Depositing a pinhole-free perovskite film is of paramount importance to achieve high performance perovskite solar cells, especially in a heterojunction device format that is free of hole transport ...material (HTM). Here, we report that high-quality pinhole-free CH3NH3PbI3 perovskite film can be controllably deposited via a facile low-temperature (<150 °C) gas–solid crystallization process. The crystallite formation process was compared with respect to the conventional solution approach, in which the needle-shaped solvation intermediates (CH3NH3PbI3·DMF and CH3NH3PbI3·H2O) have been recognized as the main cause for the incomplete coverage of the resultant film. By avoiding these intermediates, the films crystallized at the gas–solid interface offer several beneficial features for device performance including high surface coverage, small surface roughness, as well as controllable grain size. Highly efficient HTM-free perovskite solar cells were constructed with these pinhole-free CH3NH3PbI3 films, exhibiting significant enhancement of the light harvesting in the long wavelength regime with respect to the conventional solution processed one. Overall, the gas–solid method yields devices with an impressive power conversion efficiency of 10.6% with high reproducibility displaying a negligible deviation of 0.1% for a total of 30 cells.
All-optical control of plasmons can enable optical switches with high speeds, small footprints and high on/off ratios. Here we demonstrate ultrafast plasmon modulation in the near-infrared (NIR) to ...mid-infrared (MIR) range by intraband pumping of indium tin oxide nanorod arrays (ITO-NRAs). We observe redshifts of localized surface plasmon resonances arising from a change of the plasma frequency of ITO, which is governed by the conduction band non-parabolicity. We generalize the plasma frequency for non-parabolic bands, quantitatively model the fluence-dependent plasma frequency shifts, and show that different from noble metals, the lower electron density in ITO enables a remarkable change of electron distributions, yielding a significant plasma frequency modulation and concomitant large transient bleaches and induced absorptions, which can be tuned spectrally by tailoring the ITO-NRA geometry. The low electron heat capacity explains the sub-picosecond kinetics that is much faster than noble metals. Our work demonstrates a new scheme to control infrared plasmons for optical switching, telecommunications and sensing.
Organic–inorganic perovskite photovoltaics are an emerging solar technology. Developing materials and processing techniques that can be implemented in large‐scale manufacturing is extremely important ...for realizing the potential of commercialization. Here we report a hot‐casting process with controlled Cl− incorporation which enables high stability and high power‐conversion‐efficiencies (PCEs) of 18.2% for small area (0.09 cm2) and 15.4% for large‐area (≈1 cm2) single solar cells. The enhanced performance versus tri‐iodide perovskites can be ascribed to longer carrier diffusion lengths, improved uniformity of the perovskite film morphology, favorable perovskite crystallite orientation, a halide concentration gradient in the perovskite film, and reduced recombination by introducing Cl−. Additionally, Cl− improves the device stability by passivating the reaction between I− and the silver electrode. High‐quality thin films deployed over a large‐area 5 cm × 5 cm eight‐cell module have been fabricated and exhibit an active‐area PCE of 12.0%. The feasibility of material and processing strategies in industrial large‐scale coating techniques is then shown by demonstrating a “dip‐coating” process which shows promise for large throughput production of perovskite solar modules.
A hot‐casting perovskite processing technique with controlled Cl− incorporation affords a high power conversion efficiency of 18.2% for small‐area (0.09 cm2), 15.4% for large‐area (≈1 cm2) single solar cells, and 12.0% for large‐area 5 cm × 5 cm eight‐cell modules and compatibility with large throughput production techniques.
Perylenediimide (PDI)-based acceptors offer a potential replacement for fullerenes in bulk-heterojunction (BHJ) organic photovoltaic cells (OPVs). The most promising efforts have focused on creating ...twisted PDI dimers to disrupt aggregation and thereby suppress excimer formation. Here, we present an alternative strategy for developing high-performance OPVs based on PDI acceptors that promote slip-stacking in the solid state, thus preventing the coupling necessary for rapid excimer formation. This packing structure is accomplished by substitution at the PDI 2,5,8,11-positions (“headland positions”). Using this design principle, three PDI acceptors, N,N-bis(n-octyl)-2,5,8,11-tetra(n-hexyl)-PDI (Hexyl-PDI), N,N-bis(n-octyl)-2,5,8,11-tetraphenethyl-PDI (Phenethyl-PDI), and N,N-bis(n-octyl)-2,5,8,11-tetraphenyl-PDI (Phenyl-PDI), were synthesized, and their molecular and electronic structures were characterized. They were then blended with the donor polymer PBTI3T, and inverted OPVs of the structure ITO/ZnO/Active Layer/MoO3/Ag were fabricated and characterized. Of these, 1:1 PBTI3T:Phenyl-PDI proved to have the best performance with J sc = 6.56 mA/cm2, V oc = 1.024 V, FF = 54.59%, and power conversion efficiency (PCE) = 3.67%. Devices fabricated with Phenethyl-PDI and Hexyl-PDI have significantly lower performance. The thin film morphology and the electronic and photophysical properties of the three materials are examined, and although all three materials undergo efficient charge separation, PBTI3T:Phenyl-PDI is found to have the deepest LUMO, intermediate crystallinity, and the most well-mixed domains. This minimizes geminate recombination in Phenyl-PDI OPVs and affords the highest PCE. Thus, slip-stacked PDI strategies represent a promising approach to fullerene replacements in BHJ OPVs.
As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress ...charge recombination. Here we investigate two series of in-chain donor–acceptor copolymers, PTPDnT and PBTInT, based on thieno3,4-cpyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers. Thiophene addition progressively raises polymer HOMOs but marginally affects their band gaps. FT-Raman spectra indicate that PTPDnT and PBTInT conjugation lengths scale with nT catenation up to n = 3 and then saturate for longer oligomer. Furthermore, the effects of oligothiophene alkylation position are explored, revealing that the alkylation pattern greatly affects film morphology and PSC performance. The 3T with “outward” alkylation in PTPD3T and PBTI3T affords optimal π-conjugation, close stacking, long-range order, and high hole mobilities (0.1 cm2/(V s)). These characteristics contribute to the exceptional ∼80% fill factors for PTPD3T-based PSCs with PCE = 7.7%. The results demonstrate that 3T is the optimal donor unit among nTs (n = 1–4) for photovoltaic polymers. Grazing incidence wide-angle X-ray scattering, transmission electron microscopy, and time-resolved microwave conductivity measurements reveal that the terthiophene-based PTPD3T blend maintains high crystallinity with appreciable local mobility and long charge carrier lifetime. These results provide fundamental materials structure-device performance correlations and suggest guidelines for designing oligothiophene-based polymers with optimal thiophene catenation and appropriate alkylation pattern to maximize PSC performance.
We introduce a new class of molecular iodosalt compounds for application in next-generation solar cells. Unlike tin-based perovskite compounds CsSnI3 and CH3NH3SnI3, which have Sn in the 2+ oxidation ...state and must be handled in an inert atmosphere when fabricating solar cells, the Sn in the molecular iodosalt compounds is in the 4+ oxidation state, making them stable in air and moisture. As an example, we demonstrate that, using Cs2SnI6 as a hole transporter, we can successfully fabricate in air a solid-state dye-sensitized solar cell (DSSC) with a mesoporous TiO2 film. Doping Cs2SnI6 with additives helps to reduce the internal device resistance, improving cell efficiency. In this way, a Z907 DSSC delivers 4.7% of energy conversion efficiency. By using a more efficient mixture of porphyrin dyes, an efficiency near 8% with photon confinement has been achieved. This represents a significant step toward the realization of low-cost, stable, lead-free, and environmentally benign next-generation solid-state solar cells.
Careful selection of processing solvents to tune optimal active layer morphology in a donor‐acceptor copolymer blend PTB7:P(NDI2OD‐T2) yields bulk heterojunction microstructures with intradomain ...percolative pathways and enhanced charge transport. Such microstructures afford all‐polymer solar cells with power conversion efficiencies as high as 2.7%.
Over the past five years, a rapid progress in organometal‐halide perovskite solar cells has greatly influenced emerging solar energy science and technology. In perovksite solar cells, the overlying ...hole transporting material (HTM) is critical for achieving high power conversion efficiencies (PCEs) and for protecting the air‐sensitive perovskite active layer. This study reports the synthesis and implementation of a new polymeric HTM series based on semiconducting 4,8‐dithien‐2‐yl‐benzo1,2‐d;4,5‐d′bistriazole‐alt‐benzo1,2‐b:4,5‐b′dithiophenes (pBBTa‐BDTs), yielding high PCEs and environmentally‐stable perovskite cells. These intrinsic (dopant‐free) HTMs achieve a stabilized PCE of 12.3% in simple planar heterojunction cells—the highest value to date for a polymeric intrinsic HTM. This high performance is attributed to efficient hole extraction/collection (the most efficient pBBTa‐BDT is highly ordered and orients π‐face‐down on the perovskite surface) and balanced electron/hole transport. The smooth, conformal polymer coatings suppress aerobic perovskite film degradation, significantly enhancing the solar cell 85 °C/65% RH PCE stability versus typical molecular HTMs.
New in‐chain donor–acceptor semiconducting copolymers are designed and synthesized as dopant‐free perovskite solar cell hole transport materials. Combining the BDT donor and the BBTa acceptor building blocks yields pBBTa‐BDT copolymers with strong interchain interactions, substantial quinoidal π‐character, preferential π‐face‐on orientation, and therefore efficient hole extraction/collection and balanced electron/hole transport. Significant enhancement of solar cell performance and environmental stability are achieved.
Recent advances in polymer solar cell (PSC) performance have resulted from compressing the bandgap to enhance the short-circuit current while lowering the highest occupied molecular orbital to ...increase the open-circuit voltage. Nevertheless, PSC power conversion efficiencies are still constrained by low fill factors, typically below 70%. Here, we report PSCs with exceptionally high fill factors by combining complementary materials design, synthesis, processing and device engineering strategies. The donor polymers, PTPD3T and PBTI3T, when incorporated into inverted bulk-heterojunction PSCs with a PC71 BM acceptor, result in PSCs with fill factors of 76-80%. The enhanced performance is attributed to highly ordered, closely packed and properly oriented active-layer microstructures with optimal horizontal phase separation and vertical phase gradation. The result is efficient charge extraction and suppressed bulk and interfacial bimolecular recombination. The high fill factors yield power conversion efficiencies of up to 8.7% from polymers with suboptimal bandgaps, suggesting that efficiencies above 10% should be realizable by bandgap modification.
Bithiophene imide (BTI) and benzodithiophene (BDT) copolymers are synthesized for application in organic photovoltaic (OPV) cells. The electron deficiency of the BTI units leads to polymers with a ...low‐lying HOMOs (∼‐5.6 eV). Inverted solar cells are fabricated to investigate the OPV performance of the BTI‐based polymers and achieve power conversion efficiencies up to 5.5%, with substantial Vocs above 0.9 V which are among the highest Vocs reported to date for polymer/PCBM solar cells. The results indicate that the BTI is a promising building block for constructing polymer donors for OPV applications.
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