Copyright 2024 AIP Publishing LLC.

Figure 5. (a) Locations of Li cations above and below the perovskite surface, as determined by first-principles calculations, showing the effect of the MSBZM layer on cation distribution. (b) Calculated energy barrier for Li migration, illustrating the significant increase in migration resistance with the MSBZM layer. (c) Secondary ion mass spectrometry (SIMS) analysis of PSCs without and with MSBZM treatment, highlighting differences in ion migration. (d) Depth profiles of Li ions in control and MSBZM-treated perovskite films, demonstrating reduced Li-ion migration in treated films. (e) PCE tracking of unencapsulated control and MSBZM-treated devices at 60 ± 5 °C in a nitrogen-filled glovebox, with error bars indicating the standard deviation across four devices per condition. (f) MPP tracking under 1-sun illumination at 50 ± 5 °C, showing the improved stability of MSBZM-treated devices. Reproduced with permission from ref +++++++(17). Copyright 2024 American Chemical Society.

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