Latent Photoinduced Oxygen Doping Revealed from Emission Saturation of Aggregated Domains in Conjugated Polymer Nanofibers,Advanced Electronic Materials

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Latent Photoinduced Oxygen Doping Revealed from Emission Saturation of Aggregated Domains in Conjugated Polymer Nanofibers
Advanced Electronic Materials ( IF 5.3 ) Pub Date : 2020-05-18 , DOI: 10.1002/aelm.202000265
David J. Walwark ₁ , Thomas P. Martin ₂ , John K. Grey ₁

Affiliation

Photoinduced oxidation (doping) of conjugated polymers by complexation with oxygen can have a significant impact on electronic properties and performance in device environments. Nanofiber model forms of poly(3‐hexylthiophene) (P3HT) are investigated using single molecule spectroscopy that possess similar morphological qualities as their bulk thin film counterparts yet, heterogeneity is confined to the spatial dimensions of these particles. Specifically, P3HT nanofibers assembled in anisole solutions contain both aggregated and nonaggregated (amorphous) chains with distinct electronic properties. Excitation intensity dependent photoluminescence (PL) emission imaging is then used to expose differences in oxygen affinity and reactivity upon photoexcitation. Nanofiber regions with low PL yields tend to show faster PL intensity saturation that also degrade much faster following periods of high excitation intensity soaking. Conversely, other regions show gains in PL intensity and virtually no saturation. These PL “gainer” and “loser” behaviors are assigned as originating from amorphous and aggregated P3HT chains, respectively. The apparent propensity of aggregated chains to undergo latent oxygen doping indicates a greater affinity probably due to a larger extent of electronic delocalization in these structures. The results shed new light on degradation factors studied frequently at the bulk material level, which often lacks sufficient sensitivity to specific structural forms.

中文翻译：

从共轭聚合物纳米纤维中聚集域的发射饱和中揭示了潜在的光诱导氧掺杂。

与氧气络合的共轭聚合物的光诱导氧化（掺杂）可能会对器件环境中的电子性能和性能产生重大影响。使用单分子光谱技术研究了聚（3-己基噻吩）（P3HT）的纳米纤维模型形式，该分子具有与大体积薄膜对应物相似的形态学性质，但异质性仅限于这些粒子的空间尺寸。具体来说，在苯甲醚溶液中组装的P3HT纳米纤维既包含聚集的链，也包含非聚集的（无定形）链，具有不同的电子特性。激发强度相关的光致发光（PL）发射成像然后用于暴露光激发时氧亲和力和反应性的差异。具有低PL收率的纳米纤维区域往往会显示出更快的PL强度饱和度，并且在高激发强度浸泡后，降解速度也快得多。相反，其他区域显示PL强度增加，并且实际上没有饱和。这些PL“获得者”和“失败者”行为分别被指定为源自无定形和聚集P3HT链。聚集链发生潜氧掺杂的表观倾向表明其亲和力更高，这可能是由于这些结构中更大程度的电子离域作用所致。结果为在散装材料水平上经常研究的降解因子提供了新的线索，而降解因子通常对特定的结构形式缺乏足够的敏感性。其他区域显示PL强度增加，并且几乎没有饱和。这些PL“获得者”和“失败者”行为分别被指定为源自无定形和聚集P3HT链。聚集链发生潜氧掺杂的表观倾向表明其亲和力更高，这可能是由于这些结构中电子离域的程度更大。结果为在散装材料水平上经常研究的降解因子提供了新的线索，而降解因子通常对特定的结构形式缺乏足够的敏感性。其他区域显示PL强度增加，并且几乎没有饱和。这些PL“获得者”和“失败者”行为分别被指定为源自无定形和聚集的P3HT链。聚集链发生潜氧掺杂的表观倾向表明其亲和力更高，这可能是由于这些结构中更大程度的电子离域作用所致。结果为在散装材料水平上经常研究的降解因子提供了新的线索，而降解因子通常对特定的结构形式缺乏足够的敏感性。聚集链发生潜氧掺杂的表观倾向表明其亲和力更高，这可能是由于这些结构中电子离域的程度更大。结果为在散装材料水平上经常研究的降解因子提供了新的线索，而降解因子通常对特定的结构形式缺乏足够的敏感性。聚集链发生潜氧掺杂的表观倾向表明其亲和力更高，这可能是由于这些结构中更大程度的电子离域作用所致。结果为在散装材料水平上经常研究的降解因子提供了新的线索，而降解因子通常对特定的结构形式缺乏足够的敏感性。

更新日期：2020-05-18

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