Dye-sensitized solar cells (DSSCs) hold unique promise in solar photovoltaics owing to their low-cost fabrication and high efficiency in ambient conditions. However, to improve their commercial viability, effective, and low-cost methods must be employed to enhance their light harvesting capabilities, and hence photovoltaic (PV) performance. Improving the absorption of incoming light is a critical strategy for maximizing solar cell efficiency while overcoming material limitations. Mesoporous silica nanoparticles (MSNs) were employed herein as a reflective layer on the back of transparent counter electrodes. Chemically synthesized MSNs were applied to DSSCs via bar coating as a facile fabrication step compatible with roll-to-roll manufacturing. The MSNs diffusely scatter the unused incident light transmitted through the DSSCs back into the photoactive layers, increasing the absorption of light by N719 dye molecules. This resulted in a 20% increase in power conversion efficiency (PCE), from 5.57% in a standard cell to 6.68% with the addition of MSNs. The improved performance is attributed to an increase in photon absorption which led to the generation of a higher number of charge carriers, thus increasing the current density in DSSCs. These results were corroborated with electrochemical impedance spectroscopy (EIS), which showed improved charge transport kinetics. The use of MSNs as reflectors proved to be an effective practical method for enhancing the performance of thin film solar cells. Due to silica’s abundance and biocompatibility, MSNs are an attractive material for meeting the low-cost and non-toxic requirements for commercially viable integrated PVs.
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This content will become publicly available on June 22, 2024
Improving Photovoltaic Performance of Light-Responsive Double-Heterojunction Nanorod Light-Emitting Diodes
Double heterojunction nanorods enable both electroluminescence and light harvesting capabilities within the same device structure, providing a promising platform for energy-scavenging displays and related applications. However, the efficiency of the photovoltaic mode remains modest for useful power conversion and may be challenging to improve without sacrificing performance in electroluminescence. Through a facile on-film partial ligand exchange with benzenethiol integrated into the device fabrication step, we achieve an average of more than threefold increase in power conversion efficiency while maintaining the maximum external quantum efficiency and the maximum luminance in the LED mode. The improved photovoltaic performance is mainly due to the increase in the short circuit current, which we attribute to the enhanced charge separation afforded by the partial ligand exchange. The recovery of the photoluminescence lifetime under the forward bias suggests that the hole traps introduced by benzenethiols are filled prior to reaching the voltage at which light emission begins, allowing LED
performance to be maintained and possibly improved.
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- Award ID(s):
- 2132538
- NSF-PAR ID:
- 10439155
- Date Published:
- Journal Name:
- Journal of chemical physics
- Volume:
- 158
- Issue:
- 24
- ISSN:
- 1520-9032
- Page Range / eLocation ID:
- 244701
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Recently, the use of bottom-TJ geometry in LEDs, which achieves N-polar-like alignment of polarization fields in conventional metal-polar orientations, has enabled enhancements in LED performance due to improved injection efficiency. Here, we elucidate the root causes behind the enhanced injection efficiency by employing mature laser diode structures with optimized heterojunction GaN/In0.17Ga0.83N/GaN TJs and UID GaN spacers to separate the optical mode from the heavily doped absorbing p-cladding regions. In such laser structures, polarization offsets at the electron blocking layer, spacer, and quantum barrier interfaces play discernable roles in carrier transport. By comparing a top-TJ structure to a bottom-TJ structure, and correlating features in the electroluminescence, capacitance-voltage, and current-voltage characteristics to unique signatures of the N- and Ga-polar polarization heterointerfaces in energy band diagram simulations, we identify that improved hole injection at low currents, and improved electron blocking at high currents, leads to higher injection efficiency and higher output power for the bottom-TJ device throughout 5 orders of current density (0.015–1000 A/cm2). Moreover, even with the addition of a UID GaN spacer, differential resistances are state-of-the-art, below 7 × 10−4Ωcm2. These results highlight the virtues of the bottom-TJ geometry for use in high-efficiency laser diodes.
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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
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Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K. The spectral peaks for VB = 2.8 and 3.0 V both occur around = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018).more » « less
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Ultra-violet light emitting diodes (UV-LEDs) and lasers based on the III-Nitride material system are very promising since they enable compact, safe, and efficient solid-state sources of UV light for a range of applications. The primary challenges for UV LEDs are related to the poor conductivity of p-AlGaN layers and the low light extraction efficiency of LED structures. Tunnel junction-based UV LEDs provide a distinct and unique pathway to eliminate several challenges associated with UV LEDs1-4. In this work, we present for the first time, a reversed-polarization (p-down) AlGaN based UV-LED utilizing bottom tunnel junction (BTJ) design. We show that compositional grading enables us to achieve the lowest reported voltage drop of 1.1 V at 20 A/cm2 among transparent AlGaN based tunnel junctions at this Al-composition. Compared to conventional LED design, a p-down structure offers lower voltage drop because the depletion barrier for both holes and electrons is lower due to polarization fields aligning with the depletion field. Furthermore, the bottom tunnel junction also allows us to use polarization grading to realize better p- and n-type doping to improve tunneling transport. The epitaxial structure of the UV-LED was grown by plasma-assisted molecular beam epitaxy (PAMBE) on metal-organic chemical vapor deposition (MOCVD)-grown n-type Al0.3Ga0.7N templates. The transparent TJ was grown using graded n++-Al0.3Ga0.7N→ n++-Al0.4Ga0.6N (Si=3×1020 cm-3) and graded p++-Al0.4Ga0.6N →p++-Al0.3Ga0.7N (Mg=1×1020 cm-3) to take advantage of induced 3D polarization charges. The high number of charges at the tunnel junction region leads to lower depletion width and efficient hole injection to the p-type layer. The UV LED active region consists of three 2.5 nm Al0.2Ga0.8N quantum wells and 7 nm Al0.3Ga0.6N quantum barriers followed by 12 nm of p- Al0.46Ga0.64N electron blocking layer (EBL). The active region was grown on top of the tunnel junction. A similar LED with p-up configuration was also grown to compare the electrical performance. The surface morphology examined by atomic force microscopy (AFM) shows smooth growth features with a surface roughness of 1.9 nm. The dendritic features on the surface are characteristic of high Si doping on the surface. The composition of each layer was extracted from the scan by high resolution x-ray diffraction (HR-XRD). The electrical characteristics of a device show a voltage drop of 4.9 V at 20 A/cm2, which corresponds to a tunnel junction voltage drop of ~ 1.1 V. This is the best lowest voltage for transparent 30% AlGaN tunnel junctions to-date and is comparable with the lowest voltage drop reported previously on non-transparent (InGaN-based) tunnel junctions at similar Al mole fraction AlGaN. On-wafer electroluminescence measurements on patterned light-emitting diodes showed single peak emission wavelength of 325 nm at 100 A/cm2 which corresponds to Al0.2Ga0.8N, confirming that efficient hole injection was achieved within the structure. The device exhibits a wavelength shift from 330 nm to 325 nm with increasing current densities from 10A/cm2 to 100A/cm2. In summary, we have demonstrated a fully transparent bottom AlGaN homojunction tunnel junction that enables p-down reversed polarization ultraviolet light emitting diodes, and has very low voltage drop at the tunnel junction. This work could enable new flexibility in the design of future III-Nitride ultraviolet LEDs and lasers.more » « less
