Conspectus The electronic dimensionality of a material is defined by the number of spatial degrees of confinement of its electronic wave function. Low-dimensional semiconductor nanomaterials with at least one degree of spatial confinement have optoelectronic properties that are tunable with size and environment (dielectric and chemical) and are of particular interest for optoelectronic applications such as light detection, light harvesting, and photocatalysis. By combining nanomaterials of differing dimensionalities, mixed-dimensional heterojunctions (MDHJs) exploit the desirable characteristics of their components. For example, the strong optical absorption of zero-dimensional (0D) materials combined with the high charge carrier mobilities of two-dimensional (2D) materials widens the spectral response and enhances the responsivity of mixed-dimensional photodetectors, which has implications for ultrathin, flexible optoelectronic devices. MDHJs are highly sensitive to (i) interfacial chemistry because of large surface area-to-volume ratios and (ii) electric fields, which are incompletely screened because of the ultrathin nature of MDHJs. This sensitivity presents opportunities for control of physical phenomena in MDHJs through chemical modification, optical excitation, externally applied electric fields, and other environmental parameters. Since this fast-moving research area is beginning to pose and answer fundamental questions that underlie the fundamental optoelectronic behavior of MDHJs, it is an opportune time to assess progress and suggest future directions in this field. In this Account, we first outline the characteristic properties, advantages, and challenges for low-dimensional materials, many of which arise as a result of quantum confinement effects. The optoelectronic properties and performance of MDHJs are primarily determined by dynamics of excitons and charge carriers at their interfaces, where these particles tunnel, trap, scatter, and/or recombine on the time scales of tens of femtoseconds to hundreds of nanoseconds. We discuss several photophysical phenomena that deviate from those observed in bulk heterojunctions, as well as factors that can be used to vary, probe, and ultimately control the behavior of excitons and charge carriers in MDHJ systems. We then discuss optoelectronic applications of MDHJs, namely, photodetectors, photovoltaics, and photocatalysts, and identify current performance limits compared to state-of-the-art benchmarks. Finally, we suggest strategies to extend the current understanding of dynamics in MDHJs toward the realization of stimuli-driven responses, particularly with respect to exciton delocalization, quantum emission, interfacial morphology, responsivity to external stimuli, spin selectivity, and usage of chemically reactive materials.
The weak van der Waals bonding between monolayers in layered materials enables fabrication of heterostructures without the constraints of conventional heteroepitaxy. Although many novel heterostructures have been created by mechanical exfoliation and stacking, the direct growth of 2D chalcogenide heterostructures creates new opportunities for large-scale integration. This paper describes the epitaxial growth of layered, p-type tin sulfide (SnS) on n-type molybdenum disulfide (MoS2) by pulsed metal–organic chemical vapor deposition at 180 °C. The influence of precursor pulse and purge times on film morphology establishes growth conditions that favor layer-by-layer growth of SnS, which is critical for materials with layer-dependent electronic properties. Kelvin probe force microscopy measurements determine a built-in potential as high as 0.95 eV, and under illumination a surface photovoltage is generated, consistent with the expected Type-II band alignment for a multilayer SnS/MoS2 heterostructure. The bottom-up growth of a nonisostructural heterojunction comprising 2D semiconductors expands the combinations of materials available for scalable production of ultrathin devices with field-tunable responses.
Semiconductors possessing both magnetic and optoelectronic properties are rare and promise applications in opto-spintronics. Here we report the mixed-anion semiconductor BaFMn0.5Te with a band gap of 1.76 eV and a work function of 5.08 eV, harboring both antiferromagnetism (AFM) and strong red photoluminescence (PL). The synthesis of BaFMn0.5Te in quantitative yield was accomplished using the “panoramic synthesis” technique and synchrotron radiation to obtain the full reaction map, from which we determined that the compound forms upon heating at 850 °C via an intermediate unknown phase. The structure refinement required the use of a (3+1)-dimensional superspace group Cmme(α01/2)0ss. The material crystallizes into a ZrCuSiAs-like structure with alternating [BaF]+ and [Mn0.5Te]− layers and has a commensurately modulated structure with the q-vector of 1/6a* + 1/6b* + 1/2c* at room temperature arising from the unique ordering pattern of Mn2+ cations. Long-range AFM order emerges below 90 K, with two-dimensional short-range AFM correlations above the transition temperature. First-principles calculations indicate that BaFMn0.5Te is an indirect band gap semiconductor with the gap opening between Te 5p and Mn 3d orbitals, and the magnetic interactions between nearest-neighbor Mn2+ atoms are antiferromagnetic. Steady-state PL spectra show a broad strong emission centered at ∼700 nm, which we believe originates from the energy manifolds of the modulated Mn2+ sublattice and its defects. Time-resolved PL measurements reveal an increase in excited-state lifetimes with longer probe wavelengths, from 93 ns (at 650 nm) to 345 ns (at 800 nm), and a delayed growth (6.5 ± 0.3 ns) in the kinetics at 800 nm with a concomitant decay (4.1 ± 0.1 ns) at 675 nm. Together, these observations suggest that there are multiple emissive states, with higher energy states populating lower energy states by energy transfer.
Intermittent periods of low light emission (“blinking”) and time-dependent emission spectra (spectral diffusion, SD) have proven to be major obstacles to the adoption of colloidal semiconductor nanocrystals as quantum emitters. One clue to the mechanisms behind these two phenomena is how they are related, which is difficult to determine at time scales faster than can be captured using a spectrometer (∼100 ms). This work utilizes spectral correlations to access a range of time scales from 10 μs to 10 s and determines that, for quasi-2D CdSe/CdS core/shell nanoplatelets (NPLs), blinking occurs on time scales from 100 μs to seconds but is only accompanied by SD on the ∼1 s time scale and slower. This result indicates that shorter time scale blinking is due only to an equilibrium between dark and bright states with a shared, uncharged ground state, while longer time scale blinking receives contributions from an equilibrium between two distinct emissive states. The 10–15 meV energy range sampled by the NPL emission during SD implies that the two emissive states are an exciton and a trion.
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