Characterization of Interfacial Structure in Polymer-Fullerene Bulk Heterojunctions via <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mmultiscripts><mml:mrow><mml:mi mathvariant="normal">C</mml:mi></mml:mrow><mml:mprescripts/><mml:none/><mml:mrow><mml:mn>13</mml:mn></mml:mrow></mml:mmultiscripts></mml:mrow></mml:math> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mo stretchy="false">{</mml:mo><mml:mmultiscripts><mml:mrow><mml:mi mathvariant="normal">H</mml:mi></mml:mrow><mml:mprescripts/><mml:none/><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:mmultiscripts><mml:mo stretchy="false">}</mml:mo></mml:mrow></mml:math> Rotational Echo Double Resonance NMR

We introduce a new application of solid state NMR measurements towards characterizing the donor-acceptor interfaces within bulk heterojunction (BHJ) films. Rotational echo double resonance (REDOR) is used to measure dipolar couplings between ^{13}C nuclei on the acceptor phenyl-C_{61}-butyric acid methyl ester (PCBM) fullerene cage, which is ≈18% isotopically enriched with ^{13}C, and beta hydrogens on the donor poly(3-hexyl thiophene) (P3HT) main chain, which are >95% isotopically enriched with ^{2}H. The ^{13}C-^{2}H dipolar couplings are used for constraining possible models of molecular packing in the amorphous mixed phase of a P3HT/PCBM BHJ. The films studied are highly mixed (>80%) and have a maximum length scale of composition nonuniformity of ≈6 nm in the mixed phase, as demonstrated by ^{1}H spin diffusion NMR and supported by TEM. The REDOR results show that despite the lack of phase separation at length scales greater than ≈6 nm, neat P3HT and PCBM clusters exist on ≈3 nm size scales, and, for the average PCBM molecule, the number of nearest neighbors P3HTs is two.