Textile electronics embedded in clothing represent an exciting new frontier for modern healthcare and communication systems. Fundamental to the development of these textile electronics is the development of the fibers forming the cloths into electronic devices. An electronic fiber must undergo diverse scrutiny for its selection for a multifunctional textile, viz., from the material selection to the device architecture, from the wearability to mechanical stresses, and from the environmental compatibility to the end‐use management. Herein, the performance requirements of fiber‐shaped electronics are reviewed considering the characteristics of single electronic fibers and their assemblies in smart clothing. Broadly, this article includes i) processing strategies of electronic fibers with required properties from precursor to material, ii) the state‐of‐art of current fiber‐shaped electronics emphasizing light‐emitting devices, solar cells, sensors, nanogenerators, supercapacitors storage, and chromatic devices, iii) mechanisms involved in the operation of the above devices, iv) limitations of the current materials and device manufacturing techniques to achieve the target performance, and v) the knowledge gap that must be minimized prior to their deployment. Lessons learned from this review with regard to the challenges and prospects for developing fiber‐shaped electronic components are presented as directions for future research on wearable electronics.

High performance solution‐processed fluorescent and phosphorescent organic light emitting diodes (OLEDs) are achieved by water solution processing of lacunary polyoxometalates used as novel electron injection/transport materials with excellent electron mobilities and hole blocking capabilities. Green fluorescent OLEDs using poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐(1,4‐benzo‐{2,1′,3}‐thiadiazole)] (F8BT) as the emissive layer and our polyoxometalates as electron transport/hole blocking layers give a luminous efficiency up to 6.7 lm W−1 and a current efficiency up to 14.0 cd A−1 which remained nearly stable for about 500 h of operation. In addition, blue phosphorescent OLEDs (PHOLEDs) using poly(9‐vinylcarbazole) (PVK):1,3‐bis[2‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazo‐5‐yl]benzene (OXD‐7) as a host and 10.0 wt% FIrpic as the blue dopant in the emissive layer and a polyoxometalate as electron transport material give 12.5 lm W−1 and 30.0 cd A−1 power and luminous efficiency, respectively, which are among the best performance values observed to date for all‐solution processed blue PHOLEDs. The lacunary polyoxometalates exhibit unique properties such as low electron affinity and high ionization energy (of about 3.0 and 7.5 eV, respectively) which render them as efficient electron injection/hole blocking layers and, most importantly, exceptionally high electron mobility of up to 10−2 cm2 V−1 s−1.

Effective interface engineering has been shown to play a vital role in facilitating efficient charge-carrier transport, thus boosting the performance of organic photovoltaic devices. Herein, we employ water-soluble lacunary polyoxometalates (POMs) as multifunctional interlayers between the titanium dioxide (TiO) electron extraction/transport layer and the organic photoactive film to simultaneously enhance the efficiency, lifetime, and photostability of polymer solar cells (PSCs). A significant reduction in the work function (W) of TiO upon POM utilization was observed, with the magnitude being controlled by the negative charge of the anion and the selection of the addenda atom (W or Mo). By inserting a POM interlayer with ∼10 nm thickness into the device structure, a significant improvement in the power conversion efficiency was obtained; the optimized POM-modified poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2- 33 ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]:[6,6]-phenyl-C butyric acid methyl ester (PTB7:PCBM)-based PSCs exhibited an efficiency of 8.07%, which represents a 21% efficiency enhancement compared to the reference TiO cell. Similar results were obtained in POM-modified devices based on poly(3-hexylthiophene) (P3HT) with electron acceptors of different energy levels, such as PCBM or indene-C bisadduct (ICBA), which enhanced their efficiency up to 4.34 and 6.21%, respectively, when using POM interlayers; this represents a 25-33% improvement as compared to the reference cells. Moreover, increased lifetime under ambient air and improved photostability under constant illumination were observed in POM-modified devices. Detailed analysis shows that the improvements in efficiency and stability synergistically stem from the reduced work function of TiO upon POM coverage, the improved nanomorphology of the photoactive blend, the reduced interfacial recombination losses, the superior electron transfer, and the more effective exciton dissociation at the photoactive layer/POM/TiO interfaces.

In the present work, we effectively modify the TiO electron transport layer of organic solar cells with an inverted architecture using appropriately engineered porphyrin molecules. The results show that the optimized porphyrin modifier bearing two carboxylic acids as the anchoring groups and a triazine electron-withdrawing spacer significantly reduces the work function of TiO, thereby reducing the electron extraction barrier. Moreover, the lower surface energy of the porphyrin-modified substrate results in better physical compatibility between the latter and the photoactive blend. Upon employing porphyrin-modified TiO electron transport layers in PTB7:PCBM-based organic solar cells we obtained an improved average power conversion efficiency up to 8.73%. Importantly, porphyrin modification significantly increased the lifetime of the devices, which retained 80% of their initial efficiency after 500 h of storage in the dark. Because of its simplicity and efficacy, this approach should give tantalizing glimpses and generate an impact into the potential of porphyrins to facilitate electron transfer in organic solar cells and related devices.

A silanol-functionalized polyoxometalate improves the electron collecting interface.