Dopant-additive synergism enhances perovskite solar modules.

Perovskite solar cells (PSCs) are among the most promising photovoltaic technologies owing to their exceptional optoelectronic properties1,2. However, the lower efficiency, poor stability and reproducibility issues of large-area PSCs compared with laboratory-scale PSCs are notable drawbacks that hinder their commercialization3. Here we report a synergistic dopant-additive combination strategy using methylammonium chloride (MACl) as the dopant and a Lewis-basic ionic-liquid additive, 1,3-bis(cyanomethyl)imidazolium chloride ([Bcmim]Cl). This strategy effectively inhibits the degradation of the perovskite precursor solution (PPS), suppresses the aggregation of MACl and results in phase-homogeneous and stable perovskite films with high crystallinity and fewer defects. This approach enabled the fabrication of perovskite solar modules (PSMs) that achieved a certified efficiency of 23.30% and ultimately stabilized at 22.97% over a 27.22-cm2 aperture area, marking the highest certified PSM performance. Furthermore, the PSMs showed long-term operational stability, maintaining 94.66% of the initial efficiency after 1,000 h under continuous one-sun illumination at room temperature. The interaction between [Bcmim]Cl and MACl was extensively studied to unravel the mechanism leading to an enhancement of device properties. Our approach holds substantial promise for bridging the benchtop-to-rooftop gap and advancing the production and commercialization of large-area perovskite photovoltaics.

Oriented nucleation in formamidinium perovskite for photovoltaics.

The black phase of formamidinium lead iodide (FAPbI3) perovskite shows huge promise as an efficient photovoltaic, but it is not favoured energetically at room temperature, meaning that the undesirable yellow phases are always present alongside it during crystallization1-4. This problem has made it difficult to formulate the fast crystallization process of perovskite and develop guidelines governing the formation of black-phase FAPbI3 (refs. 5,6). Here we use in situ monitoring of the perovskite crystallization process to report an oriented nucleation mechanism that can help to avoid the presence of undesirable phases and improve the performance of photovoltaic devices in different film-processing scenarios. The resulting device has a demonstrated power-conversion efficiency of 25.4% (certified 25.0%) and the module, which has an area of 27.83 cm2, has achieved an impressive certified aperture efficiency of 21.4%.

Controlling Tin Halide Perovskite Oxidation Dynamics in Solution for Perovskite Optoelectronic Devices.

As a leading contender to replace lead halide perovskites, tin-based perovskites have demonstrated ever increasing performance in solar cells and light-emitting diodes (LEDs). They tend to be processed with dimethyl sulfoxide (DMSO) solvent, which has been identified as a major contributor to the Sn(II) oxidation during film fabrication, posing a challenge to the further improvement of Sn-based perovskites. Herein, we use NMR spectroscopy to investigate the kinetics of the oxidation of SnI2, revealing that autoamplification takes place, accelerating the oxidation as the reaction progresses. We propose a mechanism consistent with these observations involving water participation and HI generation. Building upon these insights, we have developed low-temperature Sn-based perovskite LEDs (PeLEDs) processed at 60 °C, achieving enhanced external quantum efficiencies (EQEs). Our research underscores the substantial potential of low-temperature DMSO solvent processes and DMSO-free solvent systems for fabricating oxidation-free Sn-based perovskites, shaping the future direction in processing Sn-containing perovskite materials and optoelectronic devices.

Fully Aromatic Self-Assembled Hole-Selective Layer toward Efficient Inverted Wide-Bandgap Perovskite Solar Cells with Ultraviolet Resistance.

Ultraviolet-induced degradation has emerged as a critical stability concern impeding the widespread adoption of perovskite solar cells (PSCs), particularly in the context of phase-unstable wide-band gap perovskite films. This study introduces a novel approach by employing a fully aromatic carbazole-based self-assembled monolayer, denoted as (4-(3,6-dimethoxy-9H-carbazol-9-yl)phenyl)phosphonic acid (MeO-PhPACz), as a hole-selective layer (HSL) in inverted wide-band gap PSCs. Incorporating a conjugated linker plays a pivotal role in promoting the formation of a dense and highly ordered HSL on substrates, facilitating subsequent perovskite interfacial interactions, and fostering the growth of uniform perovskite films. The high-quality film could effectively suppress interfacial non-radiative recombination, improving hole extraction/transport efficiency. Through these advancements, the optimized wide-band gap PSCs, featuring a band gap of 1.68 eV, attain an impressive power conversion efficiency (PCE) of 21.10 %. Remarkably, MeO-PhPACz demonstrates inherent UV resistance and heightened UV absorption capabilities, substantially improving UV resistance for the targeted PSCs. This characteristic holds significance for the feasibility of large-scale outdoor applications.

Dopant-Free Pyrene-Based Hole Transporting Material Enables Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transporting materials (HTMs) is significant to the stability of perovskite solar cells (PSCs). Here, we developed a novel star-shape arylamine HTM, termed Py-DB, with a pyrene core and carbon-carbon double bonds as the bridge units. Compared to the reference HTM (termed Py-C), the extension of the planar conjugation backbone endows Py-DB with typical intermolecular π-π stacking interactions and excellent solubility, resulting in improved hole mobility and film morphology. In addition, the lower HOMO energy level of the Py-DB HTM provides efficient hole extraction with reduced energy loss at the perovskite/HTM interface. Consequently, an impressive power conversion efficiency (PCE) of 24.33 % was achieved for dopant-free Py-DB-based PSCs, which is the highest PCE for dopant-free small molecular HTMs in n-i-p configured PSCs. The dopant-free Py-DB-based device also exhibits improved long-term stability, retaining over 90 % of its initial efficiency after 1000 h exposure to 25 % humidity at 60 °C. These findings provide valuable insights and approaches for the further development of dopant-free HTMs for efficient and reliable PSCs.

Full Solution Process of a Near-Infrared Light-Emitting Electrochemical Cell Based on Novel Emissive Ruthenium Complexes of 1,10-Phenanthroline-Derived Ligands and a Eutectic Alloy as the Top Electrode.

Near-infrared luminescent materials have recently received considerable attention for a large number of applications, including in solid-state lighting, as bioimaging agents, as photovoltaic cells, and in the telecommunication industry. By adding diverse electron-donating or withdrawing groups on ancillary ligands based on benzenethiol-phenanthroline, we synthesized and optoelectronically characterized a series of novel ionic ruthenium complexes, namely RuS, RuSCl, RuSMe, and RuSNH2, for using in a light-emitting electrochemical cell. The synthesized complexes are intense red emitters in the range of 584-605 nm in solution, which depends on the substitutions of electron donor/acceptor moieties on the ancillary ligands. To find a suitable quantum mechanical approach, benchmark calculations based on time-dependent density functional theory were carried out on these complexes. Our benchmark revealed that the M06-L method has results close to those of the experiment. Furthermore, to gain a deeper insight into electronic transitions, several excitation processes were investigated at the TD-DFT-SMD-MN12-L/gen level. The results showed that in the designed complexes, the dominant transition is between the 4dZ2 electron of Ru (particle) and the π* orbitals of the ancillary ligand (hole). The single-layer devices, including these complexes along with a Ga/In cathode by a facile deposition method without the addition of any electron or hole transport layers, were fabricated and displayed red (678 nm) to near-infrared (701 nm) emission as well as a decrease of turn-on voltage from 3.85 to 3.10 V. In particular, adding a methyl group to the ancillary ligand in the complex RuSNH2 increases the external quantum efficiency to 0.55%, one of the highest observed values in the ruthenium phenanthroline family. This simple structure of the device lets us develop the practical applications of light-emitting electrochemical cells based on injection and screen-printing methods, which are very promising for the vacuum-free deposition of top electrodes.

The evolution of triphenylamine hole transport materials for efficient perovskite solar cells.

In recent years, the dramatic increase in power conversion efficiency (PCE) coupled with a decrease in the total cost of third-generation solar cells has led to a significant increase in the collaborative research efforts of academic and industrial researchers. Such interdisciplinary studies have afforded novel materials, which in many cases are now ready to be brought to the marketplace. Within this framework, the field of perovskite solar cells (PSCs) is currently an important area of research due to their extraordinary light-harvesting properties. In particular, PSCs prepared via facile synthetic procedures, containing hole transport materials (HTMs) with versatile triphenylamine (TPA) structural cores, amenable to functionalization, have become a focus of intense global research activity. To optimize the efficiency of the solar cells to achieve efficiencies closer to rival silicon-based technology, TPA building blocks must exhibit favourable electrochemical, photophysical, and photochemical properties that can be chemically tuned in a rational manner. Although PSCs based on TPA building blocks exhibit attractive properties such as high-power efficiencies, a reduction in their synthetic costs coupled with higher stabilities and environmental considerations still need to be addressed. Considering the above, a detailed summary of the most promising compounds and current methodologies employed to overcome the remaining challenges in this field is provided. The objective of this review is to provide guidance to readers on exploring new avenues for the discovery of efficient TPA derivatives, to aid in the future development and advancement of TPA-based PSCs for commercial applications.

Strain effects on halide perovskite solar cells.

Halide perovskite solar cells (PSCs) have achieved power conversion efficiencies (PCEs) approaching 26%, however, the stability issue hinders their commercialization. Due to the soft ionic nature of perovskite materials, the strain effect on perovskite films has been recently recognized as one of the key factors that affects their opto-electronic properties and the device stability. Herein, we summarized the origins of strain, characterization techniques, and implications of strain on both perovskite film and solar cells as well as various strategies to control the strain. Finally, we proposed effective strategies for future strain engineering. We believe this comprehensive review could further facilitate researchers with a deeper understanding of strain effect and enhance the research activity in engineering the strain to further improve performance and especially the device stability toward commercialization.

Extending the π-Conjugated System in Spiro-Type Hole Transport Material Enhances the Efficiency and Stability of Perovskite Solar Modules.

Hole transport materials (HTMs) are a key component of perovskite solar cells (PSCs). The small molecular 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl)-amine-9,9'-spirobifluorene (spiro-OMeTAD, termed "Spiro") is the most successful HTM used in PSCs, but its versatility is imperfect. To improve its performance, we developed a novel spiro-type HTM (termed "DP") by substituting four anisole units on Spiro with 4-methoxybiphenyl moieties. By extending the π-conjugation of Spiro in this way, the HOMO level of the HTM matches well with the perovskite valence band, enhancing hole mobility and increasing the glass transition temperature. DP-based PSC achieves high power conversion efficiencies (PCEs) of 25.24 % for small-area (0.06 cm2 ) devices and 21.86 % for modules (designated area of 27.56 cm2 ), along with the certified efficiency of 21.78 % on a designated area of 27.86 cm2 . The encapsulated DP-based devices maintain 95.1 % of the initial performance under ISOS-L-1 conditions after 2560 hours and 87 % at the ISOS-L-3 conditions over 600 hours.

Versatile Electroluminescence Color-Tuning Strategy of an Efficient Light-Emitting Electrochemical Cell (LEC) by an Ionic Additive.

The color-tuning strategies of solid-state light-emitting devices (ss-LEDs) are mainly focused on engineering molecular structures. In this paper, for the first time, we developed a facile strategy for tuning the electroluminescence (EL) color from orange to green through the addition of the ionic additive TBAP (tetrabutylammonium perchlorate). To achieve the active ionic emissive compound for use in a light-emitting electrochemical cell (LEC), the neutral biscyclometalated bromo tetrazole iridium(III) [Ir(ppy)2(BrTz)] was exchanged to its cationic complex, [Ir(ppy)2(BrTz-Me)]ClO4 (ppy = 2-phenyl pyridine, BrTz = 4-bromo-2-pyridine tetrazole, BrTz-Me = 4-bromo-2-pyridine methyl tetrazole) with a new synthetic strategy. This method allows employing neutral Ir-cyclometalated complexes, which are ruled out for use in LECs because of their non-ionic behaviors. In the following, an LEC based on the new cationic [Ir(ppy)2(BrTz-Me)]ClO4 as the emissive layer was fabricated between the FTO (fluorine-doped tin oxide) anode and Ga:In alloy cathode without using any additive or polymers, which makes this configuration the simplest ss-LED so far. By adding the ionic additives, the electroluminescence characteristics of [Ir(ppy)2(BrTz-Me)]ClO4 were dramatically increased, including luminance (L) from 162.8 cd/m2 for the device with an additive to 212.9 and 355.9 cd/m2 for devices containing LiTFSI (bis(trifluoromethane)sulfonamide lithium salt) and TBAP, respectively. In particular, when TBAP was added to the [Ir(ppy)2(BrTz-Me)]ClO4 complex, the irradiance was significantly increased from 166.4 to 220.8 µW/cm2 with an efficacy of 1.78 cd/A and external quantum efficiency (EQE) value of 2.14%. The obtained EL results clearly showed that adding TBAP and LiTFSI significantly improved the electroluminescence characteristics and tuned the electroluminescence color.

The Chemistry of the Passivation Mechanism of Perovskite Films with Ionic Liquids.

Passivation of perovskite films by ionic liquids (ILs) improves the performance (efficiency and stability) of perovskite solar cells (PSCs). However, the role of ILs in the passivation of perovskite films is not fully understood. Here, we report the reactions of commonly used ILs with the components of perovskites. The reaction of ILs with perovskite precursors (PbI2 and methylammonium iodide or formamidinium iodide) in a 1:1:1 molar ratio affords one-dimensional (1D) salts composed of the IL cation interspersed along infinite 1D polymeric [PbI3]-n chains. If the IL is applied in excess, the resulting crystal is composed of six cations surrounding a discrete [Pb3I12]6- cluster. All the isolated salts were unambiguously characterized by single-crystal X-ray diffraction analysis, which also reveals extensive hydrogen-bonding interactions.

Green-Chemistry-Inspired Synthesis of Cyclobutane-Based Hole-Selective Materials for Highly Efficient Perovskite Solar Cells and Modules.

Hybrid lead halide perovskite solar cells (PSCs) have emerged as potential competitors to silicon-based solar cells with an unprecedented increase in power conversion efficiency (PCE), nearing the breakthrough point toward commercialization. However, for hole-transporting materials, it is generally acknowledged that complex structures often create issues such as increased costs and hazardous substances in the synthetic schemes, when translated from the laboratory to manufacture on a large scale. Here, we present cyclobutane-based hole-selective materials synthesized using simple and green-chemistry inspired protocols in order to reduce costs and adverse environmental impact. A series of novel semiconductors with molecularly engineered side arms were successfully applied in perovskite solar cells. V1366-based PSCs feature impressive efficiency of 21 %, along with long-term operational stability under atmospheric environment. Most importantly, we also fabricated perovskite solar modules exhibiting a record efficiency over 19 % with an active area of 30.24 cm2 .

Stable Perovskite Solar Cells Using Molecularly Engineered Functionalized Oligothiophenes as Low-Cost Hole-Transporting Materials.

Triarylamine-substituted bithiophene (BT-4D), terthiophene (TT-4D), and quarterthiophene (QT-4D) small molecules are synthesized and used as low-cost hole-transporting materials (HTMs) for perovskite solar cells (PSCs). The optoelectronic, electrochemical, and thermal properties of the compounds are investigated systematically. The BT-4D, TT-4D, and QT-4D compounds exhibit thermal decomposition temperature over 400 °C. The n-i-p configured perovskite solar cells (PSCs) fabricated with BT-4D as HTM show the maximum power conversion efficiency (PCE) of 19.34% owing to its better hole-extracting properties and film formation compared to TT-4D and QT-4D, which exhibit PCE of 17% and 16%, respectively. Importantly, PSCs using BT-4D demonstrate exceptional stability by retaining 98% of its initial PCE after 1186 h of continuous 1 sun illumination. The remarkable long-term stability and facile synthetic procedure of BT-4D show a great promise for efficient, stable, and low-cost HTMs for PSCs for commercial applications.

An Overview of the Recent Progress in Polymeric Carbon Nitride Based Photocatalysis.

Recently, polymeric carbon nitride (g-C3 N4 ) as a proficient photo-catalyst has been effectively employed in photocatalysis for energy conversion, storage, and pollutants degradation due to its low cost, robustness, and environmentally friendly nature. The critical review summarized the recent development, fundamentals, nanostructures design, advantages, and challenges of g-C3 N4 (CN), as potential future photoactive material. The review also discusses the latest information on the improvement of CN-based heterojunctions including Type-II, Z-scheme, metal/CN Schottky junctions, noble metal@CN, graphene@CN, carbon nanotubes (CNTs)@CN, metal-organic frameworks (MOFs)/CN, layered double hydroxides (LDH)/CN heterojunctions and CN-based heterostructures for H2 production from H2 O, CO2 conversion and pollutants degradation in detail. The optical absorption, electronic behavior, charge separation and transfer, and bandgap alignment of CN-based heterojunctions are discussed elaborately. The correlations between CN-based heterostructures and photocatalytic activities are described excessively. Besides, the prospects of CN-based heterostructures for energy production, storage, and pollutants degradation are discussed.

High-Efficiency Deep-Red Light-Emitting Electrochemical Cell Based on a Trinuclear Ruthenium(II)-Silver(I) Complex.

Turn-on time is a key factor for lighting devices to be of practical application. To decrease the turn-on time value of a deep-red light-emitting electrochemical cells (DR-LECs), two novel approaches based on molecularly engineered ruthenium phenanthroimidazole complexes were introduced. First, we found that with the incorporation of ionic methylpyridinium group to phenanthroimidazole ligand, the turn-on time of the DR-LECs device was dramatically reduced, from 79 to 27 s. By complexation of ruthenium emitter with Ag+, the turn-on time was improved by 85%, and the EQE of DR-device was increased from 0.62 to 0.71%. These results open a new avenue in decreasing the turn-on time without adding ionic electrolytes, leading to an efficient LEC.

Two in One: A Dinuclear Ru(II) Complex for Deep-Red Light-Emitting Electrochemical Cells and as an Electrochemiluminescence Probe for Organophosphorus Pesticides.

The emissive properties of two Ru(II) complexes, [Ru(dmbipy)2L1][PF6]2 (1) and [Ru2(dmbipy)4L2][PF6]4 (2), (where L1 and L2 are π-extended phenanthroline-based ligands and dmbipy = 4,4'-dimethyl-2,2'-bipyridine) have been explored for dual applications, namely, deep-red light-emitting electrochemical cells (LECs) and electrochemiluminescence (ECL) sensors for the detection of organophosphorus pesticides (OPs) that include chlorpyrifos (CPS). A simple single-layer deep-red LEC device comprising 2 is reported that outperforms both its mononuclear derivative 1 and all previously reported dinuclear LECs, with a maximum brightness of 524 cd/m2, an external quantum efficiency of 0.62%, and a turn-on voltage of 3.2 V. Optoelectronic studies reveal that the ECL response of 2 is improved when compared to its mononuclear counterpart 1 and benchmark [Ru(bipy)3]2+ (3). Modified glassy carbon electrodes coated with 2 are highly sensitive deep-red ECL sensors that facilitate the detection of CPS directly from river water and fruit samples without any complex pretreatment steps, operating over a broad logarithmic concentration range, with a low detection limit.

Molecular materials as interfacial layers and additives in perovskite solar cells.

Solar cells based on organo-metal halide perovskites have gained unprecedented research interest over the last few years due to their low-cost solution processability, high power conversion efficiency, which has recently reached a certified value of 25.2%, and abundance of raw materials. Nevertheless, the best efficiencies remain below the Shockley-Queisser theoretical limit of 32.5% due to several losses arising from either defect traps present in the bulk of the perovskite absorber or at the device heterointerfaces. While bulk defects are detrimental for the device performance by mainly limiting the open circuit voltage, interfacial layers are also crucial. They dictate the charge transfer/transport from the perovskite layer to the collecting electrodes, hence influencing the device photocurrent, but also act as protective barriers against oxygen and moisture penetration. Molecular materials and additives are widely used to improve the bulk properties of perovskite absorbers through the formation of high-quality perovskite films with superior optoelectronic properties, and improved crystallinity, and also of electronically clean interfaces with minimum losses during charge transfer/transport. In this review, we analyze the predominant pathways that contribute to voltage and current losses due to poor interfaces and also due to non-radiative recombination losses arising from inferior perovskite morphology and its inherent polycrystalline and highly defective nature. We then discuss strategies for achieving interfacial organic and inorganic molecular materials for application as electron and hole transport layers in perovskite solar cells with ideal energy levels, high charge mobilities and improved thermal, photo, and structural stability. Moreover, the prerequisites for molecular additives to achieve dimensionality engineering, defect passivation, molecular cross-linking, interfacial energy alignment and electronic doping are thoroughly discussed. Finally, we examine prospects for future research directions and commercialization.

In Situ Analysis Reveals the Role of 2D Perovskite in Preventing Thermal-Induced Degradation in 2D/3D Perovskite Interfaces.

Engineering 2D/3D perovskite interfaces is a common route to realizing efficient and stable perovskite solar cells. Whereas 2D perovskite's main function in trap passivation has been identified and is confirmed here, little is known about its 2D/3D interface properties under thermal stress, despite being one of the main factors that induces device instability. In this work, we monitor the response of two typical 2D/3D interfaces under a thermal cycle by in situ X-ray scattering. We reveal that upon heating, the 2D crystalline structure undergoes a dynamical transformation into a mixed 2D/3D phase, keeping the 3D bulk underneath intact. The observed 3D bulk degradation into lead iodide is blocked, revealing the paramount role of 2D perovskite in engineering stable device interfaces.

Perovskite Flash Memory with a Single-Layer Nanofloating Gate.

Here we use triple-cation metal-organic halide perovskite single crystals for the transistor channel of a flash memory device. Moreover, we design and demonstrate a 10 nm thick single-layer nanofloating gate. It consists of a ternary blend of two organic semiconductors, a p-type polyfluorene and an n-type fullerene that form a donor:acceptor interpenetrating network that serves as the charge storage unit, and of an insulating polystyrene that acts as the tunneling dielectric. Under such a framework, we realize the first non-volatile flash memory transistor based on a perovskite channel. This simplified, solution-processed perovskite flash memory displays unique performance metrics such as a large memory window of 30 V, an on/off ratio of 9 × 107, short write/erase times of 50 ms, and a satisfactory retention time exceeding 106 s. The realization of the first flash memory transistor using a single-crystal perovskite channel could be a valuable direction for perovskite electronics research.

Dopant-Free Hole Transport Materials Afford Efficient and Stable Inorganic Perovskite Solar Cells and Modules.

The emerging CsPbI3 perovskites are highly efficient and thermally stable materials for wide-band gap perovskite solar cells (PSCs), but the doped hole transport materials (HTMs) accelerate the undesirable phase transition of CsPbI3 in ambient. Herein, a dopant-free D-π-A type HTM named CI-TTIN-2F has been developed which overcomes this problem. The suitable optoelectronic properties and energy-level alignment endow CI-TTIN-2F with excellent charge collection properties. Moreover, CI-TTIN-2F provides multisite defect-healing effects on the defective sites of CsPbI3 surface. Inorganic CsPbI3 PSCs with CI-TTIN-2F HTM feature high efficiencies up to 15.9 %, along with 86 % efficiency retention after 1000 h under ambient conditions. Inorganic perovskite solar modules were also fabricated that exhibiting an efficiency of 11.0 % with a record area of 27 cm2 . This work confirms that using efficient dopant-free HTMs is an attractive strategy to stabilize inorganic PSCs for their future scale-up.