Modulation-doping a correlated electron insulator.

Correlated electron materials (CEMs) host a rich variety of condensed matter phases. Vanadium dioxide (VO2) is a prototypical CEM with a temperature-dependent metal-to-insulator (MIT) transition with a concomitant crystal symmetry change. External control of MIT in VO2-especially without inducing structural changes-has been a long-standing challenge. In this work, we design and synthesize modulation-doped VO2-based thin film heterostructures that closely emulate a textbook example of filling control in a correlated electron insulator. Using a combination of charge transport, hard X-ray photoelectron spectroscopy, and structural characterization, we show that the insulating state can be doped to achieve carrier densities greater than 5 × 1021 cm-3 without inducing any measurable structural changes. We find that the MIT temperature (TMIT) continuously decreases with increasing carrier concentration. Remarkably, the insulating state is robust even at doping concentrations as high as ~0.2 e-/vanadium. Finally, our work reveals modulation-doping as a viable method for electronic control of phase transitions in correlated electron oxides with the potential for use in future devices based on electric-field controlled phase transitions.

Charge polarity-dependent ion-insertion asymmetry during electrochemical doping of an ambipolar π-conjugated polymer.

Electrochemical doping is central to a host of important applications such as bio-sensing, neuromorphic computing and charge storage. However, the mechanisms that enable electrochemical dopability and the various parameters that control doping efficiencies are poorly understood. Here, employing complementary electrochemical and spectroelectrochemical measurements, we report a charge-polarity dependent ion insertion asymmetry in a diketopyrrolopyrrole-based ambipolar π-conjugated polymer. We argue that electrostatic interactions are insufficient to fully account for the observed charge-specific ion insertion into the polymer matrix. Using polymer side-chain dependent electrochemical doping studies, we show that electron density donating and accepting tendencies of polymer side-chains sufficiently describe the observed charge-polarity dependent electrochemical doping. Our observations are akin to the solvation of dopant ions by polymer side-chains. We propose that Gutmann donor/acceptor number framework qualifies the 'solvent-like' properties of polymer side-chains and provides a rational basis for designing π-conjugated polymers with favorable mixed ionic electronic transport properties.