High-Yield Dispersions of Large-Diameter Semiconducting Single-Walled Carbon Nanotubes with Tunable Narrow Chirality Distributions

Abstract

Here, we report a thorough study on the ability of fluorene-based semiconducting polymers to disperse large-diameter (average diameter ⟨d⟩ ≈ 1.3 nm) laser vaporization (LV) single-walled carbon nanotubes (SWCNTs). We demonstrate the ability to select purely semiconducting species using poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(6,6'-{2,2'-bipyridine})] (PFO-BPy) and poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(9,10-anthracene)] (PFH-A), producing samples with narrow and bright excitonic emission relative to comparable aqueous dispersions. Rapid processing and high yields offer the ability to easily incorporate these semiconducting SWCNTs into commercially scalable applications, as demonstrated by large-area thin films prepared by ultrasonic spraying. By modifying the growth temperature of the LV synthesis, we demonstrate the ability to tune the range of diameters and chiralities within dispersions by exerting synthetic control over the composition of the starting material. This synthetic control allows us to show that PFH-A preferentially disperses near-armchair semiconducting SWCNTs over a large range of diameters (0.8 nm < d < 1.4 nm) and induces unique solvatochromic shifts for the excitonic transitions of nanotubes with particular chiral indices.

Diameter dependence of TO phonon frequencies and the Kohn anomaly in armchair single-wall carbon nanotubes

“…1. The DGU method provides an enrichment of armchair chiralities in general, showing enrichment in armchair species (6,6)- (10,10) (6,6) and (7,7) enriched via DNA-IEX and (5,5) via ATPE using CoMoCAT SG65 and SG65i material, respectively. Finally, ATPE was also used to generate a (6,6)-enriched sample from CoMoCAT SG65i material [absorption spectrum Fig.…”

Semiconducting single-walled carbon nanotubes sorting with a removable solubilizer based on dynamic supramolecular coordination chemistry

“…In order to preserve the intrinsic SWNT properties, the latter method has an advantage over the former one. Recently, various methods for the separation of sem-and met-SWNTs including wrapping by SWNT solubilizers, such as DNAs 20,21 and p-conjugated or non-conjugated copolymers 11,[22][23][24] , density gradient ultracentrifugation 25,26 and gel chromatography techniques 12,14,[27][28][29][30][31][32][33][34][35][36][37][38][39] , have been reported. However, the reported techniques are rather complex and the efficiency is not very high.…”

Interação de nanotubos de carbono e cadeias de polifluoreno: Dinâmica molecular e espectroscopia

“…Dentre os copolímeros baseados em uoreno, aqueles compostos com benzotiadiazol [67] (Fig. 2.15(a)), bipiridina (Fig 2.15(b)) e antraceno (Fig 2.15(c)) [68] se mostraram capazes de suspender nanotubos de grande diâmetro. Funcionalizar os polímeros conjugados, cuja cadeia é geralmente hidrofóbica, também permite alterar sua dispersibilidade em água ao ligar radicais polares à cadeia principal [34] .…”

“…Experimentos recentes [66][67][68] mostram que o comprimento das cadeias laterais de polímeros tem de fato efeito na seletividade da suspensão dos nanotubos. Tange e seus colaboradores [67] observaram que é possível suspender nanotubos de diâmetro maior que 1,3 nm utilizando diferentes polímeros derivados de poli uoreno.…”

“…Kevin Mistry e colaboradores [68] relataram sucesso em suspender nanotubos semicondutores de grande diâmetro utilizando dois copolímeros derivados do uoreno: poli[(9,9-dioctil uorenil)-alt-{6,6 (2,2 -bipiridina)}] (PFO-BPy, Nesse trabalho, argumenta-se que tanto a coincidência dos níveis eletrônicos entre polímero e nanotubo proposta por Tange [67] quanto a interdigitação das cadeias laterais [36 e Seção 4.4] são insu cientes para explicar a seletividade e se sugere que a geometria que o PFH-A adota em torno dos tubos deve ser extremamente sensível à quiralidade, mas não se propõe um mecanismo para isso.…”