Control of Shell Morphology in p–n Heterostructured Water‐Processable Semiconductor Colloids: Toward Extremely Efficient Charge Separation

Abstract

This article describes p–n heterostructured water‐borne semiconductor naonoparticles (NPs) with unique surface structures via control of shell morphology. The shell particles, comprising PC60–[6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) composite, having n‐type semiconductor characteristics, notably influence the charge carrier behavior in the core–shell NPs. A one‐ or two‐phase methodology based on a PC60 surfactant‐water phase and PC61BM n‐type semiconductor‐organic phase provides highly specific control over the shell structure of the NPs, which promote their superior charge separation ability when combined with poly‐3‐hexyl‐thiophene (P3HT). Moreover, the resulting water‐borne NP exhibits shell morphology‐dependent carrier quenching and stability, which is characterized via luminescence studies paired with structural analysis. Corresponding to the results, outstanding performances of photovoltaic cells with over 5% efficiency are achieved. The results suggest that the surrounding shell environments, such as the shell structure, and its electronic charge density, are crucial in determining the overall activity of the core–shell p–n heterostructured NPs. Thus, this work provides a new protocol in the current fields of water‐based organic semiconductor colloids.

Recent advances in the green processing of organic photovoltaic devices from nanoparticle dispersions

“…Finally, OPV devices were prepared with these particles, resulting in a PCE of 2.62%, higher than P3HT:PC 61 BM particles prepared with non-ionic C 16 E 10 surfactant (1.68%), or with SDS (1.37%). In another paper, 37 they proposed to increase the electronic charge density of the shell of the NPs, in which the C 60 groups are surrounded by PEG moieties, by adding PC 61 BM molecules in the shell of the particles. Two preparation protocols were discussed, leading to different particles with more or less PC 61 BM in the shell (Fig.…”

Aqueous Carbon Quantum Dot-Embedded PC60-PC61BM Nanospheres for Ecological Fluorescent Printing: Contrasting Fluorescence Resonance Energy-Transfer Signals between Watermelon-like and Random Morphologies

“…Impressively, however, the inner morphology of the particles varied considerably with the PC60 concentration. Most of all, the particles decreased in diameter with the addition of PC60 (75.6 nm for 3 mg mL −1 , 73.8 nm for 6 mg mL −1 , 71.3 nm for 9 mg mL −1 , 68.7 nm for 18 mg mL −1 , 66.5 nm for 24 mg mL −1 , and 63.2 nm for 30 mg mL −1 ), consistent with our previous work, 17,18 because of the stronger interactions between the C 60 's in PC60s. The trends in the dynamic light scattering (DLS) results support this result (Figure S10).…”

“…In previous studies, a fullerene surfactant grafted with a polyethylene glycol (PEG) chain, PC60, facilitated the fabrication of a precisely separated core–shell morphology in p–n heterostructured colloids, enabling us to control the shell particles independently. This resulted in extremely efficient particle photonic dynamics, particularly charge separation, and achieved the highest photovoltaic efficiency. , The independent design of the shell particles opened up numerous possibilities to create various particle formations, such as a PC60-PC 61 BM (([6,6]-phenyl-C61-butyric acid methyl ester) mixture, and facilitated control over interactions with the core and the electronic charge density. This potential brings an additional challenge in photonic activity aspect; we have imagined that the PC60-PC 61 BM sphere with a water-soluble fluorescence material will provide a new fluorescence system, which would be utilized in ecological light-emitting display.…”

“…In our previous work, 18 we synthesized a mixture particle, PC60-PC 61 BM (PC 61 BM core-PC60 surfactant covered colloid, Figure S1c) using a homogenization process. We found that a double-layer structure of PC60 (a PEG (core)two C 60 's (shell)-PEG (second shell) micelle structure, Figure S1d) was kept in the shell part of the particle.…”

Globular Aggregates Stemming from the Self-Assembly of an Amphiphilic N-Annulated Perylene Bisimide in Aqueous Media

“…In these supramolecular aggregates, the balance between hydrophobic and hydrophilic interactions plays a major role in conditioning both the stability and the morphology of such structures [2]. At the same time, the hydrophobic effect provides robustness to the final ensembles that prompts their potential applicability in the area of functional supramolecular materials and, more specifically, in the so-called supramolecular "aquamaterials" in which water molecules favor the efficient self-assembly of small molecules that can be disassembled upon applying specific stimuli [3][4][5]. Among the vast number of supramolecular "aquamaterials", hydrogels [6] or organic nanocrystals [7] are at the forefront of the field.…”