Strengthened Surface Modification for High-Performance Inorganic Perovskite Solar Cells with 21.3% Efficiency.

Metal halide inorganic perovskites show excellent thermal stability compared to organic-inorganic perovskites. However, the performance of inorganic perovskite solar cells (PSCs) is far from theoretical values, together with unsatisfactory stability, mainly due to the poor interfacial properties. In this work, a facial but effective method is reported to realize high-performance inorganic PSCs by post-modifying the perovskite surface with 2-thiophene ethylamine (TEA). It is found that amine group from TEA can favorably interact with the undercoordinated Pb2+ via Lewis acid-based coordination, while thiophene ring with electron-rich sulfur assists such interaction by functioning as an electron donor. The synergetic interaction allows TEA to passivate perovskite film defects more efficiently, as compared to phenethylamine (PEA) with less electron-donating ability. Moreover, perovskite valence band is slightly upward shift to match with hole transport material and facilitate hole transfer. These combinations result in a reduced non-radiative charge recombination and improved charge carrier lifetime. Consequently, PSCs with TEA modification shows a drastic improvement of VOC by 54 mV, yielding a champion PCE of 21.3%, much higher than the control PSCs (19.3%), along with improved ambient stability. This work demonstrates that surface modifier with an electron-rich moiety is critical for achieving efficient and stable inorganic PSCs.

Molecular Bridge on Buried Interface for Efficient and Stable Perovskite Solar Cells.

The interface of perovskite solar cells (PSCs) is significantly important for charge transfer and device stability, while the buried interface with the impact on perovskite film growth has been paid less attention. Herein, we use a molecular modifier, glycocyamine (GDA) to build a molecular bridge on the buried interface of SnO2 /perovskite, resulting in superior interfacial contact. This is achieved through the strongly interaction between GDA and SnO2 , which also appreciably modulates the energy level. Moreover, GDA can regulate the perovskite crystal growth, yielding perovskite film with enlarged grain size and absence of pinholes, exhibiting substantially reduced defect density. Consequently, PSCs with GDA modification demonstrate significant improvement of open circuit voltage (close to 1.2 V) and fill factor, leading to an improved power conversion efficiency from 22.60 % to 24.70 %. Additionally, stabilities of GDA devices under maximum power point and 85 °C heat both perform better than the control devices.

Fluorine-Containing Passivation Layer via Surface Chelation for Inorganic Perovskite Solar Cells.

Minimizing surface defect is vital to further improve power conversion efficiency (PCE) and stability of inorganic perovskite solar cells (PSCs). Herein, we designed a passivator trifluoroacetamidine (TFA) to suppress CsPbI3-x Brx film defects. The amidine group of TFA can strongly chelate onto the perovskite surface to suppress the iodide vacancy, strengthened by additional hydrogen bonds. Moreover, three fluorine atoms allow strong intermolecular connection via intermolecular hydrogen bonds, thus constructing a robust shield against moisture. The TFA-treated PSCs exhibit remarkably suppressed recombination, yielding the record PCEs of 21.35 % and 17.21 % for 0.09 cm2 and 1.0 cm2 device areas, both of which are the highest for all-inorganic PSCs so far. The device also achieves a PCE of 39.78 % under indoor illumination, the highest for all-inorganic indoor photovoltaic devices. Furthermore, TFA greatly improves device ambient stability by preserving 93 % of the initial PCE after 960 h.

Hydrazide Derivatives for Defect Passivation in Pure CsPbI3 Perovskite Solar Cells.

All-inorganic CsPbI3 perovskite presents preeminent chemical stability and a desirable band gap as the front absorber for perovskite/silicon tandem solar cells. Unfortunately, CsPbI3 perovskite solar cells (PSCs) still show low efficiency due to high density of defects in solution-prepared CsPbI3 films. Herein, three kinds of hydrazide derivatives (benzoyl hydrazine (BH), formohydrazide (FH) and benzamide (BA)) are designed to reduce the defect density and stabilize the phase of CsPbI3 . Calculation and characterization results corroborate that the carboxyl and hydrazine groups in BH form strong chemical bonds with Pb2+ ions, resulting in synergetic double coordination. In addition, the hydrazine group in the BH also forms a hydrogen bond with iodine to assist the coordination. Consequently, a high efficiency of 20.47 % is achieved, which is the highest PCE among all pure CsPbI3 -based PSCs reported to date. In addition, an unencapsulated device showed excellent stability in ambient air.

Robust Self-Assembled Molecular Passivation for High-Performance Perovskite Solar Cells.

Defect passivation via post-treatment of perovskite films is an effective method to fabricate high-performance perovskite solar cells (PSCs). However, the passivation durability is still an issue due to the weak and vulnerable bonding between passivating functional groups and perovskite defect sites. Here we propose a cholesterol derivative self-assembly strategy to construct crosslinked and compact membranes throughout perovskite films. These supramolecular membranes act as a robust protection layer against harsh operational conditions while providing effective passivation of defects from surface toward inner grain boundaries. The resultant PSCs exhibit a power conversion efficiency of 23.34 % with an impressive open-circuit voltage of 1.164 eV. The unencapsulated devices retain 92 % of their initial efficiencies after 1600 h of storage under ambient conditions, and remain almost unchanged after heating at 85 °C for 500 h in a nitrogen atmosphere, showing significantly improved stability.

Interfaces and Interfacial Layers in Inorganic Perovskite Solar Cells.

Owing to their superior thermal stability, metal halide inorganic perovskite materials continue to attract interest for photovoltaics applications. The highest reported power conversion efficiency (PCE) for solar cells based on inorganic perovskites is over 20 %. As this PCE corresponds to 73 % of the theoretical limit, there remains more room for further improving the device PCEs than for improving organic-inorganic hybrid perovskite solar cells (PSCs). The main loss is in the photovoltage, which is limited by interfaces in terms of non-radiative recombination caused by traps and energy-level mismatch. Furthermore, inefficient charge extraction at interfacial contacts reduces the photocurrent and fill factor. This Minireview summarizes the recent developments in the fundamental understanding of how the interfaces and interfacial layers influence the performance of solar cells based on inorganic perovskite absorbers. An outlook for the development of highly efficient and stable inorganic PSCs from the interface point of view is also given.

Rational Surface-Defect Control via Designed Passivation for High-Efficiency Inorganic Perovskite Solar Cells.

Iodine vacancies (VI ) and undercoordinated Pb2+ on the surface of all-inorganic perovskite films are mainly responsible for nonradiative charge recombination. An environmentally benign material, histamine (HA), is used to passivate the VI in perovskite films. A theoretical study shows that HA bonds to the VI on the surface of the perovskite film via a Lewis base-acid interaction; an additional hydrogen bond (H-bond) strengthens such interaction owing to the favorable molecular configuration of HA. Undercoordinated Pb2+ and Pb clusters are passivated, leading to significantly reduced surface trap density and prolonged charge lifetime within the perovskite films. HA passivation also induces an upward shift of the energy band edge of the perovskite layer, facilitating interfacial hole transfer. The combination of the above raises the solar cell efficiency from 19.5 to 20.8 % under 100 mW cm-2 illumination, the highest efficiency so far for inorganic metal halide perovskite solar cells (PSCs).

Introducing manganese complexes as redox mediators for dye-sensitized solar cells.

The abundance and low toxicity of manganese have led us to explore the application of manganese complexes as redox mediators for dye sensitized solar cells (DSCs), a promising solar energy conversion technology which mimics some of the key processes in photosynthesis during its operation. In this paper, we report the development of a DSC electrolyte based on the tris(acetylacetonato)manganese(iii)/(iv), [Mn(acac)3](0/1+), redox couple. PEDOT-coated FTO glass was used as a counter electrode instead of the conventionally used platinum. The influence of a number of device parameters on the DSC performance was studied, including the concentration of the reduced and oxidized mediator species, the concentration of specific additives (4-tert-butylpyridine, lithium tetrafluoroborate, and chenodeoxycholic acid) and the thickness of the TiO2 working electrode. These studies were carried out with a new donor-π-acceptor sensitizer K4. Maximum energy conversion efficiencies of 3.8% at simulated one Sun irradiation (AM 1.5 G; 1000 W m(-2)) with an open circuit voltage (VOC) of 765 mV, a short-circuit current (JSC) of 7.8 mA cm(-2) and a fill factor (FF) of 0.72 were obtained. Application of the commercially available MK2 and N719 sensitizers resulted in an energy conversion efficiency of 4.4% with a VOC of 733 mV and a JSC of 8.6 mA cm(-2) for MK2 and a VOC of 771 mV and a JSC of 7.9 mA cm(-2) for N719. Both dyes exhibit higher incident photon to current conversion efficiencies (IPCEs) than K4.

Controlling interfacial recombination in aqueous dye-sensitized solar cells by octadecyltrichlorosilane surface treatment.

A general and convenient strategy is proposed for enhancing photovoltaic performance of aqueous dye-sensitized solar cells (DSCs) through the surface modification of titania using an organic alkyl silane. Introduction of octadecyltrichlorosilane on the surface of dyed titania photoanode as an organic barrier layer leads to the efficient suppression of electron recombination with oxidized cobalt species by restricting access of the cobalt redox couple to the titania surface. The champion ODTS-treated aqueous DSCs (0.25 mM ODTS in hexane for 5 min) exhibit a V(oc) of 821±4 mV and J(sc) of 10.17±0.21 mA cm(-2), yielding a record PCE of 5.64±0.10%. This surface treatment thus serves as a promising post-dye strategy for improving the photovoltaic performance of other aqueous DSCs.

Defect Passivation and Lithium Ion Coordination Via Hole Transporting Layer Modification for High Performance Inorganic Perovskite Solar Cells.

Metal halide inorganic perovskite solar cells (PSCs) have great potential to achieve high efficiency with excellent thermal stability. However, the surface defect traps restrain the achievement of high open circuit voltage (VOC ) and power conversion efficiency (PCE) of the devices due to the severe nonradiative charge recombination. Moreover, the state-of-the-art hole transporting layer (HTL) significantly hampers device moisture stability, even though it renders the highest solar cell efficiency. Herein, a one-stone-two-birds strategy is proposed using a biocompatible material tryptamine (TA) as an additive in HTL. First, TA bearing electron rich moieties can favorably passivate the surface defects of inorganic perovskite films, significantly reducing trap density and prolonging charge lifetime. It results in a drastic improvement of VOC from 1.192 to 1.251 V, with a VOC loss of 0.48 V. The corresponding PSCs achieve a 21.8% PCE under 100 mW cm-2 illumination. Second, TA in HTL can coordinate with lithium cations, retarding their reaction with moisture and increasing the moisture stability of HTL. Consequently, the black phase of inorganic perovskite films is well preserved, and the corresponding PSCs maintain 90% of the initial PCE after 800 h storage at relative humidity of 25-35%, much higher than the control devices.

Enhancing Stability and Efficiency of Inverted Inorganic Perovskite Solar Cells with In-Situ Interfacial Cross-Linked Modifier.

Inverted inorganic perovskite solar cells (PSCs) is potential as the top cells in tandem configurations, owing to the ideal bandgap, good thermal and light stability of inorganic perovskites. However, challenges such as mismatch of energy levels between charge transport layer and perovskite, significant non-radiative recombination caused by surface defects, and poor water stability have led to the urgent need for further improvement in the performance of inverted inorganic PSCs. Herein, the fabrication of efficient and stable CsPbI3-xBrx PSCs through surface treatment of (3-mercaptopropyl) trimethoxysilane (MPTS), is reported. The silane groups in MPTS can in situ crosslink in the presence of moisture to build a 3-dimensional (3D) network by Si-O-Si bonds, which forms a hydrophobic layer on perovskite surface to inhibit water invasion. Additionally, -SH can strongly interact with the undercoordinated Pb2+ at the perovskite surface, effectively minimizing interfacial charge recombination. Consequently, the efficiency of the inverted inorganic PSCs improves dramatically from 19.0% to 21.0% under 100 mW cm-2 illumination with MPTS treatment. Remarkably, perovskite films with crosslinked MPTS exhibit superior stability when soaking in water. The optimized PSC maintains 91% of its initial efficiency after aging 1000 h in ambient atmosphere, and 86% in 800 h of operational stability testing.

Interface Modification for Efficient and Stable Inverted Inorganic Perovskite Solar Cells.

Due to their excellent thermal stability and ideal bandgap, metal halide inorganic perovskite based solar cells (PSCs) with inverted structure are considered as an excellent choice for perovskite/silicon tandem solar cells. However, the power conversion efficiency (PCE) of inverted inorganic perovskite solar cells (PSCs) still lags far behind that of conventional n-i-p PSCs due to interfacial energy level mismatch and high nonradiative charge recombination. Herein, the performance of inverted PSCs is significantly improved by interfacial engineering of CsPbI3- x Brx films with 2-mercapto-1-methylimidazole (MMI). It is found that the mercapto group can preferably react with the undercoordinated Pb2+ from perovskite by forming Pb-S bonds, which appreciably reduces the surface trap density. Moreover, MMI modification results in a better energy level alignment with the electron-transporting material, promoting carrier transfer and reducing voltage deficit. The above combination results in an open-circuit voltage enhancement by 120 mV, yielding a champion PCE of 20.6% for 0.09 cm2 area and 17.3% for 1 cm2 area. Furthermore, the ambient, operational and heat stabilities of inorganic PSCs with MMI modification are also greatly improved. The work demonstrates a simple but effective approach for fabricating highly efficient and stable inverted inorganic PSCs.

Tailored Cysteine-Derived Molecular Structures toward Efficient and Stable Inorganic Perovskite Solar Cells.

Surface-defect-triggered non-radiative charge recombination and poor stability have become the main roadblock to continued improvement in inorganic perovskite solar cells (PSCs). Herein, the main culprits are identified on the inorganic perovskite surface by first-principles calculations, and to purposefully design a brand-new passivator, Boc-S-4-methoxy-benzyl-l-cysteine (BMBC), whose multiple Lewis-based functional groups (NH, S and CO) to suppress halide vacancies and coordinate with undercoordinated Pb2+ through typical Lewis baseacid reactions. The tailored electron-donating methoxyl group (CH3 O-) can cause an increased electron density on the benzene ring, which strengthens the interaction with undercoordinated Pb2+ via electrostatic interactions. This BMBC passivation can reduce the surface trap density, enlarge grains, prolong the charge lifetime, and cause a more suitable energy-level alignment. In addition, the hydrophobic tert-butyl in butoxycarbonyl (Boc-) group ensures that BMBC is uniformly covered and prevents harmful aggregation through steric repulsion at the perovskite/hole-transporting layer (HTL) interface, thus providing a hydrophobic umbrella to resist moisture invasion. Consequently, the combination of the above increases the efficiency of CsPbI3-x Brx PSC from 18.6% to 21.8%, the highest efficiency for this type of inorganic metal halide PSCs so far, as far as it is known. Moreover, the device exhibits higher environmental and thermal stability.

Simultaneous Lattice Engineering and Defect Control via Cadmium Incorporation for High-Performance Inorganic Perovskite Solar Cells.

Doping of all-inorganic lead halide perovskites to enhance their photovoltaic performance and stability has been reported to be effective. Up to now most studies have focused on the doping of elements in to the perovskite lattice. However, most of them cannot be doped into the perovskite lattice and the roles of these dopants are still controversial. Herein,the authors introduce CdI2 as an additive into CsPbI3-x Brx and use it as active layer to fabricate high-performance inorganic perovskite solar cells (PSCs). Cd with a smaller radius than Pb can partially substitute Pb in the perovskite lattice by up to 2 mol%. Meanwhile, the remaining Cd stays on the surface and grain boundaries (GB) of the perovskite film in the form of Cs2 CdI4-x Br-x , which is found to reduce non-radiative recombination. These effects result in prolonged charge carrier lifetime, suppressed defect formation, decreased GBs, and an upward shift of energybands in the Cd-containing film. A champion efficiency of 20.8% is achieved for Cd-incorporated PSCs, together with improved device ambient stability. This work highlights the importance of simultaneous lattice engineering, defectcontrol and atomic-level characterization in achieving high-performance inorganic PSCs with well-defined structure-property relationships.

High-conductivity thiocyanate ionic liquid interface engineering for efficient and stable perovskite solar cells.

A high-conductivity thiocyanate ionic liquid (EMIMSCN) was introduced into perovskite solar cells for the first time. The high conductivity of EMIMSCN ensures an adequate supply of free SCN- anions and EMIM+ cations, so as to multifunctionally passivate the I vacancy and Pb-I antisite defects and realize an optimized interfacial energy level. Consequently, the devices with EMIMSCN treatment achieve a high PCE of 22.55% with substantial enhancement in stability. This simple and efficient strategy provides new insights into the selection of passivation agents for efficient and stable PSCs.

Enhanced Performance of Carbon-Selenide Composite with La0.9Ce0.1NiO3 Perovskite Oxide for Outstanding Counter Electrodes in Platinum-Free Dye-Sensitized Solar Cells.

For large-scale applications, dye-sensitized solar cells (DSSCs) require the replacement of the scarce platinum (Pt)-based counter electrode (CE) with efficient and cheap alternatives. In this respect, low-cost perovskite oxides (ABO3) have been introduced as promising additives to composite-based CEs in Pt-free DSSCs. Herein, we synthesized composites from La0.9Ce0.1NiO3 (L) perovskite oxide and functionalized-multiwall-carbon-nanotubes wrapped in selenides derived from metal-organic-frameworks (f-MWCNT-ZnSe-CoSe2, "F"). L and F were then mixed with carbon black (CB) in different mass ratios to prepare L@CB, F@CB, and L@F@CB composites. The electrochemical analysis revealed that the L@F@CB composite with a mass ratio of 1.5:3:1.5 exhibits better electrocatalytic activity than Pt. In addition, the related DSSC reached a better PCE of 7.49% compared to its Pt-based counterpart (7.09%). This improved performance is the result of the increase in the oxygen vacancy by L due to the replacement of La with Ce in its structure, leading to more active sites in the L@F@CB composites. Moreover, the F@CB composite favors the contribution to the high electrical conductivity of the hybrid carbon nanotube-carbon black, which also offers good stability to the L@F@CB CE by not showing any obvious change in morphology and peak-to-peak separation even after 100 cyclic voltammetry cycles. Consequently, the corresponding L@F@CB-based device achieved enhanced stability. Our work demonstrates that L@F@CB composites with a low cost are excellent alternatives to Pt CE in DSSCs.

Improvements of photocurrent by using modified SiO(2) in the poly(ether urethane)/poly(ethylene oxide) polymer electrolyte for all-solid-state dye-sensitized solar cells.

Nanocomposite polymer electrolytes containing poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/modified SiO(2) were prepared for all-solid-state dye-sensitized solar cells with a high efficiency of 4.86% and an active area of 0.25 cm(2) under AM1.5 conditions at 100 mW cm(-2) irradiation.

Review on Recent Progress of All-Inorganic Metal Halide Perovskites and Solar Cells.

All-inorganic perovskites are considered to be one of the most appealing research hotspots in the field of perovskite photovoltaics in the past 3 years due to their superior thermal stability compared to their organic-inorganic hybrid counterparts. The power-conversion efficiency has reached 17.06% and the number of important publications is ever increasing. Here, the progress of inorganic perovskites is systematically highlighted, covering materials design, preparation of high-quality perovskite films, and avoidance of phase instabilities. Inorganic perovskites, nanocrystals, quantum dots, and lead-free compounds are discussed and the corresponding device performances are reviewed, which have been realized on both rigid and flexible substrates. Methods for stabilization of the cubic phase of low-bandgap inorganic perovskites are emphasized, which is a prerequisite for highly efficient and stable solar cells. In addition, energy loss mechanisms both in the bulk of the perovskite and at the interfaces of perovskite and charge selective layers are unraveled. Reported approaches to reduce these charge-carrier recombination losses are summarized and complemented by methods proposed from our side. Finally, the potential of inorganic perovskites as stable absorbers is assessed, which opens up new perspectives toward the commercialization of inorganic perovskite solar cells.

Improved Performance of Planar Perovskite Solar Cells Using an Amino-Terminated Multifunctional Fullerene Derivative as the Passivation Layer.

Organic-inorganic metal-halide perovskite solar cells (PSCs) have been revolutionizing the photovoltaic (PV) community in the past decade. However, the trap states in TiO2 as the electron-transport layer seriously affect the device PV performance and stability. Here, we design and synthesize a fullerene derivative C60NH2 featuring an amino-terminated group. We use C60NH2 as a passivation layer between TiO2 and perovskite in planar PSCs with a standard configuration to improve the quality of the obtained perovskite film as well as the electron-transfer efficiency, resulting in an obvious increment of PV performance and stability of the devices. The champion power conversion efficiency of 18.34% is achieved under 100 mW cm-2 illumination utilizing C60NH2 as the passivation layer with much less hysteresis. Planar PSCs demonstrate superior stability under natural sunlight and 40-50% relative humidity after C60NH2 passivation. This work enriches the choices of materials for interface engineering toward fabrication of planar PSCs with high performance.

Ba-induced phase segregation and band gap reduction in mixed-halide inorganic perovskite solar cells.

All-inorganic metal halide perovskites are showing promising development towards efficient long-term stable materials and solar cells. Element doping, especially on the lead site, has been proved to be a useful strategy to obtain the desired film quality and material phase for high efficient and stable inorganic perovskite solar cells. Here we demonstrate a function by adding barium in CsPbI2Br. We find that barium is not incorporated into the perovskite lattice but induces phase segregation, resulting in a change in the iodide/bromide ratio compared with the precursor stoichiometry and consequently a reduction in the band gap energy of the perovskite phase. The device with 20 mol% barium shows a high power conversion efficiency of 14.0% and a great suppression of non-radiative recombination within the inorganic perovskite, yielding a high open-circuit voltage of 1.33 V and an external quantum efficiency of electroluminescence of 10-4.