Perovskite‐Based Tandem Solar Cells: Get the Most Out of the Sun

Tandem solar cells (TSCs) comprising stacked narrow‐bandgap and wide‐bandgap subcells are regarded as the most promising approach to break the Shockley–Queisser limit of single‐junction solar cells. As the game‐changer in the photovoltaic community, organic–inorganic hybrid perovskites became the front‐runner candidate for mating with other efficient photovoltaic technologies in the tandem configuration for higher power conversion efficiency, by virtue of their tunable and complementary bandgaps, excellent photoelectric properties, and solution processability. In this review, a perspective that critically dilates the progress of perovskite material selection and device design for perovskite‐based TSCs, including perovskite/silicon, perovskite/copper indium gallium selenide, perovskite/perovskite, perovskite/CdTe, and perovskite/GaAs are presented. Besides, all‐inorganic perovskite CsPbI₃ with high thermal stability is proposed as the top subcell in TSCs due to its suitable bandgap of ≈1.73 eV and rapidly increasing efficiency. To minimize the optical and electrical losses for high‐efficiency TSCs, the optimization of transparent electrodes, recombination layers, and the current‐matching principles are highlighted. Through big data analysis, wide‐bandgap perovskite solar cells with high open‐circuit voltage (V_oc) are in dire need in further study. In the end, opportunities and challenges to realize the commercialization of TSCs, including long‐term stability, area upscaling, and mitigation of toxicity, are also envisioned.     

Enhanced Photocurrent Spectral Response in Low‐Bandgap Polyfluorene and C70‐Derivative‐Based Solar Cells

Plastic solar cells have been fabricated using a low‐bandgap alternating copolymer of fluorene and a donor–acceptor–donor moiety (APFO‐Green1), blended with 3′‐(3,5‐bis‐trifluoromethylphenyl)‐1′‐(4‐nitrophenyl)pyrazolino[70]fullerene (BTPF70) as electron acceptor. The polymer shows optical absorption in two wavelength ranges, λ < 500 nm and 600 < λ < 1000 nm. The BTPF70 absorbs light at λ < 700 nm. A broad photocurrent spectral response in the wavelength range 300 < λ < 1000 nm is obtained in solar cells. A photocurrent density of 3.4 mA cm^–2, open‐circuit voltage of 0.58 V, and power‐conversion efficiency of 0.7 % are achieved under illumination of AM1.5 (1000 W m^–2) from a solar simulator. Synthesis of BTPF70 is presented. Photoluminescence quenching and electrochemical studies are used to discuss photoinduced charge transfer.     

Saccharide Blocking Layers in Solid State Dye Sensitized Solar Cells

The adsorption of saccharides on dye sensitized, nanocrystalline metal oxide films is shown to improve the efficiency of solid state dye sensitized solar cells. The function of the saccharide treatment is evaluated by transient optical studies, and correlated with device photovoltaic performance. A range of saccharides, including cyclodextrins and their linear analogue amylose, are investigated. The saccharide blocking layer is shown to retard interfacial charge recombination losses, resulting in increased device open circuit voltage. Highest device performance is achieved with linear saccharide amylose, resulting in a 60 % improvement in device efficiency relative to the non‐treated control, with a device open circuit voltage of 1 V.     

A Near‐Infrared cis‐Configured Squaraine Co‐Sensitizer for High‐Efficiency Dye‐Sensitized Solar Cells

A cis‐configured squaraine dye (HSQ1), synthesized by incorporation of a strongly electron‐withdrawing dicyanovinyl group into the central squaric acid moiety, is employed in dye‐sensitized solar cells (DSCs). In solution, HSQ1 displays an intense absorption in the near‐infrared region with a maximum at 686 nm and when the dye is adsorbed on a TiO₂ surface, the absorption spectrum broadens in both the blue and the near‐infrared regions, which is favorable for efficient light harvesting over a broad wavelength range. A solar cell sensitized with HSQ1 shows a broader incident photon‐to‐current conversion efficiency (IPCE) spectrum (from 400 to 800 nm) and a higher IPCE in the long‐wavelength region (71% at 700 nm) than a cell sensitized with squaraine dye SQ1. Furthermore, a solar cell co‐sensitized with HSQ1 and N3 dye shows remarkably improved short‐circuit current density and open‐circuit voltage compared to those of a DSC based on N3 alone and fabricated under the same conditions. The energy‐conversion efficiency of the co‐sensitized DSC is 8.14%, which is the highest reported efficiency for a squaraine dye–based co‐sensitized DSC without using Al₂O₃ layer.     

Copolymers of Cyclopentadithiophene and Electron‐Deficient Aromatic Units Designed for Photovoltaic Applications

Alternating copolymers based on cyclopentadithiophene (CPDT) and five different electron‐deficient aromatic units with reduced optical band gaps are synthesized via Suzuki coupling. All polymers show a significant photovoltaic response when mixed with a fullerene acceptor. The frontier orbital levels of the new polymers are designed to minimize energy losses by increasing the open‐circuit voltage with respect to the optical band gap, while maintaining a high coverage of the absorption with the solar spectrum. The best cells are obtained for a copolymer of CPDT and benzooxadiazole (BO) with a band gap of 1.47 eV. This cell gives a short‐circuit current of 5.4 mA cm^?2, an open‐circuit voltage of 0.78 V, and a fill factor of 0.6, resulting in a power conversion efficiency of about 2.5%.     

Performance Analysis of Printed Bulk Heterojunction Solar Cells

In this paper we report on printed bulk heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) with power efficiencies of over 4 %. Devices have been produced by doctor blading, which is a reel‐to‐reel compatible large‐area coating technique. Devices exhibit a short‐circuit current of over 11.5 mA cm^–2, a fill factor of 58 %, and an open‐circuit voltage of 615 mV, resulting in an AM1.5 power efficiency of over 4.0 % at 25 °C and under 100 mW cm^–2. The mismatch factor of the solar simulator is cross‐calibrated by determining the spectral quantum efficiency of organic devices as well as of a calibrated Si device, and by the combination of outdoor tests; these efficiencies are precise within less than 3 % relative variation. Although the devices are regarded as fairly optimized, analysis in terms of a one‐diode equivalent circuit reveals residual losses and loss mechanisms. Most interestingly, the analysis points out the different properties of spin‐coated versus bladed devices. Based on this analysis, the future efficiency potential of P3HT–PCBM solar cells is analyzed.     

Novel Near‐Infrared Squaraine Sensitizers for Stable and Efficient Dye‐Sensitized Solar Cells

A new molecular design strategy for tuning the energy levels of cis‐configured squaraine sensitizers for dye‐sensitized solar cells is described. The Hammett substituent constant and the π‐conjugation length are used as quantitative indicators to modify the central squarate moiety of the sensitizer dyes; specifically, novel near‐infrared squaraine dyes HSQ3 and HSQ4 are synthesized by incorporation of an electron‐withdrawing and π‐extending ethyl cyanoacetate unit on the central squarate moiety. The solution absorption maximum of HSQ4 occurs at 703 nm, and the energy levels of the lowest unoccupied molecular orbital and the highest occupied molecular orbital are in the ideal range for energetically efficient electron injection and regeneration of the oxidized dye. A solar cell sensitized with HSQ4 exhibits a broad incident photo­n‐to‐current conversion efficiency spectrum, extending into the near‐infrared region with a maximum value of 80% at 720 nm, which is is the highest value reported for a squaraine dye–based dye‐sensitized solar cell. The HSQ4‐sensitized solar cell also exhibits excellent durability during light soaking, owing to the double anchors attaching the dye to the TiO₂ surface and to the long alkyl chains extending outward from the surface.     

Transparent conductive oxide‐less three‐dimensional cylindrical dye‐sensitized solar cell fabricated with flexible metal mesh electrode

A cylindrical transparent conductive oxide‐less dye‐sensitized solar cell (DSSC) consisting of glass tube/stainless steel mesh–TiO₂–dye/gel electrolytes/Pt‐Ti rod having capability of self‐light trapping is reported. Replacing the glass tube with heat‐shrinkable tube to reduce electrolyte gap and optical loss due to light transmission and reflection led to the enhancement in the power conversion efficiency from 2.61% to 3.91%. Profiling of the current distribution measured by laser beam‐induced current exhibited nearly the same current in the axial and radial directions, suggesting that light reflection on a cylindrical DSSC does not affect the efficiency seriously. Optimized best DSSC in this novel device architecture gave a short‐circuit current density of 11.94 mA/cm², an open‐circuit voltage of 0.71 V and a fill factor of 0.66 leading to the power conversion efficiency of 5.58% at AM 1.5 under simulated solar irradiation. Copyright © 2011 John Wiley & Sons, Ltd.     

Coral‐shaped ZnO nanostructures for dye‐sensitized solar cell photoanodes

A highly efficient ZnO photoanode for dye‐sensitized solar cells was successfully grown by a simple, low cost, and scalable method. A nanostructured coral‐shaped Zn layer was deposited by sputtering onto fluorine‐doped tin oxide/glass slices at room temperature and then thermally oxidized in ambient atmosphere. Stoichiometry, crystalline phase, quality, and morphology of the film were investigated, evidencing the formation of a highly porous branched nanostructure, with a pure wurtzite crystalline structure. ZnO‐based dye‐sensitized solar cells were fabricated with customized microfluidic architecture. Dye loading on the oxide surface was analyzed with ultraviolet‐visible spectroscopy, and the dependence of the cell efficiency on sensitizer incubation time and film thickness was studied by current‐voltage electrical characterization, incident photon‐to‐electron conversion efficiency, and impedance spectroscopy measurements, showing the promising properties of this material for the fabrication of dye‐sensitized solar cell photoanodes with a solar conversion efficiency up to 4.58%. Copyright © 2012 John Wiley & Sons, Ltd.     

The 2,2,6,6‐Tetramethyl‐1‐piperidinyloxy Radical: An Efficient,Iodine‐ Free Redox Mediator for Dye‐Sensitized Solar Cells

A promising redox system, offering an alternative to the widely used iodide/triiodide couple, based on the stable organic radical 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) has been employed in dye‐sensitized solar cells. The photovoltaic performance of this new redox couple has been evaluated by employing nanocrystalline TiO₂ films with different thickness. Judicious selections of a 5.0 μm photoanode made from TiO₂ mesoscopic particles and an organic sensitizer with a high molar extinction coefficient yield an overall solar‐to‐electric power conversion efficiency of 5.4 % under AM 1.5 illumination at 100 mW cm^–2, which is unprecedented for an iodine‐free mediator system.     

17.87% Efficiency All-Polymer Tandem Solar Cell Enabled by Complementary Absorbing Polymer Acceptors

All-polymer solar cells (all-PSCs) possess distinguished advantages of excellent morphology stability, thermal stability, and mechanical flexibility. Tandem solar cells, by stacking two sub-cells, can absorb more photons in a wider wavelength range and can reduce thermal losses. However, limitation of polymer acceptors with suitable bandgaps hinders the development of tandem all-PSCs. Herein, highly efficient tandem all-PSCs are fabricated by employing two polymerized small molecular acceptors (PSMAs) of wide bandgap PIDT (1.66 eV) in the front cell and narrow bandgap PY-IT (1.4 eV) in the rear cell. The two sub-cells with the polymer donors of PM7 in front cell and PM6 in rear cell show high open circuit voltage (V_oc) of 1.10 V for the front cell and 0.94 V for the rear cell. By rational device optimizations, the best power conversion efficiency of 17.87% is achieved for the tandem all-PSCs with high V_oc of 2.00 V. 17.87% is one of the highest efficiency for the all-PSCs, and 2.00 V is one of the highest V_oc for all the tandem organic solar cells. Moreover, the tandem all-PSCs show excellent thermal and light-soaking stability compared with their small-molecule counterparts. The results provide insight to the potential of bandgap tuning in PSMAs, and indicate that the tandem architecture is an effective strategy to boost performance of the all-PSCs.     

Charge Generation and Photovoltaic Operation of Solid‐State Dye‐Sensitized Solar Cells Incorporating a High Extinction Coefficient Indolene‐Based Sensitizer

An investigation of the function of an indolene‐based organic dye, termed D149, incorporated in to solid‐state dye‐sensitized solar cells using 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxypheny‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as the hole transport material is reported. Solar cell performance characteristics are unprecedented under low light levels, with the solar cells delivering up to 70% incident photon‐to‐current efficiency (IPCE) and over 6% power conversion efficiency, as measured under simulated air mass (AM) 1.5 sun light at 1 and 10 mW cm^?2. However, a considerable nonlinearity in the photocurrent as intensities approach “full sun” conditions is observed and the devices deliver up to 4.2% power conversion efficiency under simulated sun light of 100 mW cm^?2. The influence of dye‐loading upon solar cell operation is investigated and the thin films are probed via photoinduced absorption (PIA) spectroscopy, time‐correlated single‐photon counting (TCSPC), and photoluminescence quantum efficiency (PLQE) measurements in order to deduce the cause for the non ideal solar cell performance. The data suggest that electron transfer from the photoexcited sensitizer into the TiO₂ is only between 10 to 50% efficient and that ionization of the photo excited dye via hole transfer directly to spiro‐OMeTAD dominates the charge generation process. A persistent dye bleaching signal is also observed, and assigned to a remarkably high density of electrons “trapped” within the dye phase, equivalent to 1.8 × 10¹⁷ cm^?3 under full sun illumination. it is believed that this localized space charge build‐up upon the sensitizer is responsible for the non‐linearity of photocurrent with intensity and nonoptimum solar cell performance under full sun conditions.     

2D/3D Heterostructure for Semitransparent Perovskite Solar Cells with Engineered Bandgap Enables Efficiencies Exceeding 25% in Four‐Terminal Tandems with Silicon and CIGS

Wide‐bandgap perovskite solar cells (PSCs) with optimal bandgap (E_g) and high power conversion efficiency (PCE) are key to high‐performance perovskite‐based tandem photovoltaics. A 2D/3D perovskite heterostructure passivation is employed for double‐cation wide‐bandgap PSCs with engineered bandgap (1.65 eV ≤ E_g ≤ 1.85 eV), which results in improved stabilized PCEs and a strong enhancement in open‐circuit voltages of around 45 mV compared to reference devices for all investigated bandgaps. Making use of this strategy, semitransparent PSCs with engineered bandgap are developed, which show stabilized PCEs of up to 25.7% and 25.0% in four‐terminal perovskite/c‐Si and perovskite/CIGS tandem solar cells, respectively. Moreover, comparable tandem PCEs are observed for a broad range of perovskite bandgaps. For the first time, the robustness of the four‐terminal tandem configuration with respect to variations in the perovskite bandgap for two state‐of‐the‐art bottom solar cells is experimentally validated.     

Solution‐Processed Organic Tandem Solar Cells

A solution‐processed polymer tandem cell fabricated by stacking two single cells in series is demonstrated. The two bulk‐heterojunction subcells have complementary absorption maxima at λ_max ～ 850 nm and λ_max ～ 550 nm, respectively. A composite middle electrode is applied that serves both as a charge‐recombination center and as a protecting layer for the first cell during spin‐coating of the second cell. The subcells are electronically coupled in series, which leads to a high open‐circuit voltage of 1.4 V, equal to the sum of each subcell. The layer thickness of the first (bottom) cell is tuned to maximize the optical absorption of the second (top) cell. The performance of the tandem cell is presently limited by the relatively low photocurrent generation in the small‐bandgap polymer of the top cell. The combination of our tandem architecture with more efficient small‐bandgap materials will enable the realization of highly efficient organic solar cells in the near future.     

Thiocyanate‐Free Ru(II) Sensitizers with a 4,4′‐Dicarboxyvinyl‐2,2′‐bipyridine Anchor for Dye‐Sensitized Solar Cells

A new class of thiocyanate‐free Ru(II) sensitizers with 4,4′‐dicarboxyvinyl‐2,2′‐bipyridine anchor and two trans‐oriented pyrid‐2‐yl pyrazolate (or triazolate) functional chromophores is synthesized, characterized, and evaluated in dye‐sensitized solar cells (DSCs). Despite their enhanced red response and absorptivity when compared to the parent sensitizer TFRS‐2 that possesses standard 4,4′‐dicarboxyl‐2,2′‐bipyridine anchor and shows the best conversion efficiency of η = 9.82%, the newly synthesized carboxyvinyl‐pyrazolate sensitizers, TFRS‐11 – TFRS‐13 , exhibit inferior performance characteristics in terms of short‐circuit current density (J_SC), open‐circuit voltage (V_OC), and power conversion efficiency (η), the latter being recorded to be in the range 5.60–7.62%. The reduction in device efficiencies is attributed to a combination of poor packing of these sensitizers on the TiO₂ surface and less positive ground‐state oxidation potentials, which, respectively, increase charge recombination with I₃^? in electrolytes and impede the regeneration of sensitizers by I^? anions. The latter obstacle can be circumvented in part by the replacement of the pyrazolates with triazolates, forming the TFRS‐14 sensitizer, which exhibits an improved J_SC, V_OC, and η of 16.4 mAcm^?2, 0.77 V, and 9.02%, respectively.     

Non‐Corrosive,Non‐Absorbing Organic Redox Couple for Dye‐Sensitized Solar Cells

A new colorless electrolyte containing an organic redox couple, tetramethylthiourea (TMTU) and its oxidized dimer tetramethylformaminium disulfide dication ([TMFDS]²⁺), is applied to dye‐sensitized solar cells (DSCs). Advantages of this redox couple include its non‐corrosive nature, low cost, and easy handling. More impressively, it operates well with carbon electrodes. The DSCs fabricated with a lab‐made HCS‐CB carbon counter‐electrode can present up to 3.1% power conversion efficiency under AM 1.5 illumination of 100 mW·cm^?2 and 4.5% under weaker light intensities. This result distinctly outperforms the identical DSCs with a Pt electrode. Corrosive experiments reveal that Al and stainless steel (SS) sheets are stable in the [TMFDS]²⁺/TMTU‐based electrolyte. Its electrochemical impedance spectrum (EIS) is used to evaluate the influence of different counter‐electrodes on the cell performance, and preliminary investigations reveal that carbon electrodes with large surface areas and ideal corrosion‐inertness toward the sulfur‐containing [TMFDS]²⁺/TMTU redox couple exhibit promise for application in iodine‐free DSCs.     

Evaluation of subcell power conversion efficiencies of radiation‐damaged triple‐junction solar cells using photoluminescence decays

We characterize the radiation‐induced damage of InGaP/GaAs/Ge solar cells for various proton irradiation energies and fluences using conventional current‐voltage (I‐V) measurements, external quantum efficiency, and a noncontact time‐resolved photoluminescence (PL) technique. From the I‐V curves, we obtain the conversion efficiency of the entire device. The external quantum efficiency showed that the short‐circuit current is only determined by the top InGaP subcell. To obtain accurate information about the point of maximum power, a new PL technique is introduced. The PL time decays of the InGaP and GaAs subcells are measured to obtain the characteristic decay time constants of carrier separation and recombination. We empirically verify that the time‐resolved PL method can be used to predict the electrical conversion efficiency of the subcells. We find that the limiting subcell at the point of maximum power is different from that for short‐circuit current. Radiation damage in unexpected regions of the device is revealed using this optical method.     

Wide‐bandgap p‐type microcrystalline silicon oxycarbide using additional trimethylboron for silicon heterojunction solar cells

We report a new wide‐bandgap p‐type microcrystalline silicon oxycarbide (p‐μc‐SiO_xC_y:H) film prepared by plasma‐enhanced chemical vapor deposition. As an additional doping gas, trimethylboron was introduced into the standard processing gas‐mixture of silane, carbon dioxide, hydrogen, and diborane. With both trimethylboron and diborane as doping gases, the optical bandgap (E ₀₄) of the formed p‐μc‐SiO_xC_y:H film was 0.18 eV higher than that of reference microcrystalline silicon oxide (p‐μc‐SiO_x:H) processed with only diborane doping gas for the same levels of film thickness and electrical conductivity. To demonstrate the effectiveness of the developed p‐layer, we applied it as an emitter in silicon heterojunction solar cells, which delivered a markedly high open circuit voltage of 0.702 V and a power conversion efficiency of 18.9% based on a non‐textured flat wafer. Copyright © 2017 John Wiley & Sons, Ltd.     

Design of conduction band structure of TiO2 electrode using Nb doping for highly efficient dye‐sensitized solar cells

A barrier layer of undoped TiO₂ was deposited on the Nb‐doped TiO₂ electrode to suppress the recombination at the Nb‐doped TiO₂/dye–electrolyte interface for highly efficient dye‐sensitized solar cells (DSCs). The Nb content in TiO₂ was varied in a range of 0.7–3.5 mol% to modify the TiO₂ energy‐band structure. Nb‐doped TiO₂/dye interfaces were characterized by a combination of ultraviolet photoemission spectroscopy and optical absorption spectroscopy measurements, allowing the determination of the conduction band minimum (CBM) of the TiO₂ electrode and the lowest unoccupied molecular orbital of the N719 dye. The lowering of TiO₂ CBM by Nb doping induced the increase in short‐circuit current of DSCs. However, open‐circuit voltage and fill factor are decreased, and this result was ascribed to the enhanced recombination at the Nb‐doped TiO₂/dye–electrolyte interface. The effect of doping on charge transport in DSCs was analyzed using electrochemical impedance spectroscopy. We have shown that by introducing of TiO₂ barrier layer, the Nb doping content, which results in DSC highest efficiency, can be increased because of the suppression of the dopant‐induced recombination. The energy conversion efficiency of the solar cells increased from 7.8% to 9.0% when undoped TiO₂ electrode is replaced with electrode doped with 2.7 mol% of Nb because of the improvement of the electron injection and collection efficiencies. The correlation between the electronic structure of the TiO₂ electrode, charge transfer characteristics, and photovoltaic parameters of DSCs is discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Interface Engineering Enhances the Photovoltaic Performance of Wide Bandgap FAPbBr3 Perovskite for Application in Low-Light Environments

Underwater solar cells (UWSCs) provide an ideal alternative to the energy supply for long-endurance autonomous underwater vehicles. However, different from conventional solar cells situated on land or above water, UWSCs give preference to use wide bandgap semiconductors (≥1.8 eV) as light absorber to match underwater solar spectra. Among wide bandgap semiconductors, FAPbBr₃ perovskite is under prime consideration owing to its matching optical bandgap (≈2.3 eV), outstanding photoelectric properties, easier processability, etc. Unfortunately, for FAPbBr₃ solar cells, substantial interface defects greatly limit the charge carrier extraction efficiency, thus limiting the device performance, especially in underwater low-light environments. This study employs a molecular self-assembly strategy to effectively eliminate the interfacial defects. As a result, a great improvement in power conversion efficiency (PCE) from 6.44% to 7.49% is obtained, which is among the best efficiency reported for inverted FAPbBr₃ solar cells up to date. Besides, a champion PCE of 30% is obtained under 520 nm monochromatic light irradiation (4.8 mW cm⁻²). These results demonstrate that FAPbBr₃ solar cells present a tremendously promising application in UWSCs.