Interfacial Charge Recombination Research Articles

D 6 h Symmetric Radical Donor–Acceptor Nanographene Modulated Interfacial Carrier Transfer for High-Performance Perovskite Solar Cells

<i>D</i> ^{6 <i>h</i>} Symmetric Radical Donor–Acceptor Nanographene Modulated Interfacial Carrier Transfer for High-Performance Perovskite Solar Cells

TiO2/CdS/CdSe quantum dots co-sensitized solar cell with the staggered-gap (type-II) heterojunctions for the enhanced photovoltaic performance

The effect of co-sensitization and ZnS passivation on the photovoltaic performance of CdS quantum dot sensitized solar cells (QDSSCs) were investigated. The deposition of CdS, CdSe quantum dots (QD) and ZnS passivation on TiO2 photoanode was carried out by successive ionic layer adsorption and reaction (SILAR) method. CdS/CdSe co-sensitization developed two staggered type-II heterojunctions at TiO2/CdS and CdS/CdSe interfaces and resulted a cascade energy band structure. This suitable band alignment facilitated the double charge transfer mechanism at each heterojunction and transported the electrons easily into the photoanode. The narrow bandgap sensitizers CdS and CdSe significantly improved the potential utilization of solar spectrum with more charge carrier generation. ZnS passivation on QD surface suppressed electrode/electrolyte interfacial charge recombination and facilitated more electron injection from QDs into TiO2 photoanode. The EDAX elemental mapping results inferred that CdS, CdSe and ZnS have efficiently covered the TiO2 surface. TiO2/CdS and CdS/CdSe interfaces and the amorphous nature of ZnS could be verified with HRTEM images. Hence, the co-sensitization and surface passivation played a significant role to enhance the PCE of CdS QDSSC from 1.9% to 4.05%.

Effect of ZrS2 load single/dual-atom catalysts on the hydrogen evolution reaction: A first-principles study.

The hydrogen evolution effect of ZrS2 carrier loaded with transition metal single-atom (SA) was explored by first-principles method. ZrS2 was constructed with transition metal single-atom and dual-atom. The structure-activity relationship of supported single-atom catalysts was described by electronic properties and hydrogen evolution kinetics. The results show that the ZrS2 carrier-loaded atomic-level catalysts are more likely to occur in acidic environments, where the Mo SA load has a higher hydrogen precipitation capacity than the Pt SA. In the case of dual-atom adsorption, most of the hydrogen reduction processes are higher than that of single atom loading, which indicates that the outer orbital hybridization is more likely to lead to the interfacial charge recombination of the catalyst. Thereinto, Ni/Pt @ZrS2 has the lowest Gibbs free energy (0.08 eV), and the synergistic effect of transition metals induces the deviation of the center of the d-band from the Fermi level and improves the dissociation ability of H ions. The design provides a new catalytic model for the HER and provides some ideas for understanding the two-site catalysis.

Chemical Bath Deposition of NiOx‐NiSO4 Heterostructured Hole Transport Layer for Perovskite Solar Cells

Herein, the scalable chemical bath deposited NiOx‐NiSO4 heterostructured films are reported as the efficient hole transport layers (HTLs) in perovskite solar cells. The NiOx‐NiSO4 films show excellent hole extraction ability and reduce interfacial charge recombination in solar cell devices. By using NiOx‐NiSO4 HTLs, a high power conversion efficiency of 20.55% is obtained, which is about 12.23% greater than that of the pure NiOx transport layer. This study provides a simple solution‐processing route toward the large‐area production and fabrication of full inorganic transport layers for perovskite photovoltaics.

Interface-Enhanced Charge Recombination in the Heterojunction between Perovskite Nanocrystals and BiOI Nanosheets Serves as an S-Scheme Photocatalyst for CO2 Reduction

We designed an S-heterojunction system with a perovskite nanocrystal, Cs1-xFAxPbBr3 (CF), coupled with a bismuth oxyiodide (BiOI) nanosheet to form a perovskite heterojunction (PHJ) photocatalyst. On the basis of femtosecond transient absorption measurements, the pristine CF sample has two charge recombination periods, 100 and 900 ps, corresponding to surface and bulk trap-state relaxations, respectively. When CF was in contact with BiOI to form an S-heterojunction, rapid interfacial charge recombination occurred to show two decay components with time coefficients 1 and 35 ps, responsible for the electron-hole recombination in the surface and bulk states, respectively. We observed a new photoinduced absorption band on the blue side of the photobleach band of PHJ that gives relaxation more rapid than that of pristine CF, presumably due to doping of bismuth cations creating defect states to enhance the charge recombination that leads to photocatalytic performance for the PHJ catalyst poorer than for the pristine CF sample.

Facile NaF Treatment Achieves 20% Efficient ETL-Free Perovskite Solar Cells.

Electron transporting layer (ETL)-free perovskite solar cells (PSCs) exhibit promising progress in photovoltaic devices due to the elimination of the complex and energy-/time-consuming preparation route of ETLs. However, the performance of ETL-free devices still lags behind conventional devices because of mismatched energy levels and undesired interfacial charge recombination. In this study, we introduce sodium fluoride (NaF) as an interface layer in ETL-free PSCs to align the energy level between the perovskite and the FTO electrode. KPFM measurements clearly show that the NaF layer covers the surface of rough underlying FTO very well. This interface modification reduces the work function of FTO by forming an interfacial dipole layer, leading to band bending at the FTO/perovskite interface, which facilitates an effective electron carrier collection. Besides, the part of Na+ ions is found to be able to migrate into the absorber layer, facilitating enlarged grains and spontaneous passivation of the perovskite layer. As a result, the efficiency of the NaF-treated cell reaches 20%, comparable to those of state-of-the-art ETL-based cells. Moreover, this strategy effectively enhances the operational stability of devices by preserving 94% of the initial efficiency after storage for 500 h under continuous light soaking at 55 °C. Overall, these improvements in photovoltaic properties are clear indicators of enhanced interface passivation by NaF-based interface engineering.

Managing Challenges in Organic Photovoltaics: Properties and Roles of Donor/Acceptor Interfaces

AbstractOrganic photovoltaics (OPVs) have demonstrated increasing potential for use in large‐area, flexible, and light‐weight applications. To date, the rapid development of nonfullerene acceptors (NFAs) and their conjugated polymeric donors have increased the efficiency of OPV by over 19%. Nevertheless, OPV is still suffering from high energy loss, which primarily derives from the donor (D)/acceptor (A) interfacial charge recombination. In particular, the voltage loss occurring at the D/A interface accounts for the current bottleneck, hampering further enhancement of the OPV efficiency. In this review, the recent discovery of D/A interfacial photophysics in NFA‐based OPVs, including the comparison with its fullerene‐based counterpart, is covered. Additionally, the factors governing interfacial energy loss, such as interfacial energetics and local morphologies, which causes the trade‐off relationship between photovoltage and photocurrent in OPV are highlighted. Accordingly, the control of D/A interfacial properties to create an “ideal” interface for charge generation in OPVs is reviewed; and emphasized that the D/A interfacial modifications can serve as a powerful tool to manage the challenges in OPVs path toward future practical applications.

Maximizing Merits of Undesirable δ‐FAPbI3 by Constructing yellow/black Heterophase Bilayer for Efficient and Stable Perovskite Photovoltaics

AbstractYellow‐phase formamidinium lead iodide (δ‐FAPbI3) as a degradation product of black perovskite phase is usually unwelcome in perovskite solar cells (PSCs). However, it also shows high potential in passivating defects and protecting perovskite films from moisture intrusion due to its water‐stable nature. Herein, the utilization of δ‐FAPbI3 to construct a yellow/black heterophase bilayer is reported, in which the perovskite layer is shielded by in situ formed δ‐FAPbI3 species on the surface, for PSCs with enhanced efficiency and stability. It is found that the δ‐FAPbI3 layer with a broader bandgap than the black‐phase perovskite can efficiently suppress the charge recombination at the interface, offering a high PSC efficiency of 23.10%. More importantly, the δ‐FAPbI3‐modified devices exhibit preferable stability against various external stresses to that of the control ones. Compared to those using the disliked δ‐FAPbI3 in the literature, the strategy, which maximizes its merits in reducing the interfacial charge recombination and stabilizing the perovskite structure, is more simple yet effective to realize highly efficient and stable PSCs.

Alkali Metal Cations Modulate the Energy Level of SnO2 via Micro-agglomerating and Anchoring for Perovskite Solar Cells.

N-type tin oxide (SnO2) films are commonly used as an electron transport layer (ETL) in perovskite solar cells (PSCs). However, SnO2 films are of poor quality due to facile agglomeration under a low-temperature preparation method. In addition, energy level mismatch between the SnO2 and perovskite (PVK) layer as well as interfacial charge recombination would cause open-circuit voltage loss. In this work, alkali metal oxalates (M-Oxalate, M = Li, Na, and K) are doped into the SnO2 precursor to solve these problems. First, it is found that the hydrolyzed alkali metal cations tend to change colloid size distribution of SnO2, in which Na-Oxalate with suitable basicity leads to most uniform colloid size distribution and high-quality SnO2-Na films. Second, the electron conductivity is enhanced by slightly agglomerated SnO2-Na, which facilitates the transmission of electrons. Third, alkali metal cations increase the conduction band level of SnO2 in the sequence of K+, Na+, and Li+ to promote band alignment between ETLs and perovskite. Based on the optimized film quality and energy states of SnO2-Na, the best PSC efficiency of 20.78% is achieved with a significantly enhanced open-circuit voltage of 1.10 V. This work highlights the function of alkali metal salts on the colloid particle distribution and energy level modulation of SnO2.

D-A-π-A organic dyes with fluorenyl-substituted bulky donor for efficient dye-sensitized solar cells

Improving light-harvesting efficiency and suppressing interfacial charge recombination are of paramount importance to the development of Cu (II/I) redox shuttle-based dye-sensitized solar cells (DSSCs). Here, we present a rational molecular engineering on D-A-π-A organic sensitizers featuring with fluorenyl-substituted bulky donor (HY57, HY60, and HY61) for Cu (II/I) mediated DSSCs. By gradually enhancing conjugation and rigidity of the π-spacer and auxiliary acceptor moieties, the light-harvesting and electron-injection efficiencies can be simultaneously improved. The large size of fluorenyl-substituted arylamine donor together with abundant alkyl chains decorated on the molecular structures assist dense assembly of dye monolayer at surface of nanocrystalline TiO2, which largely suppress interfacial charge recombination losses. When applied in Cu (II/I) mediated DSSCs, the combination of an auxiliary acceptor of phenanthrene-fused-quinoxaline (PFQ) and a π-spacer of cyclopentadithiophene (CPDT) in dye HY61 results in a simultaneous enhancement in short-circuit current (JSC) and open-circuit voltage (VOC), thus improving the power conversion efficiency (PCE) from 7.3% for reference dye HY59 to 10.3% for HY61. This study demonstrates that rigid and fused building block is promising towards constructing highly efficient organic sensitizers.

Synergetic Regulation of Oriented Crystallization and Interfacial Passivation Enables 19.1% Efficient Wide‐Bandgap Perovskite Solar Cells

AbstractWide‐bandgap (WBG) perovskite solar cells (PSCs) suffer from severe voltage loss, which significantly limits the enhancement of photovoltaic performance. Here, 4‐fluoro‐phenylethylammonium iodide (FPEAI) is used as a dual‐functional agent for oriented crystallization and comprehensive passivation of WBG PSCs. The additive of FPEAI promotes crystals to grow along with the (100) orientation with improved crystallinity and to spontaneously form Ruddlesden–Popper 2D perovskite on the grain boundary and surface of 3D crystals, which can passivate defects and protect the perovskite film from moisture erosion as well as suppressed ion migration. In addition, the 2D/3D heterostructure induces a matched energy‐level alignment, which mitigates the detrimental interfacial charge recombination at the interface of the 3D perovskite and hole transport layer. Consequently, the modified WBG PSCs exhibit an improved open‐circuit voltage to 1.3 V and a fill factor of 77.8%, leading to a remarkable power conversion efficiency of 19.1% with negligible hysteresis. Furthermore, the WBG PSCs maintain 85% of the original efficiency after 1000 h in air, demonstrating outstanding humidity stability. This work indicates that FPEAI can be used as a dual‐functional agent to significantly enhance the efficiency of WBG PSCs.

Hydrogen bonding drives the self-assembling of carbazole-based hole-transport material for enhanced efficiency and stability of perovskite solar cells

Designing a hole-transport material (HTM) that guarantees effective hole transport while self-assembling at the perovskite|HTM interface with the formation of an ordered interlayer, has recently emerged as a promising strategy for high-performance and stable perovskite solar cells (PSCs). Hydrogen bonding (HB) is a versatile multi-functional tool for the design of small molecular HTMs. However, to date, its employment is mostly limited to p-i-n inverted PSCs. This study demonstrates the advantages of a novel HTM design that can self-assemble into a long-range ordered interlayer on the perovskite surface via HB association. A hydro-functional HTM (O1) is compared to a reference HTM (O2) that cannot form HB due to the replacement of the amide group of O1 with a plain butyl alkyl chain in O2. As a result, O1-based n-i-p PSCs display enhanced hole extraction reaction, suppressed interfacial charge recombination, reduced hysteresis effect, and an increase in Voc (by 60 mV), FF (>11% increase), and overall power conversion efficiency, PCE (32% increase) compared to the case of HB-free O2-based devices. Remarkable stability is observed for unencapsulated O1 cells, with a T80 lifetime of 35.5 h under continuous maximum power point tracking in air. This work emphasizes the role of HB-directed self-assembling in simultaneously enhancing both the PCE and stability of popular n-i-p PSCs. This study paves the way for the development of new hydro-functional charge-transport material designs for efficient and stable PSCs.

Location effect of triptycene on the photovoltaic performance of carbazole-based dyes

Due to the unique three-dimensional spatial structure and special electronic properties, triptycene has been applied in dye-sensitized solar cells. Herein, two dyes JY76/JY77 featuring triptycene at the different substitution position of carbazole donor have been synthesized, and location effect of triptycene on the photovoltaic performance of devices has been investigated. Lateral derived triptycene endows JY77 much more enhanced capability of impeding the interface charge recombination than JY76 which triptycene was decorated at terminal. Finally, JY77-sensitized solar cells exhibit around 20% higher power conversion efficiency (PCE) than that of JY76. The photovoltaic properties are further tuned by co-sensitization strategy, and better PCEs are obtained. Under AM 1.5G irradiation, cells fabricated by the synergic adsorption of JY77 and JY75, achieve the highest PCE of 8.01%.

Interface Effects in Triazine‐Based g‐C3N4/MAPbI3 Van der Waals Heterojunctions: A First‐Principles Study

2D materials (TDMs) have demonstrated their great potential as functional materials in perovskite solar cells (PSCs) to boost conversion efficiency. As a versatile TDM, g‐C3N4 has far less applications in PSCs than in medical science, energy storage, supercapacitors, and catalysis. Is 2D g‐C3N4 naturally incompatible with perovskites limiting their cooperation? Herein, the capacity of two kinds of triazine‐based g‐C3N4 as interfacial modifiers for CH3NH3PbI3 (MAPbI3) perovskite based on density functional theory is discussed. Due to the existence of two feasible atomically exposed surfaces in MAPbI3 perovskite, denoted as PbI and MAI interfaces, four heterojunction structures are constructed. The interfacial carrier transport kinetics and charge recombination region distribution of the heterojunctions are systematically investigated. The results show that the NPCN/MAI heterojunction facilitates the separation and transport of charges due to its type‐II energy band alignment and smaller charge recombination region. Herein, a promising interface‐modified 2D material for perovskite photoactive layer is introduced and an avenue to reduce the charge recombination loss in PSCs is provided.

Combining Polymer Zwitterions and Zinc Oxide for High-Performance Inverted Organic Solar Cells.

Zinc oxide (ZnO) is a widely used cathode interlayer material in inverted organic solar cells (OSCs). However, there are lots of surfaces or bulk film defects in ZnO layers, which degrade solar cell performance. Here, the typical phosphorylcholine- and sulfobetaine-based polymer zwitterions (PMPC and PDMAPS) are synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization to modify ZnO interlayers for inverted OSCs. The polymer zwitterions can efficiently passivate the defects in ZnO films and thus increase the conductivity of the ZnO interlayers. Both PMPC and PDMAPS modified ZnO interlayers show some general advantages in improving the performance of fullerene-based and non-fullerene-based OSCs. The highest efficiency of 16.69% is achieved by using PMPC modified ZnO interlayers in PM6:Y6 based solar cell devices, which is among the best performance in inverted OSCs. Such an improvement in device performance is attributed to the work function reduction of the polymer zwitterions modified ZnO films, which provides an efficient cathode platform to extract and transport electrons from the active layers, to the benefit of suppressing interfacial charge recombination. As a result, the organic-inorganic hybrid composites (ZnO: polymer zwitterions) show efficient interfacial modification to align energy levels at the device interface, which have promising application prospects in organic electronics.

Tailored Polymeric Hole-Transporting Materials Inducing High-Quality Crystallization of Perovskite for Efficient Inverted Photovoltaic Devices.

For achieving high-performance p-i-n perovskite solar cells (PSCs), hole transporting materials (HTMs) are critical to device functionality and represent a major bottleneck to further enhancing device stability and efficiency in the inverted devices. Three dopant-free polymeric HTMs are developed based on different linkage sites of triphenylamine and phenylenevinylene repeating units in their main backbone structures. The backbone curvatures of the polymeric HTMs affect the morphology and hole mobility of the polymers and further change the crystallinity of perovskite films. By using PTA-mPV with moderate molecular curvature, p-i-n PSCs with high efficiency of 19.5% and long-term stability can be achieved. The better performance is attributed to the more effective hole extraction ability, higher charge-carrier mobility, and lower interfacial charge recombination. Furthermore, these three polymeric HTMs are synthesized without any noble metal catalyst, and show great advantages in future application owing to the low-cost.

Designed p-type graphene quantum dots to heal interface charge transfer in Sn-Pb perovskite solar cells

In Sn-Pb based low bandgap perovskite solar cells (LB-PSCs), the large energy loss of ~0.5 eV lags its development, originating from unfavorable band alignment at the interface and serious charge recombination in the device. Here, judiciously designed graphene quantum dots by functional N/Cl doping are applied at PEDOT:PSS/perovskite interface to modulate the energy level and charge transfer simultaneously. Among three designed graphene quantum dots, the N, Cl codoped one (N,Cl-GQDs) induces the best band alignment, because of the enhanced p-doping. Besides, N,Cl-GQDs best regulate the charge distribution and passivate the defect states at the interface by π-conjugated effect and electronegative Cl, paving the way for efficient interface charge transport. Upon N,Cl-GQDs optimization, the FA0.6MA0.4Sn0.6Pb0.4I3 based PSCs achieves impressive efficiency of 21.5% (1 sun, AM1.5) with a high photovoltage of ~0.89 V (energy loss of ~0.36 eV) and fill factor over 80%, which are among the best parameters in reported LB-PSCs. The N,Cl-GQDs modified device exhibits the best shelf stability after 1000 h, due to the least trap states and reformative interface. This work highlights designed graphene quantum dots for photovoltaic applications.

Room Temperature Fabrication of SnO2 Electrodes Enabling Barrier‐Free Electron Extraction for Efficient Flexible Perovskite Photovoltaics

AbstractRoom temperature‐processed electron transport layers (RT‐ETLs) demonstrate vast potential to be used in fabricating high‐performance flexible perovskite solar cells (PSCs) in an energy‐saving manner. However, the RT‐ETL normally suffers from inferior crystallinity, mismatched energy level, and high surface trap‐state density, which would result in under‐optimized interfacial electron extraction and undesirable interfacial charge recombination at ETL/perovskite interface, thus limiting the device performance. Herein, a novel strategy is demonstrated to prepare annealing‐free RT‐ETL based on precrystalline metal ion‐modified SnO2 nanocrystals, which perfectly optimizes the interfacial energy level alignment between ETL and perovskite layer, achieving nearly zero‐barrier charge transfer at the interface. As a result, the charge extraction has been remarkably accelerated and the interfacial charge recombination has been largely suppressed, leading to a ≈26% enhancement in device efficiency. The best‐performing flexible PSCs achieve efficiencies up to 19.3%, accompanied by outstanding mechanical strength under repeated bending cycle tests, which, to the best of the knowledge, is one of the highest reported values for the flexible perovskite photovoltaics fabricated with RT‐ETLs.

Highly improved efficiency and stability of planar perovskite solar cells via bifunctional phytic acid dipotassium anchored SnO2 electron transport layer

The defects at the interface of SnO2 electron transport layers (ETLs) /perovskite layer hinder extraction and transfer of charge, which restrict the further improvement of the photoelectric conversion efficiency (PCE) of SnO2-based perovskite solar cells (PSCs). Herein, an effective bifunctional anchoring strategy is developed to passivate SnO2/perovskite interface defects by adequate chelate sites in polydentate phytic acid dipotassium (PAD) to anchor SnO2 colloids. It is confirmed that polydentate PAD anchoring can form new Sn-O-P bonds with uncoordinated Sn2+, which can efficiently passivate the SnO2 surface defects and alleviate the interfacial charge recombination between SnO2 and perovskite layer. The reduction of SnO2 surface defects enhances the electron transport efficiency and increases the conductivity of the PAD-SnO2 ETLs to 2.1 times that of SnO2 ETLs. Meanwhile, the anchoring group potassium ions (K+) in PAD can promote the in-plane growth of perovskite grains and increase the average grain size of perovskite from 560 nm to 850 nm. As a consequence, the PCE of the PAD-SnO2-based PSCs increased sharply to 21.61%, which is 10.7% higher than that of the PSCs made with SnO2 ETLs (19.52%). The unencapsulated PSCs deposited on PAD-SnO2 ETLs can remain 99.5% of their initial efficiency after 60 days under 25–30% humidity.

Zn-doped CdS/CdSe as efficient strategy to enhance the photovoltaic performance of quantum dot sensitized solar cells

Metal ion doping is a suitable approach for optimizing quantum dots (QDs), which can change the recombination dynamics and charge separation of QDs via creating electronic states within their band gap, and improve their optical and electrical properties. In this work, the transition metal Zn-doped CdS and CdSe QDs are performed by SILAR (successive ionic layer adsorption and reaction) method. And the sensitized solar cells (QDSSCs) based on the Zn-doped CdS and CdSe QDs are assembled. The effect of Zn-doping concentration on the optical properties and charge carrier transport characteristics of photoanodes is investigated. Based on these QDs sensitized TiO2 photoanodes, the assembled QDSSCs with Zn-dopant of a molar concentration of 1.6 mol % exhibited a maximum power conversion efficiency (PCE) of 5.59 %, which is increased by 26.76 % in comparison with that of the QDSSC (4.41%) without Zn-doping. The significantly enhanced PCE of QDSSCs was attributed to improved current density and open-circuit voltage, particularly arising from enhanced light absorbance by narrowing the band gap with the midgap states and upshift of Fermi level promoted by the high electrons concentration due to the ionization of Zn impurities. In addition, the Zn-doping contributes to attenuation of the interfacial charge recombination rate and prolongs the electron lifetime, resulting in more efficient charge collection in QDSSCs.