Optical Studies of Doped Two-Dimensional Lead Halide Perovskites: Evidence for Rashba-Split Branches in the Conduction Band.

Two-dimensional (2D) hybrid organic/inorganic perovskites are an emerging materials class for optoelectronic and spintronic applications due to strong excitonic absorption and emission, large spin-orbit coupling, and Rashba spin-splitting effects. For many of the envisioned applications, tuning the majority charge carrier (electron or hole) concentration is desirable, but electronic doping of metal-halide perovskites has proven to be challenging. Here, we demonstrate electron injection into the lower-energy branch of the Rashba-split conduction band of 2D phenethylammonium lead iodide by means of n-type molecular doping at room temperature. The molecular dopant, benzyl viologen (BV), is shown to compensate adventitious p-type impurities and can lead to a tunable Fermi level above the conduction band minimum and increased conductivity in intrinsic samples. The doping-induced carrier concentration is monitored by the observation of free-carrier absorption and intraband optical transitions in the infrared spectral range. These optical measurements allow for an estimation of the Rashba splitting energy ER ≈38 ± 4 meV. Photoinduced quantum beating measurements demonstrate that the excess electron density reduces the electron spin g-factor by ca. 6%. This work demonstrates controllable carrier concentrations in hybrid organic/inorganic perovskites and yields potential for room temperature spin control through the Rashba effect.

Controlling the thermoelectric properties of organo-metallic coordination polymers through backbone geometry.

Poly(nickel-benzene-1,2,4,5-tetrakis(thiolate)) (Ni-btt), an organometallic coordination polymer (OMCP) characterized by the coordination between benzene-1,2,4,5-tetrakis(thiolate) (btt) and Ni2+ ions, has been recognized as a promising p-type thermoelectric material. In this study, we employed a constitutional isomer based on benzene-1,2,3,4-tetrakis(thiolate) (ibtt) to generate the corresponding isomeric polymer, poly(nickel-benzene-1,2,3,4-tetrakis(thiolate)) (Ni-ibtt). Comparative analysis of Ni-ibtt and Ni-btt reveals several common infrared (IR) and Raman features attributed to their similar square-planar nickel-sulfur (Ni-S) coordination. Nevertheless, these two polymer isomers exhibit substantially different backbone geometries. Ni-btt possesses a linear backbone, whereas Ni-ibtt exhibits a more undulating, zig-zag-like structure. Consequently, Ni-ibtt demonstrates slightly higher solubility and an increased bandgap in comparison to Ni-btt. The most noteworthy dissimilarity, however, manifests in their thermoelectric properties. While Ni-btt exhibits p-type behavior, Ni-ibtt demonstrates n-type carrier characteristics. This intriguing divergence prompted further investigation into the influence of OMCP backbone geometry on the electronic structure and, particularly, the thermoelectric properties of these materials.

Closed-Loop Error-Correction Learning Accelerates Experimental Discovery of Thermoelectric Materials.

The exploration of thermoelectric materials is challenging considering the large materials space, combined with added exponential degrees of freedom coming from doping and the diversity of synthetic pathways. Here, historical data is incorporated, and is updated using experimental feedback by employing error-correction learning (ECL). This is achieved by learning from prior datasets and then adapting the model to differences in synthesis and characterization that are otherwise difficult to parameterize. This strategy is thus applied to discovering thermoelectric materials, where synthesis is prioritized at temperatures <300 °C. A previously unexplored chemical family of thermoelectric materials, PbSe:SnSb, is documented, finding that the best candidate in this chemical family, 2 wt% SnSb doped PbSe, exhibits a power factor more than 2× that of PbSe. The investigations herein reveal that a closed-loop experimentation strategy reduces the required number of experiments to find an optimized material by a factor as high as 3× compared to high-throughput searches powered by state-of-the-art machine-learning (ML) models. It is also observed that this improvement is dependent on the accuracy of the ML model in a manner that exhibits diminishing returns: once a certain accuracy is reached, factors that are instead associated with experimental pathways begin to dominate trends.

Backbone-driven host-dopant miscibility modulates molecular doping in NDI conjugated polymers.

Molecular doping is the key to enabling organic electronic devices, however, the design strategies to maximize doping efficiency demands further clarity and comprehension. Previous reports focus on the effect of the side chains, but the role of the backbone is still not well understood. In this study, we synthesize a series of NDI-based copolymers with bithiophene, vinylene, and acetylenic moieties (P1G, P2G, and P3G, respectively), all containing branched triethylene glycol side chains. Using computational and experimental methods, we explore the impact of the conjugated backbone using three key parameters for doping in organic semiconductors: energy levels, microstructure, and miscibility. Our experimental results show that P1G undergoes the most efficient n-type doping owed primarily to its higher dipole moment, and better host-dopant miscibility with N-DMBI. In contrast, P2G and P3G possess more planar backbones than P1G, but the lack of long-range order, and poor host-dopant miscibility limit their doping efficiency. Our data suggest that backbone planarity alone is not enough to maximize the electrical conductivity (σ) of n-type doped organic semiconductors, and that backbone polarity also plays an important role in enhancing σ via host-dopant miscibility. Finally, the thermoelectric properties of doped P1G exhibit a power factor of 0.077 µW m-1 K-2, and ultra-low in-plane thermal conductivity of 0.13 W m-1K-1 at 5 mol% of N-DMBI, which is among the lowest thermal conductivity values reported for n-type doped conjugated polymers.

Molecular Doping of a Naphthalene Diimide-Bithiophene Copolymer and SWCNTs for n-Type Thermoelectric Composites.

Molecular doping is a powerful tool to tune the thermoelectric (TE) properties of solution-processed semiconductors. In this work, we prepared a binary composite and effectively doped both of its constituents, that is, naphthalene diimide-bithiophene copolymers (PNDI2OD-T2) and single-walled carbon nanotubes (SWCNTs), by a 1H-benzimidazole derivative (N-DMBI). The doped composites show an n-type character and an in-plane TE figure of merit (ZT), exceeding the values obtained with the doped polymers. The use of SWCNTs consistently results in a higher σ with a maximum value above 102 S/cm, resulting in the highest power factor of 18.1 µW/mK2 for an SWCNT loading of 45.5 wt %. Furthermore, an SWCNT content up to 9 wt % does not compromise the low thermal conductivity of the polymer matrices, leading to a ZT value of 0.0045. The n-type composites show good solution processability and relatively stable Seebeck coefficients upon air exposure for 8 months.

The ultralow thermal conductivity and tunable thermoelectric properties of surfactant-free SnSe nanocrystals.

Most studies to date on SnSe thermal transport are focused on single crystals and polycrystalline pellets that are obtained using high-temperature processing conditions and sophisticated instruments. The effects of using sub-10 nm-size SnSe nanocrystals on the thermal transport and thermoelectric properties have not been studied to the best of our knowledge. Here, we report the synthesis of sub-10 nm colloidal surfactant-free SnSe NCs at a relatively low temperature (80 °C) and investigate their thermoelectric properties. Pristine SnSe NCs exhibit p-type transport but have a modest power factor of 12.5 µW m-1 K-2 and ultralow thermal conductivity of 0.1 W m-1 K-1 at 473 K. Interestingly, the one-step post-synthesis treatment of NC film with methylammonium iodide can switch the p-type transport of the pristine film to n-type. The power factor improved significantly to 20.3 µW m-1 K-2, and the n-type NCs show record ultralow thermal conductivity of 0.14 W m-1 K-1 at 473 K. These surfactant-free SnSe NCs were then used to fabricate flexible devices that show superior performance to rigid devices. After 20 bending cycles, the flexible device shows a 34% loss in the power factor at room temperature (295 K). Overall, this work demonstrates p- and n-type transport in SnSe NCs via the use of simple one-step post-synthesis treatment, while retaining ultralow thermal conductivity.

Halide Perovskites: Thermal Transport and Prospects for Thermoelectricity.

The recent re-emergence of halide perovskites has received escalating interest for optoelectronic applications. In addition to photovoltaics, the multifunctional nature of halide perovskites has led to diverse applications. The ultralow thermal conductivity coupled with decent mobility and charge carrier tunability led to the prediction of halide perovskites as a possible contender for future thermoelectrics. Herein, recent advances in thermal transport of halide perovskites and their potentials and challenges for thermoelectrics are reviewed. An overview of the phonon behavior in halide perovskites, as well as the compositional dependency is analyzed. Understanding thermal transport and knowing the thermal conductivity value is crucial for creating effective heat dissipation schemes and determining other thermal-related properties like thermo-optic coefficients, hot-carrier cooling, and thermoelectric efficiency. Recent works on halide perovskite-based thermoelectrics together with theoretical predictions for their future viability are highlighted. Also, progress on modulating halide perovskite-based thermoelectric properties using light and chemical doping is discussed. Finally, strategies to overcome the limiting factors in halide perovskite thermoelectrics and their prospects are emphasized.

Giant Humidity Effect on Hybrid Halide Perovskite Microstripes: Reversibility and Sensing Mechanism.

Despite the exceptional performance of hybrid perovskites in photovoltaics, their susceptibility to ambient factors, particularly humidity, gives rise to the well-recognized stability issue. In the present work, microstripes of CH3NH3PbI3 are fabricated on flexible substrates, and they exhibit much larger response to relative humidity (RH) levels than continuous films and single crystals. The resistance of microstripes decreases by four orders of magnitude on changing the RH level from 10 to 95%. Fast response and recovery time of 100 and 500 ms, respectively, are recorded. Because bulk diffusion and defect trapping are much slower processes, our result indicates a surface-dictated mechanism related to hydrate formation and electron donation. In addition, water uptake behavior of perovskites is studied for the first time, which correlates well with the resistance decrease of the CH3NH3PbI3 microstripes. Furthermore, we report that the photoresponse decreases with increasing humidity, and at the 85% RH level, the perovskite device is not photoresponsive anymore. Our work underscores patterned structures as a new platform to investigate the interaction of hybrid perovskites with ambient factors and reveals the importance of the humidity effect on optoelectronic performance.

Stable Bandgap-Tunable Hybrid Perovskites with Alloyed Pb-Ba Cations for High-Performance Photovoltaic Applications.

The intrinsic poor stability of MAPbI3 hybrid perovskites in the ambient environment remains as the major challenge for photovoltaic applications. In this work, complementary first-principles calculations and experimental characterizations reveal that metal cation alloyed perovskite (MABa xPb1- xI3) can be synthesized and exhibit substantially enhanced stability via forming stronger Ba-I bonds. The Ba-Pb alloyed perovskites remain phase-pure in ambient air for more than 15 days. Furthermore, the bandgap of MABa xPb1- xI3 is tailored in a wide window of 1.56-4.08 eV. Finally, MABa xPb1- xI3 is used as a capping layer on MAPbI3 in solar cells, resulting in significantly improved power conversion efficiency (18.9%) and long-term stability (>30 days). Overall, our results provide a simple but reliable strategy toward stable less-Pb perovskites with tailored physical properties.

Narrow bandgap oxide nanoparticles coupled with graphene for high performance mid-infrared photodetection.

The pursuit of optoelectronic devices operating in the mid-infrared regime is driven by both fundamental interests and envisioned applications ranging from imaging, sensing to communications. Despite continued achievements in traditional semiconductors, notorious obstacles such as the complicated growth processes and cryogenic operation preclude the usage of infrared detectors. As an alternative path towards high-performance photodetectors, hybrid semiconductor/graphene structures have been intensively explored. However, the operation bandwidth of such photodetectors has been limited to visible and near-infrared regimes. Here we demonstrate a mid-infrared hybrid photodetector enabled by coupling graphene with a narrow bandgap semiconductor, Ti2O3 (Eg = 0.09 eV), which achieves a high responsivity of 300 A W-1 in a broadband wavelength range up to 10 µm. The obtained responsivity is about two orders of magnitude higher than that of the commercial mid-infrared photodetectors. Our work opens a route towards achieving high-performance optoelectronics operating in the mid-infrared regime.

Overcoming the Ambient Manufacturability-Scalability-Performance Bottleneck in Colloidal Quantum Dot Photovoltaics.

Colloidal quantum dot (CQD) solar cells have risen rapidly in performance; however, their low-cost fabrication under realistic ambient conditions remains elusive. This study uncovers that humid environments curtail the power conversion efficiency (PCE) of solar cells by preventing the needed oxygen doping of the hole transporter during ambient fabrication. A simple oxygen-doping step enabling ambient manufacturing irrespective of seasonal humidity variations is devised. Solar cells with PCE > 10% are printed under high humidity at industrially viable speeds. The devices use a tiny fraction of the ink typically needed and are air stable over a year. The humidity-resilient fabrication of efficient CQD solar cells breaks a long-standing compromise, which should accelerate commercialization.

Embedding 1D Conducting Channels into 3D Isoporous Polymer Films for High-Performance Humidity Sensing.

Isoporous block copolymer (BCP) films have received exponential interest as highly selective membranes, stemming from their unique morphological features, but their applications in functional devices remain to be realized. Now single-walled carbon nanotubes (CNTs) were efficiently incorporated into isoporous block copolymer films for chemiresistive sensing at room temperature. Leveraging the efficient charge extraction ability of CNTs together with nanochannel arrays aligned perpendicular to the surface of the films, an ultrafast response time of 0.3 s was achieved for humidity detection with a sensor response of about 800 on changing humidity from 10 % to 95 %. Furthermore, the sensor also responds to various organic vapors, underscoring its promising detection capability.

High-Performance Ultraviolet-to-Infrared Broadband Perovskite Photodetectors Achieved via Inter-/Intraband Transitions.

A high-performance vertically injected broadband UV-to-IR photodetector based on Gd-doped ZnO nanorods (NRs)/CH3NH3PbI3 perovskite heterojunction was fabricated on metal substrates. Our perovskite-based photodetector is sensitive to a broad spectral range, from ultraviolet to infrared light region (λ = 250-1357 nm). Such structure leads to a high photoresponsivity of 28 and 0.22 A/W, for white light and IR illumination, respectively, with high detectivity values of 1.1 × 1012 and 9.3 × 109 Jones. Optical characterizations demonstrate that the IR detection is due to intraband transition in the perovskite material. Metal substrate boosts carrier injection, resulting in higher responsivity compared to the conventional devices grown on glass, whereas the presence of Gd increases the ZnO NRs performance. For the first time, the perovskite-based photodetector is demonstrated to extend its detection capability to IR (>1000 nm) with high room temperature responsivity across the detected spectrum, leading to a high-performance ingenious cost-effective UV-to-IR broadband photodetector design for large-scale applications.

A Photodetector Based on p-Si/n-ZnO Nanotube Heterojunctions with High Ultraviolet Responsivity.

Enhanced ultraviolet (UV) photodetectors (PDs) with high responsivity comparable to that of visible and infrared photodetectors are needed for commercial applications. n-Type ZnO nanotubes (NTs) with high-quality optical, structural, and electrical properties on a p-type Si(100) substrate are successfully fabricated by pulsed laser deposition (PLD) to produce a UV PD with high responsivity, for the first time. We measure the current-voltage characteristics of the device under dark and illuminated conditions and demonstrated the high stability and responsivity (that reaches ∼101.2 A W-1) of the fabricated UV PD. Time-resolved spectroscopy is employed to identify exciton confinement, indicating that the high PD performance is due to optical confinement, the high surface-to-volume ratio, the high structural quality of the NTs, and the high photoinduced carrier density. The superior detectivity and responsivity of our NT-based PD clearly demonstrate that fabrication of high-performance UV detection devices for commercial applications is possible.

Effects of High Temperature and Thermal Cycling on the Performance of Perovskite Solar Cells: Acceleration of Charge Recombination and Deterioration of Charge Extraction.

In this work, we investigated the effects of high operating temperature and thermal cycling on the photovoltaic (PV) performance of perovskite solar cells (PSCs) with a typical mesostructured (m)-TiO2-CH3NH3PbI3-xClx-spiro-OMeTAD architecture. After temperature-dependent grazing-incidence wide-angle X-ray scattering, in situ X-ray diffraction, and optical absorption experiments were carried out, the thermal durability of PSCs was tested by subjecting the devices to repetitive heating to 70 °C and cooling to room temperature (20 °C). An unexpected regenerative effect was observed after the first thermal cycle; the average power conversion efficiency (PCE) increased by approximately 10% in reference to the as-prepared device. This increase of PCE was attributed to the heating-induced improvement of the crystallinity and p doping in the hole transporter, spiro-OMeTAD, which promotes the efficient extraction of photogenerated carriers. However, further thermal cycles produced a detrimental effect on the PV performance of PSCs, with the short-circuit current and fill factor degrading faster than the open-circuit voltage. Similarly, the PV performance of PSCs degraded at high operation temperatures; both the short-circuit current and open-circuit voltage decreased with increasing temperature, but the temperature-dependent trend of the fill factor was the opposite. Our impedance spectroscopy analysis revealed a monotonous increase of the charge-transfer resistance and a concurrent decrease of the charge-recombination resistance with increasing temperature, indicating a high recombination of charge carriers. Our results revealed that both thermal cycling and high temperatures produce irreversible detrimental effects on the PSC performance because of the deteriorated interfacial photocarrier extraction. The present findings suggest that the development of robust charge transporters and proper interface engineering are critical for the deployment of perovskite PVs in harsh thermal environments.

Crystal structure of hexa-kis-(dimethyl sulfoxide-κO)manganese(II) tetra-iodide.

The title salt, [Mn(C2H6OS)6]I4, is made up from discrete [Mn(DMSO)6]2+ (DMSO is dimethyl sulfoxide) units connected through non-classical hydrogen bonds to linear I42- tetra-iodide anions. The MnII ion in the cation, situated on a position with site symmetry -3., is octa-hedrally coordinated by O atoms of the DMSO mol-ecule with an Mn-O distance of 2.1808 (12) Å. The I42- anion contains a neutral I2 mol-ecule weakly coordinated by two iodide ions, forming a linear centrosymmetric tetra-iodide anion. The title compound is isotypic with the Co, Ni, Cu, and Zn analogues.

Perovskite Photodetectors Operating in Both Narrowband and Broadband Regimes.

Photodetectors are designed, which operate in the broadband regime upon bottom illumination (from the indium tin oxide (ITO) side) and in the narrowband regime upon top illumination (from the air/perovskite side). The narrowband photodetectors show high external quantum efficiency of above 104 %. The operational spectrum of the photodetectors can also be tuned by adjusting the halide composition in the active material.

Fast Crystallization and Improved Stability of Perovskite Solar Cells with Zn2SnO4 Electron Transporting Layer: Interface Matters.

Here we report that mesoporous ternary oxide Zn2SnO4 can significantly promotes the crystallization of hybrid perovskite layers and serves as an efficient electron transporting material in perovskite solar cells. Such devices exhibit an energy conversion efficiency of 13.34%, which is even higher than that achieved with the commonly used TiO2 in the similar experimental conditions (9.1%). Simple one-step spin coating of CH3NH3PbI3-xClx on Zn2SnO4 is found to lead to rapidly crystallized bilayer perovskite structure without any solvent engineering. Furthermore, ultrafast transient absorption measurement reveals efficient charge transfer at the Zn2SnO4/perovskite interface. Most importantly, solar cells with Zn2SnO4 as the electron-transporting material exhibit negligible electrical hysteresis and exceptionally high stability without encapsulation for over one month. Besides underscoring Zn2SnO4 as a highly promising electron transporting material for perovskite solar cells, our results demonstrate the significant role of interfaces on improving the perovskite crystallization and photovoltaic performance.

CH3NH3PbCl3 Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector.

Single crystals of hybrid perovskites have shown remarkably improved physical properties compared to their polycrystalline film counterparts, underscoring their importance in the further development of advanced semiconductor devices. Here we present a new method of growing sizable CH3NH3PbCl3 single crystals based on the retrograde solubility behavior of hybrid perovskites. We show, for the first time, the energy band structure, charge recombination, and transport properties of CH3NH3PbCl3 single crystals. These crystals exhibit trap-state density, charge carrier concentration, mobility, and diffusion length comparable with the best quality crystals of methylammonium lead iodide or bromide perovskites reported so far. The high quality of the crystal along with its suitable optical band gap enabled us to build an efficient visible-blind UV-photodetector, demonstrating its potential in optoelectronic applications.