Eliminating Resistance-Capacitance Coupling Shielding for Depicting the Defect Landscape in Perovskite Solar Cells by Capacitance Spectroscopy.

Capacitance spectroscopy techniques have been widely utilized to evaluate the defect properties in perovskites, which contribute to the efficiency and operation stability development for perovskite solar cells (PSCs). Yet the interplay between the charge transporting layer (CTL) and the perovskite on the capacitance spectroscopy results is still unclear. Here, they show that a pseudo-trap-state capacitance signal is generated in thermal admittance spectroscopy (TAS) due to the enhanced resistance capacitance (RC) coupling caused by the carrier freeze-out of the CTL in PSCs, which could be discerned from the actual defect-induced trap state capacitance signal by tuning the series resistance of PSCs. By eliminating the RC coupling shielding effect on the defect-induced capacitance spectroscopy, it is obtain the actual defect density which is 4-folds lower than the pseudo-trap density, and the spatial distribution of defects in PSCs which reveals that the commonly adopted interface passivators can passivate the defects about 60 nm away from the decorated surface. It is further revealed that phenethylammonium ions (PEA+) possess a better passivation capability over octylammonium ions (OA+) due to the deeper passivation depth for PEA+ on the surface defects in perovskite films.

Visualizing the Structure-Property Nexus of Wide-Bandgap Perovskite Solar Cells under Thermal Stress.

Wide-bandgap perovskite solar cells (PSCs) toward tandem photovoltaic applications are confronted with the challenge of device thermal stability, which motivates to figure out a thorough cognition of wide-bandgap PSCs under thermal stress, using in situ atomic-resolved transmission electron microscopy (TEM) tools combing with photovoltaic performance characterizations of these devices. The in situ dynamic process of morphology-dependent defects formation at initial thermal stage and their proliferations in perovskites as the temperature increased are captured. Meanwhile, considerable iodine enables to diffuse into the hole-transport-layer along the damaged perovskite surface, which significantly degrade device performance and stability. With more intense thermal treatment, atomistic phase transition reveals the perovskite transform to PbI2 along the topo-coherent interface of PbI2/perovskite. In conjunction with density functional theory calculations, a mutual inducement mechanism of perovskite surface damage and iodide diffusion is proposed to account for the structure-property nexus of wide-bandgap PSCs under thermal stress. The entire interpretation also guided to develop a thermal-stable monolithic perovskite/silicon tandem solar cell.

Direct growth of graphene on hyper-doped silicon to enhance carrier transport for infrared photodetection.

The importance of infrared photodetectors cannot be overstated, especially in fields such as security, communication, and military. While silicon-based infrared photodetectors are widely used due to the maturity of the semiconductor industry, their band gap of 1.12 eV limits their infrared light absorption above 1100 nm, making them less effective. To overcome this limitation, we report a novel infrared photodetector prepared by growing graphene on the surface of zinc hyper-doped silicon. This technique utilizes hyper-doping to introduce deep level assisted infrared light absorption benefit from the enhanced carrier collection capacity of graphene. Without introducing new energy consumption, the hyper-doped substrate annealing treatment is completed during the growth of graphene. By the improvement of transport and collection of charge carriers, the graphene growth adjusts the band structure to upgrade electrode contact, resulting in a response of 1.6 mA W-1under laser irradiation with a wavelength of 1550 nm and a power of 2 mW. In comparison, the response of the photodetector without graphene was only 0.51 mA W-1, indicating a three-fold performance improvement. Additionally, the device has lower dark current and lower noise current, resulting in a noise equivalent power of 7.6 × 10-8W Hz-0.5. Thus, the combination of transition metal hyper-doping and graphene growth technology has enormous potential for developing the next generation of infrared photodetectors.

Tandem Electro-Oxidative C-C and C-N Coupling and Aromatization for the Construction of Pyrazine-Fused Bis-aza[7]helicene.

Repeated tandem electro-oxidative C-C and C-N coupling and aromatization were employed for the efficient construction of aza[7]helicene (BA7) as a key intermediate and the targeted pyrazine-fused bis-aza[7]helicene (PBBA7) derivatives in 90.0-93.2% isolated yields under a controlled potential. The electrosynthetic protocol showed high selectivity and enabled rapid access to functionalized organic conjugated materials from readily available polycyclic aromatic amines. A synthetic mechanistic study along with an investigation of the photoelectrical properties and application of PBBA7-C16 as a potential hole-transporting material for perovskite solar cells were performed.

High detectivity graphene/si heterostructure photodetector with a single hydrogenated graphene atomic interlayer for passivation and carrier tunneling.

Hydrogenated graphene is easy to prepare and chemically stable. Besides, hydrogenation of graphene can open the band gap, which is vital for electronic and optoelectronic applications. Graphene/Si photodetector (PD) has been widely studied in imaging, telecommunications, and other fields. The direct contact between graphene and Si can form a Schottky junction. However, it suffers from poor interface state, where the carrier recombination at the interface causes serious leakage current, which in turn leads to a decrease in the detectivity. Hence, in this study, hydrogenated graphene is used as an interfacial layer, which passivates the interface of graphene/Si (Gr/Si) heterostructure. Besides, the single atomic layer thickness of hydrogenated graphene is also crucial for the tunneling transport of charge carriers and its suitable energy band position reduces the recombination of carrier. The fabricated graphene/hydrogenated-graphene/Si (Gr/H-Gr/Si) heterostructure PD showed an extremely low dark current about 10-7A. As a result, it had low noise current and exhibited a high specific detectivity of âˆ¼2.3 × 1011Jones at 0 V bias with 532 nm laser illumination. Moreover, the responsivity of the fabricated PD was found to be 0.245 A W-1at 532 nm illumination with 10µW power. These promising results show a great potential of hydrogenated graphene to be used as an interface passivation and carrier tunneling layer for the fabrication of high-performance Gr/Si heterostructure PDs.

Phase-Stable Wide-Bandgap Perovskites for Four-Terminal Perovskite/Silicon Tandem Solar Cells with Over 30% Efficiency.

Wide-bandgap perovskite solar cells (PSCs) with an optimal bandgap between 1.7 and 1.8 eV are critical to realize highly efficient and cost-competitive silicon tandem solar cells (TSCs). However, such wide-bandgap PSCs easily suffer from phase segregation, leading to performance degradation under operation. Here, it is evident that ammonium diethyldithiocarbamate (ADDC) can reduce the detrimental I2 back to I- in precursor solution, thereby reducing the density of deep level traps in perovskite films. The resultant perovskite film exhibits great phase stability under continuous illumination and 30-60% relative humidity conditions. Due to the suppression of defect proliferation and ion migration, the PSCs deliver great operation stability which retain over 90% of the initial power conversion efficiency (PCE) after 500 h maximum power point tracking. Finally, a highly efficient semitransparent PSC with a tailored bandgap of 1.77 eV, achieving a PCE approaching 18.6% with a groundbreaking open-circuit voltage (VOC ) of 1.24 V enabled by ADDC additive in perovskite films is demonstrated. Integrated with a bottom silicon solar cell, a four-terminal (4T) TSC with a PCE of 30.24% is achieved, which is one of the highest efficiencies in 4T perovskite/silicon TSCs.

Stabilizing Fullerene for Burn-in-Free and Stable Perovskite Solar Cells under Ultraviolet Preconditioning and Light Soaking.

It is crucial to make perovskite solar cells sustainable and have a stable operation under natural light soaking before they become commercially acceptable. Herein, a small amount of the small molecule bathophenanthroline (Bphen) is introduced into [6,6]-phenyl-C61 -butyric acid methyl ester and it is found that Bphen can stabilize the C60 -cage well through formation of much more thermodynamically stable charge-transfer complexes. Such a strengthened complex is used as an interlayer at the in-light perovskite/SnO2 side to achieve a champion device with efficiency of 23.09% (certified 22.85%). Most importantly, the stability of the resulting devices can be close to meeting the requirements of the International Electrotechnical Commission 61215 standard under simulated UV preconditioning and light-soaking testing. They can retain over 95% and 92% of their initial efficiencies after 1100 h UV irradiation and 1000 h continuous illumination of maximum power point tracking at 60 °C, respectively.

Identifying the functional groups effect on passivating perovskite solar cells.

Many organic molecules with various functional groups have been used to passivate the perovskite surface for improving the efficiency and stability of perovskite solar cell (PSCs). However, the intrinsic attributes of the passivation effect based on different chemical bonds are rarely studied. Here, we comparatively investigate the passivation effect among 12 types of functional groups on para-tert-butylbenzene for PSCs and find that the open circuit voltage (VOC) tends to increase with the chemical bonding strength between perovskite and these passivation additive molecules. Particularly, the para-tert-butylbenzoic acid (tB-COOH), with the extra intermolecular hydrogen bonding, can stabilize the surface passivation of perovskite films exceptionally well through formation of a crystalline interlayer with water-insoluble property and high melting point. As a result, the tB-COOH device achieves a champion power conversion efficiency (PCE) of 21.46%. More importantly, such devices, which were stored in ambient air with a relative humidity of ≃45%, can retain 88% of their initial performance after a testing period of more than 1 year (10,080 h). This work provides a case study to understand chemical bonding effects on passivation of perovskite.

All-vacuum deposited and thermally stable perovskite solar cells with F4-TCNQ/CuPc hole transport layer.

Hole transporting layers (HTLs) play a crucial role in the realization of efficient and stable perovskite solar cells (PSCs). Copper phthalocyanine (CuPc) is a promising HTL owing to its thermal stability and favorable band alignment with the perovskite absorber. However, the power conversion efficiency (PCE) of PSCs with a CuPc HTL is still lagging behind highly efficient solar cells. Herein, a p-type tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) is employed as an interlayer between the perovskite and CuPc HTL in all-vacuum deposited PSCs. The F4-TCNQ interlayer improves the conductivity of both MAPbI3 and CuPc, reduces the shunt pathway and facilitates an efficient photoexcited holes transfer from the valance band of the MAPbI3 to the LUMO of the F4-TCNQ. Consequently, the best solar cell device with an F4-TCNQ interlayer achieved a PCE of 13.03% with a remarkable improvement in fill factor. Moreover, the device showed superior stability against thermal stress at 85 °C over 250 h and retained ∼95% of its initial efficiency. This work demonstrates a significant step towards all-vacuum deposited perovskite solar cells with high thermal stability.

An Interlayer with Strong Pb-Cl Bond Delivers Ultraviolet-Filter-Free, Efficient, and Photostable Perovskite Solar Cells.

The inorganic metal oxides (IMOs), including titanium dioxide (TiO2) and tin dioxide (SnO2), inevitably induce decomposition of perovskite under UV illumination owing to their photocatalytic activity, and the use of a UV filter will add extra cost and reduce the effective power output. Here, we first reveal that the weak Pb-I bond in I-based perovskite is prone to breakage under UV photocatalysis, leading to serious degradation of the SnO2/perovskite interface. We introduced a chlorine-rich mixed-halide perovskite interlayer (ClMPI), which possesses an excellent tolerance to photocatalysis owing to the strong Pb-Cl bond, between the SnO2 and I-based perovskite. The ClMPI-based device achieves an enhanced efficiency of up to 21.01% (certified 20.17%). Most importantly, the resultant devices can maintain >94% of their initial performance after 180 h under outdoor solar irradiation, >80% after 500 h under UV irradiation, and 500 h under continuous full spectrum illumination at their maximum power points.

CsPbBr3 quantum dots assisted crystallization of solution-processed perovskite films with preferential orientation for high performance perovskite solar cells.

The performance of hybrid perovskite solar cells (PSCs) is significantly influenced by the crystallization and morphology of perovskite films. Herein, a novel method of CsPbBr3 quantum dots (QDs) assisted nucleation is applied to prepare high quality solution-processed methylammonium lead iodide (MAPbI3) films by employing CsPbBr3 QDs as an additive into diethyl ether anti-solvent. The appropriate amount of CsPbBr3 QDs can act as effective heterogeneous nucleation centers, leading to the formation of smooth and pinhole-free perovskite films with increased grain size. Furthermore, the growth direction of MAPbI3 grains is regulated by CsPbBr3 QDs, exhibiting preferential orientation of (110) plane. Therefore, the MAPbI3 films with CsPbBr3 QDs modification show reduced defects and increased carrier lifetime. As a result, the champion PSC with a maximum power conversion efficiency (PCE) up to 20.17% is achieved and 85% of its initial PCE is maintained after aging 1000 h at room temperature under a relative humidity of 50%. This work demonstrates a feasible way to prepare high quality perovskite films for optoelectronic applications.

Perovskite Bifunctional Device with Improved Electroluminescent and Photovoltaic Performance through Interfacial Energy-Band Engineering.

Currently, photovoltaic/electroluminescent (PV/EL) perovskite bifunctional devices (PBDs) exhibit poor performance due to defects and interfacial misalignment of the energy band. Interfacial energy-band engineering between the perovskite and hole-transport layer (HTL) is introduced to reduce energy loss, through adding corrosion-free 3,3'-(2,7-dibromo-9H-fluorene-9,9-diyl) bis(n,n-dimethylpropan-1-amine) (FN-Br) into a HTL free of lithium salt. This strategy can turn the n-type surface of perovskite into p-type and thus correct the misalignment to form a well-defined N-I-P heterojunction. The tailored PBD achieves a high PV efficiency of up to 21.54% (certified 20.24%) and 4.3% EL external quantum efficiency. Free of destructive additives, the unencapsulated devices maintain >92% of their initial PV performance for 500 h at maximum power point under standard air mass 1.5G illumination. This strategy can serve as a general guideline to enhance PV and EL performance of perovskite devices while ensuring excellent stability.