Chiu-Hun Su

Competition between Fullerene Aggregation and Poly(3-hexylthiophene) Crystallization upon Annealing of Bulk Heterojunction Solar Cells

Concomitant development of [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) aggregation and poly(3-hexylthiophene) (P3HT) crystallization in bulk heterojunction (BHJ) thin-film (ca. 85 nm) solar cells has been revealed using simultaneous grazing-incidence small-/wide-angle X-ray scattering (GISAXS/GIWAXS). With enhanced time and spatial resolutions (5 s/frame; minimum q ≈ 0.004 Å(-1)), synchrotron GISAXS has captured in detail the fast growth in size of PCBM aggregates from 7 to 18 nm within 100 s of annealing at 150 °C. Simultaneously observed is the enhanced crystallization of P3HT into lamellae oriented mainly perpendicular but also parallel to the substrate. An Avrami analysis of the observed structural evolution indicates that the faster PCBM aggregation follows a diffusion-controlled growth process (confined by P3HT segmental motion), whereas the slower development of crystalline P3HT nanograins is characterized by constant nucleation rate (determined by the degree of supercooling and PCBM demixing). These two competing kinetics result in local phase separation with space-filling PCBM and P3HT nanodomains less than 20 nm in size when annealing temperature is kept below 180 °C. Accompanying the morphological development is the synchronized increase in electron and hole mobilities of the BHJ thin-film solar cells, revealing the sensitivity of the carrier transport of the device on the structural features of PCBM and P3HT nanodomains. Optimized structural parameters, including the aggregate size and mean spacing of the PCBM aggregates, are quantitatively correlated to the device performance; a comprehensive network structure of the optimized BHJ thin film is presented.

Non-volatile organic field-effect transistor memory comprising sequestered metal nanoparticles in a diblock copolymer film

In this study, we fabricated p-channel-type non-volatile organic field-effect transistor (OFET) memory devices featuring an asymmetric PS-b-P4VP diblock copolymer layer incorporating high- and low-work-function metal nanoparticles (NPs) in the hydrophilic and hydrophobic blocks, respectively. We chose the highly asymmetric diblock copolymer PS56k-b-P4VP8k as the polymer electret to create the memory windows, and used the different work functions of the ex situ-synthesized metal NPs to tune the memory window for either p- or n-channel applications. The transfer curves of non-volatile OFET memory devices incorporating an asymmetric PS56k-b-P4VP8k layer embedded with high-work-function Pt NPs (5.65 eV) in the P4VP block exhibited a positive threshold voltage shift and a large memory window (ca. 27 V). In contrast, the transfer curves of the corresponding non-volatile OFET memory devices featuring embedded low-work-function (4.26 eV) Ag NPs exhibited a negative threshold voltage shift and a smaller memory window (ca. 19 V). This approach provides a versatile way to fabricate p- or possibly n-channel-type non-volatile organic field-effect transistor (OFET) memory devices with the same processing procedure.