skip to main content


Title: Photothermal and photovoltaic properties of transparent thin films of porphyrin compounds for energy applications
To address the critical issues in solar energy, the current research has focused on developing advanced solar harvesting materials that are low cost, lightweight, and environmentally friendly. Among many organic photovoltaics (PVs), the porphyrin compounds exhibit unique structural features that are responsible for strong ultraviolet (UV) and near infrared absorptions and high average visible transmittance, making them ideal candidates for solar-based energy applications. The porphyrin compounds have also been found to exhibit strong photothermal (PT) effects and recently applied for optical thermal insulation of building skins. These structural and optical properties of the porphyrin compounds enable them to function as a PT or a PV device upon sufficient solar harvesting. It is possible to develop a transparent porphyrin thin film with PT- and PV-dual-modality for converting sunlight to either electricity or thermal energy, which can be altered depending on energy consumption needs. A building skin can be engineered into an active device with the PT- and PV-dual modality for large-scale energy harvesting, saving, and generation. This review provides the current experimental results on the PT and PV properties of the porphyrin compounds such as chlorophyll and chlorophyllin. Their PT and PV mechanisms are discussed in correlations to their electronic structures. Also discussed are the synthesis routes, thin film deposition, and potential energy applications of the porphyrin compounds.  more » « less
Award ID(s):
1635089 1953009
NSF-PAR ID:
10249241
Author(s) / Creator(s):
Date Published:
Journal Name:
Applied physics reviews
Volume:
8
ISSN:
1931-9401
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Photovoltaic solar cells have been extensively used for various applications and are considered one of the most efficient green energy sources. However, their 2D surface area solar harvesting has limitations, and there is an increasing need to explore the possibility of multiple layer solar harvest for enhanced energy density. To address this, we have developed spectral-selective transparent thin films based on porphyrin and iron oxide compounds that allow solar light to penetrate multiple layers, significantly increasing solar harvesting surface area and energy density. These thin films are designed as photovoltaic (PV) and photothermal (PT) panels that can convert photons into either electricity or thermal energy for various green energy applications, such as smart building skins and solar desalination. The advantages of this 3D solar harvesting system include enlarged solar light collecting surface area and increased energy density. The multilayer system transforms the current 2D to 3D solar harvesting, enabling efficient energy generation. This review discusses recent developments in the synthesis and characterization of PV and PT transparent thin films for solar harvesting and energy generation using multilayers. Major applications of the 3D solar harvesting system are reviewed, including thermal energy generation, multilayered DSSC PV system, and solar desalination. Some preliminary data on transparent multilayer DSSC PVs are presented. 
    more » « less
  2. null (Ed.)
    The photothermal experiments on the incident light angle dependence are carried out using simulated solar light on thin films of both iron oxides (Fe3O4 and Fe3O4@Cu2-xS) and porphyrin compounds (chlorophyll and chlorophyllin). Fe3O4 and Fe3O4@Cu2-xS are synthesized using various solution methods that produce mono-dispersed nanoparticles on the order of 10 nm. Chlorophyll is extracted from fresh spinach and chlorophyllin sodium copper is a commercial product. These photothermal (PT) materials are dispersed in polymethyl methacrylate (PMMA) solutions and deposited on glass substrates via spin coating that result in clear and transparent thin films. The iron-oxide based thin films show distinctive absorption spectra; Fe3O4 exhibits a strong peak near UV and gradually decreases into the visible and NIR regions; the absorption of Fe3O4@Cu2-xS is similar in the UV region but shows a broad absorption in the NIR region. Both chlorophyll and chlorophyllin are characterized with absorption peaks near UV and NIR showing a “U”-shaped spectrum, ideally required for efficient solar harvest and high transparency in energy-efficient single-pane window applications. Upon coating of the transparent PT films on the window inner surfaces, solar irradiation induces the photothermal effect, consequently raising the film temperature. In this fashion, the thermal loss through the window can be significantly lowered by reducing the temperature difference between the window inner surface and the room interior, based on a new concept of so-called “optical thermal insulation” (OTI) without any intervention medium, such as air/argon, as required in the glazing technologies. Single-panes are therefore possible to replace double- or triple panes. As OTI is inevitably affected by seasonal and daily sunlight changes, an incident light angle dependence of the photothermal effect is crucial in both thin film and window designs. It is found that the heating curves reach their maxima at small angles of incidence while the photothermal effect is considerably reduced at large angles. This angle dependence is well explained by light reflection by the thin film surface, however, deviated from what is predicted by the Fresnel’s law, attributable to non-ideal surfaces of the substrates. The angle dependence data provides an important reference for OTI that window exposure to sun is greater at winter solstice while that is considerably reduced in the summer. This conclusion indicates much enhanced solar harvesting and heat conversion via optically insulated windows in the winter season, resulting in much lower U-factors. 
    more » « less
  3.  
    more » « less
  4. Abstract

    A fundamental challenge in energy sustainability is efficient utilization of solar energy towards energy‐neutral systems. The current solar cell technologies have been most widely employed to achieve this goal, but are limited to a single‐layer 2D surface. To harvest solar light more efficiently, a multilayer system capable of harvesting solar light in a cuboid through transparent photothermal thin films of iron oxide and a porphyrin compound is developed. Analogous to a multilayer capacitor, an array of transparent, spectral selective, photothermal thin films allows white light to penetrate them, not only collecting photon energy in a 3D space, but generating sufficient heat on each layer with significantly increased total surface area. In this fashion, thermal energy is generated via a multilayer photothermal system that functions as an efficient solar collector, energy converter and generator with high energy density. A solar‐activated thermal energy generator that can produce heat without any power supply and reach a maximum temperature of 76.1 °C is constructed. With a constant incoming white light (0.4 W cm−2), the thermal energy generated can be amplified 12‐fold via multilayers. The multilayer system extends another dimension in solar harvesting and paves a new path to energy generation for the energy‐neutral system.

     
    more » « less
  5. Cadmium telluride (CdTe) solar cells are a promising photovoltaic (PV) technology for producing power in space owing to their high-efficiency (> 22.1 %), potential for specific power, and cost-effective manufacturing processes. In contrast to traditional space PVs, the high-Z (atomic number) CdTe absorbers can be intrinsically robust under extreme space radiation, offering long-term stability. Despite these advantages, the performance assessment of CdTe solar cells under high-energy particle irradiation (e.g., photons, neutrons, charged particles) is limited in the literature, and their stability is not comprehensively studied. In this work, we present the PV response of n-CdS / p-CdTe PVs under accelerated neutron irradiation. We measure PV properties of the devices at different neutron/photon doses. The equivalent dose deposited in the CdTe samples is simulated with deterministic and Monte Carlo radiation transport methods. Thin-film CdTe solar cells were synthesized on a fluorine-doped tin oxide (FTO) coated glass substrate (≈ 4 cm × 4 cm). CdS:O (≈ 100 nm) was reactively RF sputtered in an oxygen/argon ambient followed by a close-spaced sublimation deposition of CdTe (≈ 3.5 μm) in an oxygen/helium ambient. The sample was exposed to a 10 min vapor CdCl2 in oxygen/helium ambient at 430˚C. The samples were exposed to a wet CuCl2 solution prior to anneal 200ºC. A gold back-contact was formed on CdTe via thermal evaporation. The final sample contains 16 CdTe devices. For neutron irradiation, we cleaved the CdTe substrate into four samples and exposed two samples to ≈ 90 kW reactor power neutron radiation for 5.5 hours and 8.2 hours, respectively, in our TRIGA (Training, Research, Isotopes, General Atomics) reactor. We observed a noticeable color change of the glass substrates to brown after the neutron/gamma reactor exposure. Presumably, the injected high-energy neutrons caused the breaking of chemical bonds and the displacement of atoms in the glass substrates, creating point defects and color centers. The I-V characteristics showed noticeable deterioration with over 8 hour radiations. Specifically, the saturation current of the control devices was ≈ 25 nA increasing to 1 μA and 10 μA for the 5.5-hour and 8.2-hour radiated samples, respectively. The turn-on voltage of the control devices (≈ 0.85 V) decreased with the irradiated sample (≈ 0.75 V for 5.5-hour and ≈ 0.5 V for 8.2-hour exposures), implying noticeable radiation damage occurred at the heterojunction. The higher values of the ideality factor for irradiated devices (n > 2.2) compared to that of the control devices (n ≈ 1.3) also support the deterioration of the p-n junction. We observed the notable decrease in shunt resistance (RSH) and the increase in series resistance (Rs) with the neutron dose. It is possible that Cu ions introduced during the CuCl2 treatment may migrate into CdTe grain boundaries (GBs). The presence of Cu ions at GBs can create additional leakage paths for photocarrier transport, deteriorating the overall PV performance. We estimated the radiation dose of CdTe in comparison to Si (conventional PV) using a UUTR model (e.g., MCNP6 2D UTR Reactor simulations). In this model, we simulated Si and CdTe at the center point of the triangular fuel lattice and used an “unperturbed flux” tally in the water. Our simulations yielded a dose rate of 6916 Gy/s of neutrons and 16 Gy/s of photons for CdTe, and 1 Gy/s of neutrons and 21 Gy/s of photons for Si (doses +/- <1%). The large dose rate of neutrons in CdTe is mainly attributed to the large thermal neutron absorption cross-section of 113Cd. Based on this estimation, we calculate that the exposure of our CdTe PVs is equivalent to several million years in LEO (Low-Earth Orbit), or about 10,000 years for Si in LEO. Currently, we are working on a low-dose neutron/photon radiation on CdTe PVs and their light I-Vs and microstructural characterizations to gain better understanding on the degradation of CdTe PVs. 
    more » « less