Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties,Advanced Functional Materials

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Competition between Exceptionally Long‐Range Alkyl Sidechain Ordering and Backbone Ordering in Semiconducting Polymers and Its Impact on Electronic and Optoelectronic Properties
Advanced Functional Materials ( IF 18.5 ) Pub Date : 2018-12-12 , DOI: 10.1002/adfm.201806977
Joshua H. Carpenter ₁ , Masoud Ghasemi ₁ , Eliot Gann ₂ , Indunil Angunawela ₁ , Samuel J. Stuard ₁ , Jeromy James Rech ₃ , Earl Ritchie ₃ , Brendan T. O'Connor ₄ , Joanna Atkin ₃ , Wei You ₃ , Dean M. DeLongchamp ₂ , Harald Ade ₁

Affiliation

Intra‐ and intermolecular ordering greatly impacts the electronic and optoelectronic properties of semiconducting polymers. The interrelationship between ordering of alkyl sidechains and conjugated backbones has yet to be fully detailed, despite much prior effort. Here, the discovery of a highly ordered alkyl sidechain phase in six representative semiconducting polymers, determined from distinct spectroscopic and diffraction signatures, is reported. The sidechain ordering exhibits unusually large coherence lengths (≥70 nm), induces torsional/twisting backbone disorder, and results in a vertically multilayered nanostructure with ordered sidechain layers alternating with disordered backbone layers. Calorimetry and in situ variable temperature scattering measurements in a model system poly{4‐(5‐(4,8‐bis(3‐butylnonyl)‐6‐methylbenzo[1,2‐b:4,5‐b′]dithiophen‐2‐yl)thiophen‐2‐yl)‐2‐(2‐butyloctyl)‐5,6‐difluoro‐7‐(5‐methylthiophen‐2‐yl)‐2H‐benzo[d][1,2,3]triazole} (PBnDT‐FTAZ) clearly delineate this competition of ordering that prevents simultaneous long‐range order of both moieties. The long‐range sidechain ordering can be exploited as a transient state to fabricate PBnDT‐FTAZ films with an atypical edge‐on texture and 2.5× improved field‐effect transistor mobility. The observed influence of ordering between the moieties implies that improved molecular design can produce synergistic rather than destructive ordering effects. Given the large sidechain coherence lengths observed, such synergistic ordering should greatly improve the coherence length of backbone ordering and thereby improve electronic and optoelectronic properties such as charge transport and exciton diffusion lengths.

中文翻译：

半导体聚合物中异常长烷基侧链有序与骨架有序之间的竞争及其对电子和光电性能的影响

分子内和分子间的排序极大地影响了半导体聚合物的电子和光电性能。尽管有许多先前的努力，但是烷基侧链的顺序和共轭主链之间的相互关系还没有被完全详述。在此，报道了在六个代表性的半导体聚合物中发现高阶烷基侧链相的情况，这是由不同的光谱和衍射特征确定的。侧链有序表现出异常大的相干长度（≥70 nm），诱发扭转/扭曲的主链无序，并导致垂直多层纳米结构，其中有序的侧链层与无序的主链层交替排列。聚{4-（5-（4,8-双（3-丁基壬基）-6-甲基苯并[1,2-b：4，5-b']二噻吩-2-基）噻吩-2-基）-2-（2-丁基辛基）-5,6-二氟-7-（5-甲基噻吩-2-基）-2H-苯并[d] [1,2,3]三唑}（PBnDT‐FTAZ）清楚地描述了这种有序竞争，从而阻止了两个部分同时进行长距离有序化。远程侧链排序可作为一种过渡状态来利用，以制造具有非典型边缘上纹理和2.5倍改进的场效应晶体管迁移率的PBnDT-FTAZ膜。观察到的部分之间有序的影响暗示改进的分子设计可以产生协同作用而不是破坏性的有序作用。考虑到观察到的较大的侧链相干长度，这种协同排序应大大改善主链排序的相干长度，从而改善电子和光电特性，例如电荷传输和激子扩散长度。

更新日期：2018-12-12

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