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Ambipolar polymer semiconductors are highly suited for use in flexible, printable, and large-area electronics as they exhibit both n-type (electron-transporting) and p-type (hole-transporting) operations within a single layer. This allows for cost-effective fabrication of complementary circuits with high noise immunity and operational stability. Currently, the performance of ambipolar polymer semiconductors lags behind that of their unipolar counterparts. Here, we report on the side-chain engineering of conjugated, alternating electron donor-acceptor (D-A) polymers using diketopyrrolopyrrole-selenophene copolymers with hybrid siloxane-solubilizing groups (PTDPPSe-Si) to enhance ambipolar performance. The alkyl spacer length of the hybrid side chains was systematically tuned to boost ambipolar performance. The optimized three-dimensional (3-D) charge transport of PTDPPSe-Si with pentyl spacers yielded unprecedentedly high hole and electron mobilities of 8.84 and 4.34 cm(2) V(-1) s(-1), respectively. These results provide guidelines for the molecular design of semiconducting polymers with hybrid side chains.

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While the regioregularity (RR) of conjugated polymers is known to have a strong influence on their inherent properties, systematic study of the RR effect has been limited due to the lack of a synthetic methodology. Herein, we successfully produced a series of poly(3-hexylthiophene)s (P3HTs) having a wide range of RR from 64 to 98%. Incorporation of controlled amounts of head-to-head (H−H) coupled dimer in modified Grignard metathesis polymerization allows a facile tuning of the RR of the P3HTs with comparable molecular weight and low polydispersity. Then, we investigated the effect of RR on structural, electrical, and mechanical properties of P3HTs in which a higher content of H−H regio-defects, namely lower RR, systematically lowered the degree of crystallinity. Although high RR P3HT (98%) had higher charge carrier mobility (1.81 × 10 −1 cm 2 V −1 s −1 ), its strong crystallinity induced high brittleness and stiffness, resulting in device failure under a very small strain, as shown in tensile and bending tests. The tensile modulus was reduced significantly from 287 MPa (RR 98%) to 13 MPa (RR 64%), and also the RR 64% P3HT film had much better mechanical resilience with an order of magnitude higher elongation at break than that of the RR 98% polymer. Our findings suggest that the mechanical and electrical properties of conjugated polymers can be systematically tuned by controlling the RR to meet the purposes of various organic electronic applications, i.e., flexible portable devices vs high-performance panels.

The photoelectronic characteristics of single‐crystalline nanowire organic phototransistors (NW‐OPTs) are studied using a high‐performance n‐channel organic semiconductor, N,N′‐bis(2‐phenylethyl)‐perylene‐3,4:9,10‐tetracarboxylic diimide (BPE‐PTCDI), as the photoactive layer. The optoelectronic performances of the NW‐OPTs are analyzed by way of their current–voltage (I–V) characteristics on irradiation at different wavelengths, and comparison with corresponding thin‐film organic phototransistors (OPTs). Significant enhancement in the charge‐carrier mobility of NW‐OPTs is observed upon light irradiation as compared with when performed in the dark. A mobility enhancement is observed when the incident optical power density increases and the wavelength of the light source matches the light‐absorption range of the photoactive material. The photoswitching ratio is strongly dependent upon the incident optical power density, whereas the photoresponsivity is more dependent on matching the light‐source wavelength with the maximum absorption range of the photoactive material. BPE‐PTCDI NW‐OPTs exhibit much higher external quantum efficiency (EQE) values (≈7900 times larger) than thin‐film OPTs, with a maximum EQE of 263 000%. This is attributed to the intrinsically defect‐free single‐crystalline nature of the BPE‐PTCDI NWs. In addition, an approach is devised to analyze the charge‐transport behaviors using charge accumulation/release rates from deep traps under on/off switching of external light sources.

Utilizing its integrated camera as a spectrometer, we demonstrate the use of a smartphone as the detection instrument for a label-free photonic crystal biosensor. A custom-designed cradle holds the smartphone in fixed alignment with optical components, allowing for accurate and repeatable measurements of shifts in the resonant wavelength of the sensor. Externally provided broadband light incident upon an entrance pinhole is subsequently collimated and linearly polarized before passing through the biosensor, which resonantly reflects only a narrow band of wavelengths. A diffraction grating spreads the remaining wavelengths over the camera's pixels to display a high resolution transmission spectrum. The photonic crystal biosensor is fabricated on a plastic substrate and attached to a standard glass microscope slide that can easily be removed and replaced within the optical path. A custom software app was developed to convert the camera images into the photonic crystal transmission spectrum in the visible wavelength range, including curve-fitting analysis that computes the photonic crystal resonant wavelength with 0.009 nm accuracy. We demonstrate the functionality of the system through detection of an immobilized protein monolayer, and selective detection of concentration-dependent antibody binding to a functionalized photonic crystal. We envision the capability for an inexpensive, handheld biosensor instrument with web connectivity to enable point-of-care sensing in environments that have not been practical previously.

Systematic side-chain engineering has been performed for diketopyrrolopyrrole-selenophene vinylene selenophene (DPP-SVS) polymers to determine the optimal side-chain geometries for the most efficient charge transport, and the structure-property relationship has been thoroughly investigated using a range of analyses. A series of DPP-SVS polymers, ranging from 25-DPP-SVS to 32-DPP-SVS, with branched alkyl groups containing linear spacer groups from C2 to C9 has been synthesized, and the electrical performance of these polymers is significantly dependent on both the length of the spacer group and its odd-even characteristics. Spacer groups with even numbers of carbon atoms exhibit chargecarrier mobilities that are one order of magnitude higher than those with odd numbers of carbon atoms. The optimized charge transport has been obtained from 29-DPP-SVS with C6 spacer, showing the maximum mobility of 13.9 cm 2 V −1 s −1 (V GS , V DS = −100 V) and 17.8 cm 2 V −1 s −1 (V GS , V DS = −150 V). Longer spacer groups deviate from the odd-even trend. In addition to the exceptionally high charge-carrier mobilities of the DPP-SVS polymers, the results obtained herein provide new insight into the molecular design of high-performance polymer semiconductors.

Tuning the side chains of conjugated polymers is a simple, yet effective strategy for modulating their structural and electrical properties, but their impact on n‐type conjugated polymers has not been studied extensively, particularly in the area of all‐polymer solar cells (all‐PSCs). Herein, the effects of side chain engineering of P(NDI2OD‐T2) polymer (also known as Polyera Activink N2200) are investigated, which is the most widely used n‐type polymer in all‐PSCs and organic field‐effect transistors (OFETs), on their structural and electronic properties. A series of naphthalenediimide‐bithiophene‐based copolymers (P(NDIR‐T2)) is synthesized, with different side chains (R) of 2‐hexyldecyl (2‐HD), 2‐octyldodecyl (2‐OD), and 2‐decyltetradecyl (2‐DT). The P(NDI2HD‐T2) exhibits more noticeable crystalline behaviors than P(NDI2OD‐T2) and P(NDI2DT‐T2), thereby facilitating superior 3D charge transport. For example, the P(NDI2HD‐T2) shows the highest OFET electron mobility (1.90 cm2 V−1 s−1). Also, a series of all‐PSCs is produced using different electron donors of PTB7‐Th, PTB7, and PPDT2FBT. The P(NDI2HD‐T2) based all‐PSCs produce much higher power conversion efficiency (PCE) irrespective of the electron donors. In particular, the PTB7‐Th:P(NDI2HD‐T2) forms highly ordered, strong face‐on interchain stackings, and has better intermixed bulk‐heterojunction morphology, producing the highest PCE of 6.11% that has been obtained by P(NDIR‐T2) based all‐PSCs to date.