Siraj Sidhik

Bio: Siraj Sidhik is an academic researcher from Rice University. The author has contributed to research in topics: Perovskite (structure) & Materials science. The author has an hindex of 13, co-authored 36 publications receiving 444 citations. Previous affiliations of Siraj Sidhik include Central Glass and Ceramic Research Institute & University of Kerala.

Deterministic fabrication of 3D/2D perovskite bilayer stacks for durable and efficient solar cells

Abstract: Realizing solution-processed heterostructures is a long-enduring challenge in halide perovskites because of solvent incompatibilities that disrupt the underlying layer. By leveraging the solvent dielectric constant and Gutmann donor number, we could grow phase-pure two-dimensional (2D) halide perovskite stacks of the desired composition, thickness, and bandgap onto 3D perovskites without dissolving the underlying substrate. Characterization reveals a 3D–2D transition region of 20 nanometers mainly determined by the roughness of the bottom 3D layer. Thickness dependence of the 2D perovskite layer reveals the anticipated trends for n-i-p and p-i-n architectures, which is consistent with band alignment and carrier transport limits for 2D perovskites. We measured a photovoltaic efficiency of 24.5%, with exceptional stability of T99 (time required to preserve 99% of initial photovoltaic efficiency) of >2000 hours, implying that the 3D/2D bilayer inherits the intrinsic durability of 2D perovskite without compromising efficiency. Description Pure perovskite topcoats Two-dimensional (2D) halide perovskite passivation layers grown on three-dimensional (3D) perovskite can boost the power conversion efficiency (PCE) of solar cells, but spin-coating of these layers usually forms heterogeneous 2D phases or only ultrathin layers. Sidhik et al. found that solvents with the appropriate dielectric constant and donor strength could grow phase-pure 2D phases of controlled thickness and composition on 3D substrates without dissolving them. Solar cells maintained a peak PCE of 24.5% for 2000 hours with less than 1% degradation under continuous light at 55°C and 65% relative humidity. —PDS Solvents enable growth of phase-pure two-dimensional perovskites without dissolving three-dimensional perovskite substrates.

Improving the Optoelectronic Properties of Mesoporous TiO2 by Cobalt Doping for High-Performance Hysteresis-free Perovskite Solar Cells

Abstract: We for the first time report the incorporation of cobalt into a mesoporous TiO2 electrode for application in perovskite solar cells (PSCs). The Co-doped PSC exhibits excellent optoelectronic properties; we explain the improvements by passivation of electronic trap or sub-band-gap states arising due to the oxygen vacancies in pristine TiO2, enabling faster electron transport and collection. A simple postannealing treatment is used to prepare the cobalt-doped mesoporous electrode; UV-visible spectroscopy, X-ray photoemission spectroscopy, space charge-limited current, photoluminescence, and electrochemical impedance measurements confirm the incorporation of cobalt, enhanced conductivity, and the passivation effect induced in the TiO2. An optimized doping concentration of 0.3 mol % results in the maximum power conversion efficiency of 18.16%, 21.7% higher than that of a similar cell with an undoped TiO2 electrode. Also, the device shows negligible hysteresis and higher stability, retaining 80.54% of the initial efficiency after 200 h.

Operating Mechanisms of Mesoscopic Perovskite Solar Cells through Impedance Spectroscopy and J–V Modeling

Abstract: The performance of perovskite solar cell (PSC) is highly sensitive to deposition conditions, the substrate, humidity, and the efficiency of solvent extraction. However, the physical mechanism involved in the observed changes of efficiency with different deposition conditions has not been elucidated yet. In this work, PSCs were fabricated by the antisolvent deposition (AD) and recently proposed air-extraction antisolvent (AAD) process. Impedance analysis and J–V curve fitting were used to analyze the photogeneration, charge transportation, recombination, and leakage properties of PSCs. It can be elucidated that the improvement in morphology of perovskite film promoted by AAD method leads to increase in light absorption, reduction in recombination sites, and interstitial defects, thus enhancing the short-circuit current density, open-circuit voltage, and fill factor. This study will open up doors for further improvement of device and help in understanding its physical mechanism and its relation to the depos...

Ultrasensitive SERS Substrate for Label-Free Therapeutic-Drug Monitoring of Paclitaxel and Cyclophosphamide in Blood Serum.

Abstract: Surface-enhanced Raman spectroscopy (SERS) has recently emerged as an innovative tool for therapeutic-drug monitoring (TDM), making it an ideal candidate for personalized treatment. Herein, we report a layer-by-layer (LbL) approach for the fabrication of a highly reproducible hybrid SERS substrate based on graphene oxide (GO)-supported l-cysteine-functionalized starlike gold nanoparticles (SAuNPs). These designed substrates were utilized for TDM of paclitaxel and cyclophosphamide in blood serum. The SAuNPs' efficient binding at the edges of GO creates a better SERS hotspot with enhanced Raman sensitivity because of the spacing of ∼2.28 nm between the SAuNPs. In addition, the hierarchically modified substrate with a self-assembled monolayer of zwitterionic amino acid l-cysteines acts like a brush layer to prevent SERS-hotspot blockages and fouling by blood-serum proteins. The antifouling nature of the substrate was determined quantitatively by a bichinchonic acid assay using bovine-serum albumin (BSA) as a protein model on the l-cysteine SAuNPs@GO hybrid substrate (the test) and a cysteamine SAuNPs@GO substrate (the control). The l-cysteine SAuNPs@GO hybrid exhibited 80.57% lower BSA fouling compared with that of the cysteamine SAuNPs@GO substrate. The SERS spectra were acquired within 20 s, with detection limits of 1.5 × 10-8 M for paclitaxel and 5 × 10-9 M for cyclophosphamide in blood serum. Such sensitivities are 4 times and 1 order of magnitude higher than the currently available sophisticated analytical techniques, which involve high costs with each analysis.

From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer.

Abstract: Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA+), which results in a series of Ruddlesden–Popper (RP) structures with the formula (PA)2(MA)n−1PbnI3n+1 (n = 3, 4) and a new homologous series of “step-like” (SL) structures where the PbI6 octahedra connect in a corner- and face-sharing motif with the general formula (PA)2m+4(MA)m−2Pb2m+1I7m+4 (m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra “insulated” by ...

State of the Art and Prospects for Halide Perovskite Nanocrystals.

Abstract: Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

The 2D Halide Perovskite Rulebook: How the Spacer Influences Everything from the Structure to Optoelectronic Device Efficiency.

Abstract: Two-dimensional (2D) halide perovskites have emerged as outstanding semiconducting materials thanks to their superior stability and structural diversity. However, the ever-growing field of optoelectronic device research using 2D perovskites requires systematic understanding of the effects of the spacer on the structure, properties, and device performance. So far, many studies are based on trial-and-error tests of random spacers with limited ability to predict the resulting structure of these synthetic experiments, hindering the discovery of novel 2D materials to be incorporated into high-performance devices. In this review, we provide guidelines on successfully choosing spacers and incorporating them into crystalline materials and optoelectronic devices. We first provide a summary of various synthetic methods to act as a tutorial for groups interested in pursuing synthesis of novel 2D perovskites. Second, we provide our insights on what kind of spacer cations can stabilize 2D perovskites followed by an extensive review of the spacer cations, which have been shown to stabilize 2D perovskites with an emphasis on the effects of the spacer on the structure and optical properties. Next, we provide a similar explanation for the methods used to fabricate films and their desired properties. Like the synthesis section, we will then focus on various spacers that have been used in devices and how they influence the film structure and device performance. With a comprehensive understanding of these effects, a rational selection of novel spacers can be made, accelerating this already exciting field.