skip to main content

Title: Tailoring carrier dynamics in perovskite solar cells via precise dimension and architecture control and interfacial positioning of plasmonic nanoparticles
Placing plasmonic nanoparticles (NPs) in close proximity to semiconductor nanostructures renders effective tuning of the optoelectronic properties of semiconductors through the localized surface plasmon resonance (LSPR)-induced enhancement of light absorption and/or promotion of carrier transport. Herein, we report on, for the first time, the scrutiny of carrier dynamics of perovskite solar cells (PSCs) via sandwiching monodisperse plasmonic/dielectric core/shell NPs with systematically varied dielectric shell thickness yet fixed plasmonic core diameter within an electron transport layer (ETL). Specifically, a set of Au NPs with precisely controlled dimensions ( i.e. , fixed Au core diameter and tunable SiO 2 shell thickness) and architectures (plain Au NPs and plasmonic/dielectric Au/SiO 2 core/shell NPs) are first crafted by capitalizing on the star-like block copolymer nanoreactor strategy. Subsequently, these monodisperse NPs are sandwiched between the two consecutive TiO 2 ETLs. Intriguingly, there exists a critical dielectric SiO 2 shell thickness, below which hot electrons from the Au core are readily injected to TiO 2 ( i.e. , hot electron transfer (HET)); this promotes local electron mobility in the TiO 2 ETL, leading to improved charge transport and increased short-circuit current density ( J sc ). It is also notable that the HET effect moves up the Fermi level of TiO 2 , resulting in an enhanced built-in potential and open-circuit voltage ( V oc ). Taken together, the PSCs constructed by employing a sandwich-like TiO 2 /Au NPs/TiO 2 ETL exhibit both greatly enhanced J sc and V oc , delivering champion PCEs of 18.81% and 19.42% in planar and mesostructured PSCs, respectively. As such, the judicious positioning of rationally designed monodisperse plasmonic NPs in the ETL affords effective tailoring of carrier dynamics, thereby providing a unique platform for developing high-performance PSCs.  more » « less
Award ID(s):
1914562 1903981
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Energy & Environmental Science
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Surface recombination is a major bottleneck for realizing highly efficient micro/nanostructure solar cells. Here, parametric studies of the influence of Si microwire (SiMW) surface‐facet orientation (rectangular with flat‐facets, {110}, {100} and circular), with a fixed height of 10 µm, diameter (D= 1.5–9.5 µm), and sidewall spacing (S= 2.5–8.5 µm), and mesh‐grid density (1–16 mm−2) on recombination and carrier collection in SiMW solar cells with radial p‐n junctions are reported. An effective surface passivation layer composed of thin thermally grown silicon dioxide (SiO2) and silicon nitride (SiNx) layers is employed. For a fixedDof 1.5 µm, tight SiMW spacing results in improved short‐circuit current density (Jsc= 30.1 mA cm−2) and sparse arrays result in open‐circuit voltages (Voc= 0.552 V) that are similar to those of control Si planar cells. For a fixedS, smallerDresults in better light trapping at shorter wavelengths and higherJscwhile largerDexhibits better light trapping at larger wavelengths and a higherVoc. With a mesh‐grid electrode the power conversion efficiency increases to 15.3%. These results provide insights on the recombination mechanisms in SiMW solar cells and provide general design principles for optimizing their performance.

    more » « less
  2. Donor polymer fluorination has proven to be an effective method to improve the power conversion efficiency of fullerene-based polymer solar cells (PSCs). However, this fluorine effect has not been well-studied in systems containing new, non-fullerene acceptors (NFAs). Here, we investigate the impact of donor polymer fluorination in NFA-based solar cells by fabricating devices with either a fluorinated conjugated polymer (FTAZ) or its non-fluorinated counterpart (HTAZ) as the donor polymer and a small molecule NFA (ITIC) as the acceptor. We found that, similar to fullerene-based devices, fluorination leads to an increased open circuit voltage ( V oc ) from the lowered HOMO level and improved fill factor (FF) from the higher charge carrier mobility. More importantly, donor polymer fluorination in this NFA-based system also led to a large increase in short circuit current ( J sc ), which stems from the improved charge transport and extraction in the fluorinated device. This study demonstrates that fluorination is also advantageous in NFA-based PSCs and may improve performance to a higher extent than in fullerene-based PSCs. In the context of other recent reports on demonstrating higher photovoltaic device efficiencies with fluorinated materials, fluorination appears to be a valuable strategy in the design and synthesis of future donors and acceptors for PSCs. 
    more » « less
  3. Air‐stable p‐type SnF2:Cs2SnI6with a bandgap of 1.6 eV has been demonstrated as a promising material for Pb‐free halide perovskite solar cells. Crystalline Cs2SnI6phase is obtained with CsI, SnI2, and SnF2salts in gamma‐butyrolactone solvent, but not with dimethyl sulfoxide andN,N‐dimethylformamide solvents. Cs2SnI6is found to be stable for at least 1000 h at 100 °C when dark annealed in nitrogen atmosphere. In this study, Cs2SnI6has been used in a superstrate n–i–p planar device structure enabled by a spin‐coated absorber thickness of ≈2 μm on a chemical bath deposited Zn(O,S) electron transport layer. The best device power conversion efficiency reported here is 5.18% withVOCof 0.81 V, 9.28 mA cm−2JSC, and 68% fill factor. The dark saturation current and diode ideality factor are estimated as 1.5 × 10−3 mA cm−2and 2.18, respectively. The devices exhibit a highVOCdeficit and low short‐circuit current density due to high bulk and interface recombination. Device efficiency can be expected to increase with improvement in material and interface quality, charge transport, and device engineering.

    more » « less
  4. Abstract

    Although tip‐enhanced tribo‐tunneling in metal/semiconductor point nanocontact is capable of producing DC with high current density, scaling up the process for power harvesting for practical applications is challenging due to the complexity of tip array fabrication and insufficient voltage output. Here, it is demonstrated that mechanical contact between a carbon aerogel and silicon (SiO2/Si) interface naturally forms multiple nanocontacts for tribo‐tunneling current generation with an open‐circuit voltage output (VOC) reaching 2 V, and short‐circuit DC current output (ISC) of ≈15 µA. It has a theoretical current density ( J*) on the order of 100 A m−2. Molecular dynamics simulation and atomistic field theory show that a strong localized electronic excitation can be induced at a dynamic carbon/SiO2sliding interface, which is in good agreement with the experimental results. The DC power output is enhanced by the intense local pressure at the presence of nanocontacts, as well as the increased sliding velocityv. To demonstrate the method for practical applications, light‐emitting diodes (LEDs) with different colors are successfully lighted by a single‐carbon aerogel monolith/SiO2sliding unit, and the DC electricity is stored in a capacitor without an additional rectification circuit.

    more » « less
  5. Abstract

    The combined effects of compact TiO2(c‐TiO2) electron‐transport layer (ETL) are investigated without and with mesoscopic TiO2(m‐TiO2) on top, and without and with an iodine‐terminated silane self‐assembled monolayer (SAM), on the mechanical behavior, opto–electronic properties, photovoltaic (PV) performance, and operational‐stability of solar cells based on metal‐halide perovskites (MHPs). The interfacial toughness increases almost threefold in going from c‐TiO2without SAM to m‐TiO2with SAM. This is attributed to the synergistic effect of the m‐TiO2/MHP nanocomposite at the interface and the enhanced adhesion afforded by the iodine‐terminated silane SAM. The combination of m‐TiO2and SAM also offers a significant beneficial effect on the photocarriers extraction at the ETL/MHP interface, resulting in perovskite solar cells (PSCs) with power‐conversion efficiency (PCE) of over 24% and 20% for 0.1 and 1 cm2active areas, respectively. These PSCs also have exceptionally long operational‐stability lives: extrapolatedT80 (duration at 80% initial PCE retained) is ≈18 000 and 10 000 h for 0.1 and 1 cm2active areas, respectively.Postmortemcharacterization and analyses of the operational‐stability‐tested PSCs are performed to elucidate the possible mechanisms responsible for the long operational‐stability.

    more » « less