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Two-dimensional conjugated polymers (2DCPs), composed of multiple strands of linear conjugated polymers with extended in-plane π-conjugation, are emerging crystalline semiconducting polymers for organic (opto)electronics. They are represented by two-dimensional π-conjugated covalent organic frameworks, which typically suffer from poor π-conjugation and thus low charge carrier mobilities. Here we overcome this limitation by demonstrating two semiconducting phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type 2DCPs (2DCP-MPc, with M = Cu or Ni), which are constructed from octaaminophthalocyaninato metal(ii) and naphthalenetetracarboxylic dianhydride by polycondensation under solvothermal conditions. The 2DCP-MPcs exhibit optical bandgaps of ~1.3 eV with highly delocalized π-electrons. Density functional theory calculations unveil strongly dispersive energy bands with small electron–hole reduced effective masses of ~0.15m0for the layer-stacked 2DCP-MPcs. Terahertz spectroscopy reveals the band transport of Drude-type free carriers in 2DCP-MPcs with exceptionally high sum mobility of electrons and holes of ~970 cm2V−1s−1at room temperature, surpassing that of the reported linear conjugated polymers and 2DCPs. This work highlights the critical role of effective conjugation in enhancing the charge transport properties of 2DCPs and the great potential of high-mobility 2DCPs for future (opto)electronics.

Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are emerging as a unique class of semiconducting 2D conjugated polymers for (opto)electronics and energy storage. Doping is one of the common, reliable strategies to control the charge carrier transport properties, but the precise mechanism underlying COF doping has remained largely unexplored. Here we demonstrate molecular iodine doping of a metal–phthalocyanine-based pyrazine-linked 2D c-COF. The resultant 2D c-COF ZnPc-pz-I2maintains its structural integrity and displays enhanced conductivity by 3 orders of magnitude, which is the result of elevated carrier concentrations. Remarkably, Hall effect measurements reveal enhanced carrier mobility reaching ∼22 cm2V–1s–1for ZnPc-pz-I2, which represents a record value for 2D c-COFs in both the direct-current and alternating-current limits. This unique transport phenomenon with largely increased mobility upon doping can be traced to increased scattering time for free charge carriers, indicating that scattering mechanisms limiting the mobility are mitigated by doping. Our work provides a guideline on how to assess doping effects in COFs and highlights the potential of 2D c-COFs to display high conductivities and mobilities toward novel (opto)electronic devices.

π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, and conductivity in π-conjugated 2D COFs remains elusive. Here, we report a detailed characterization for the electronic properties of two novel samples consisting of Zn– and Cu–phthalocyanine-based pyrazine-linked 2D COFs. These 2D COFs are synthesized by condensation of metal–phthalocyanine (M = Zn and Cu) and pyrene derivatives. The obtained polycrystalline-layered COFs are p-type semiconductors both with a band gap of ∼1.2 eV. A record device-relevant mobility up to ∼5 cm2/(V s) is resolved in the dc limit, which represents a lower threshold induced by charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) and terahertz (THz) spectroscopy (ac limit) in combination with density functional theory (DFT) calculations demonstrate that varying metal center from Cu to Zn in the phthalocyanine moiety has a negligible effect in the conductivity (∼5 × 10–7S/cm), charge carrier density (∼1012cm–3), charge carrier scattering rate (∼3 × 1013s–1), and effective mass (∼2.3m0) of majority carriers (holes). Notably, charge carrier transport is found to be anisotropic, with hole mobilities being practically null in-plane and finite out-of-plane for these 2D COFs.

Metal–organic frameworks (MOFs) are hybrid materials based on crystalline coordination polymers that consist of metal ions connected by organic ligands. In addition to the traditional applications in gas storage and separation or catalysis, the long-range crystalline order in MOFs, as well as the tunable coupling between the organic and inorganic constituents, has led to the recent development of electrically conductive MOFs as a new generation of electronic materials. However, to date, the nature of charge transport in the MOFs has remained elusive. Here we demonstrate, using high-frequency terahertz photoconductivity and Hall effect measurements, Drude-type band-like transport in a semiconducting, π–d conjugated porous Fe3(THT)2(NH4)3(THT, 2,3,6,7,10,11-triphenylenehexathiol) two-dimensional MOF, with a room-temperature mobility up to ~ 220 cm2V–1s–1. The temperature-dependent conductivity reveals that this mobility represents a lower limit for the material, as mobility is limited by impurity scattering. These results illustrate the potential for high-mobility semiconducting MOFs as active materials in thin-film optoelectronic devices.

Hot carrier cooling processes represent one of the major efficiency losses in solar energy conversion. Losses associated with cooling can in principle be circumvented if hot carrier extraction toward selective contacts is faster than hot carrier cooling in the absorber (in so-called hot carrier solar cells). Previous work has demonstrated the possibility of hot electron extraction in quantum dot (QD)-sensitized systems, in particular, at low temperatures. Here we demonstrate a room-temperature hot electron transfer (HET) with up to unity quantum efficiency in strongly coupled PbS quantum dot-sensitized mesoporous SnO2. We show that the HET efficiency is determined by a kinetic competition between HET rate (KHET) and the thermalization rate (KTH) in the dots. KHETcan be modulated by changing the excitation photon energy; KTHcan be modified through the lattice temperature. DFT calculations demonstrate that the HET rate and efficiency are primarily determined by the density of the state (DoS) of QD and oxide. Our results provide not only a new way to achieve efficient hot electron transfer at room temperature but also new insights on the mechanism of HET and the means to control it.

The long-term stability of dye-sensitized solar cells (DSSCs) is determined to a large extent by the photodegradation of their sensitizers. Understanding the mechanism of light-induced decomposition of dyes sensitizing a mesoporous oxide matrix may therefore contribute to solutions to increase the life span of DSSCs. Here, we investigate, using ultrafast terahertz photoconductivity measurements, the evolution of interfacial electron-transfer (ET) dynamics in Ru(4,4′-dicarboxylic acid-2,2′-bipyridine)2(NCS)2(N3) dye-sensitized mesoporous TiO2electrodes upon dye photodegradation. Under inert environment, interfacial ET dynamics do not change over time, indicating that the dye is stable and photodegradation is absent; the associated ET dynamics are characterized by a sub-100 fs rise of the photoconductivity, followed by long-lived (≫1 ns) electrons in the oxide electrode. When the N3–TiO2sample is exposed to air under identical illumination conditions, dye photodegradation is evident from the disappearance of the optical absorption associated with the dye. Remarkably, approximately half of the sub-100 fs ET is observed to still occur but is followed by very rapid (∼10 ps) electron–hole recombination. Laser desorption/ionization mass spectrometry, attenuated total reflection–Fourier transform infrared, and terahertz photoconductivity analyses reveal that the photodegraded ET signal originates from the N3 dye photodegradation product as bi-isonicotinic acid (4,4′-dicarboxylic acid-2,2′-bipyridine), which remains bonded to the TiO2surface via either bidentate chelation or bridging-type geometry.

We investigate photoinduced carrier dynamics by time-resolved terahertz spectroscopy (TRTS) in Pt nanoparticle decorated CdSe tetrapods as a function of Pt nanoparticles size (and identical areal density). We find that the collection efficiency of electrons photogenerated in the tetrapods by the Pt particle increases as a function of Pt nanoparticle size. However, the photocatalytic H2generation efficiency is reduced for tetrapods decorated with larger Pt particles. Our results demonstrate a competition between electron capture efficiency at the semiconducting/metal interface, increasing with nanoparticles size, and electron release efficiency at the metal/water interface, decreasing with nanoparticles size. This trade-off defines an optimum for photocatalytic H2generation in Pt cocatalyst decorated CdSe tetrapods as a function of Pt size.

Reducing the donor–acceptor excess energy (ΔGET) associated with electron transfer (ET) across quantum dot (QD)/oxide interfaces can boost photoconversion efficiencies in sensitized solar cell and fuel architectures. One proposed path for engineering ΔGETlosses at interfaces refers to the tuning of sensitizer workfunction by exploiting QD dipolar molecular capping treatments. However, the change in workfunction per debye in QD solids has been reported to be ∼20-fold larger when compared to the effect achieved in QD-sensitized architectures. The origin behind the modest workfunction tunability in QD-sensitized oxides remains unclear. Here, we investigate the interplay between QD dipolar molecular capping, interfacial QD–oxide ET rates, and QD workfunction in PbS QD/SnO2-sensitized interfaces. We find that interfacial QD-to-oxide ET is invariant to both the nature and strength of the specific QD dipolar capping treatment. Photoelectron spectroscopy reveals that the resolved invariance in ET rates is the result of a lack of QD workfunction (and hence ΔGET) tuning, despite effective molecular dipolar capping. We therefore conclude that Fermi level pinning precludes tuning donor–acceptor energetics by dipolar molecular capping in strongly coupled quantum dot-sensitized oxides.