Doping strategies for inorganic lead-free halide perovskite solar cells: progress and challenges.

In recent years, remarkable advancements have been achieved in the field of halide perovskite solar cells (PSCs). However, the commercialization of PSCs has been impeded by challenges such as Pb leakage and the instability of hybrid organic-inorganic perovskites (HOIPs). Hence, the future lies in the development of environmentally friendly inorganic lead-free halide perovskites (LFHPs) based on elements like Sn, Ge, Bi, Sb, and Cu, which show great promise for photovoltaic applications. However, LFHP photovoltaic cells still face challenges such as low efficiency, poor film quality, and stability in comparison to HOIPs. These limitations significantly hinder their further development. To address these issues, element doping strategies, including cationic and anionic doping, as well as the use of additives, are frequently employed. These strategies aim to improve film quality, passivate defects, reduce the band gap, and enhance device performance and stability. In this paper, we aim to provide a comprehensive review of the recent research progress in doping strategies for LFHPs.

A simple strategy to obtain graphitic carbon nitride modified TiO2layer for efficient perovskite solar cells.

The power conversion efficiency (PCE) of perovskite solar cells (PSCs) can be improved through the concurrent strategies of enhancing charge transfer and passivating defects. Graphite carbon nitride (g-C3N4) has been demonstrated as a promising modifier for optimizing energy level alignment and reducing defect density in PSCs. However, its preparation process can be complicated. A simple one-step calcination approach was used in this study to prepare g-C3N4-modified TiO2via the incorporation of urea into the TiO2precursor. This modification simultaneously tunes the energy level alignment and passivates interface defects. The comprehensive research confirms that the addition of moderate amounts of g-C3N4to TiO2results in an ideal alignment of energy levels with perovskite, thereby enhancing the ability to separate and transfer charges. Additionally, the g-C3N4-modified perovskite films exhibit an increase in grain size and crystallinity, which reduces intrinsic defects density and extends charge recombination time. Therefore, the g-C3N4-modified PSC achieves a champion PCE of 20.00%, higher than that of the control PSC (17.15%). Our study provides a systematic comprehension of the interfacial engineering strategy and offers new insights into the development of high-performance PSCs.

Enhanced performance of BiI3-incorporated CsPbBr3 solar cells.

CsPbBr3 all-inorganic perovskite solar cells (PSCs) have been extensively investigated due to their remarkable stability. However, their limited film quality and wide bandgap result in a low photoelectric conversion efficiency (PCE). In this study, BiI3 was incorporated into CsPbBr3 films to synergistically enhance light absorption and film quality. It was found that the partial substitution of Pb2+ and Br- with Bi3+ and I- in CsPbBr3 improved film quality, enhanced light absorption, and facilitated charge transfer and extraction. The device incorporating BiI3-incorporated CsPbBr3 as a light absorbing layer achieved an efficiency of 9.54%, exhibiting a significant enhancement of 19.4% compared to the undoped device. This work provides a new incorporating strategy that collaboratively improves light absorption and film quality.

One-Step Gas-Solid-Phase Diffusion-Induced Elemental Reaction for Bandgap-Tunable CuaAgm1Bim2In/CuI Thin Film Solar Cells.

Lead-free inorganic copper-silver-bismuth-halide materials have attracted more and more attention due to their environmental friendliness, high element abundance, and low cost. Here, we developed a strategy of one-step gas-solid-phase diffusion-induced reaction to fabricate a series of bandgap-tunable CuaAgm1Bim2In/CuI bilayer films due to the atomic diffusion effect for the first time. By designing and regulating the sputtered Cu/Ag/Bi metal film thickness, the bandgap of CuaAgm1Bim2In could be reduced from 2.06 to 1.78 eV. Solar cells with the structure of FTO/TiO2/CuaAgm1Bim2In/CuI/carbon were constructed, yielding a champion power conversion efficiency of 2.76%, which is the highest reported for this class of materials owing to the bandgap reduction and the peculiar bilayer structure. The current work provides a practical path for developing the next generation of efficient, stable, and environmentally friendly photovoltaic materials.

Novel Ag-based thin film solar cells: concept, materials, and challenges.

Novel Ag-based thin film solar cells have attracted extensive attention in recent years in the photovoltaic (PV) field due to their outstanding properties like a high light absorption coefficient, low toxicity, abundance, and an appropriate band gap. The emerging Ag-based thin film materials such as Ag2S, AgBiS2, Ag3CuS2, AgInS2, AgBiSe2, Ag2ZnSnS4, Ag(In1-x,Gax)Se2, AgaBibIc, Cs2AgBiBr6, and Cu2AgBiI6 are becoming ideal materials for light absorbing layers in the new generation of PV devices. Although the efficiency of ATFSCs has improved significantly in recent years, it is much lower than those of other PV devices. The relatively low efficiency of ATFSCs is mainly caused by structural defects such as poor crystallinity, voids, and instability which occur during the preparation of light absorbing layers. This paper defines the concept and classification of Ag-based materials and introduces in detail a thin film preparation method by overcoming structural defects. Finally, the vision of achieving high-efficiency ATFSCs by improving structural defects is proposed.

Synthesis of highly crystalline imine-linked covalent organic frameworks via controlling monomer feeding rates in an open system.

Covalent organic frameworks (COFs) have enormous potential in various applications because of their high crystallinity and superior surface area. However, it is still challenging to synthesize crystalline COFs using a convenient and effective synthetic strategy. Herein, we report a strategy to synthesize four highly crystalline imine COFs, namely, TATB-DATP-COF, PDA-TAPB-COF, OMePDA-TAPB-COF and COF-320, by polymerization with a dropwise monomer feeding method in an open system, without using additional templates or modulators. By controlling the feeding rates of the monomer, the reversibility of imine formation, defect self-healing and error correction can be improved.

Hydrogen Bond Activation by Pyridinic Nitrogen for the High Proton Conductivity of Covalent Triazine Framework Loaded with H3 PO4.

Under high temperature anhydrous conditions, it is still a formidable challenge to improve the performance of proton-conducting materials based on H3 PO4 and elucidate its proton conduction mechanism. Herein, a highly stable covalent triazine frameworks (CTFs) based on H3 PO4 is reported. The more pyridinic nitrogen CTFs contain, the higher proton conductivity is. Compared with H3 PO4 @CTF-L with less pyridinic nitrogen, H3 PO4 @CTF-H has a higher proton conductivity of 1.6×10-1  S cm-1 at 150 °C under anhydrous conditions, which does not decay after about 18 months exposure in air. The high proton conductivity is associated with the formation and breaking of the activated Ntriazine ⋯H+ ⋯H2 PO4 - pairs by pyridinic nitrogen of CTFs. The outstanding long-term stability is mainly attributed to the ultra-strong triazine skeleton structure of CTFs.

Crystalline Covalent Triazine Frameworks with Fibrous Morphology via a Low-Temperature Polycondensation of Planar Monomer.

The morphology regulation of covalent triazine frameworks (CTFs) is a great challenge, which may be due to the difficulty in controlling its morphology by traditional synthesis methods. Herein, a general approach to fabricate morphology controllable CTFs by a mild polycondensation reaction in mixed solvents without any templating agents is reported. As a proof of concept, a type of crystalline CTFs with distinctive fibrous morphology (MS-F-CTF-1) (MS: Mixed Solvent; F: Fibrous Morphology) is developed by adjusting the ratio of mixed solvents to control the solubility of monomers, so that the nucleation, crystal growth, and subsequent self-assembly are controlled, which facilitates the formation of fibrous morphology. The resultant crystalline MS-F-CTF-1 shows uniform fibrous morphology with a diameter of about 100 nm and a length of several micrometers. Notably, the fibrous morphology of CTFs can efficiently improve the photocatalytic hydrogen evolution performance, in which the hydrogen evolution rate can be boosted by about two times in comparison to block ones.

The O/S heteroatom effects of covalent triazine frameworks for photocatalytic hydrogen evolution.

S/O heterocyclic covalent triazine frameworks (CTFs i.e., CTF-7 and CTF-8) were synthesized using thiophene and furan as building blocks, respectively. The hydrogen evolution rate of CTF-7 is 7430 µmol g-1 h-1, which is about 5.6 times that of CTF-8. Due to their low electronegativity, sulfur heteroatoms are more favorable for charge separation than oxygen heteroatoms in CTFs. This work provides a guiding principle for the design of high efficiency photocatalyst structures.

Environment-friendly Cu-based thin film solar cells: materials, devices and charge carrier dynamics.

Cu-based thin films are ideal absorbing layer materials for new-generation thin-film solar cells, which have many advantages, such as environment-friendly components, abundant raw materials, low cost, simple manufacturing process, strong anti-interference, radiation resistance, high light absorption coefficient and suitable band gap. Copper indium gallium selenide (CIGS) thin-film solar cells, which have the highest photoelectric conversion efficiency (23.35%) among the various Cu-based materials, have been intensively investigated and exploited. To promote the progress of Cu-based thin-film solar cells, the rational design of efficient materials and devices and the in-depth understanding of their photophysical mechanisms are not only urgently required, but also have plenty of room for research. Accordingly, herein, we firstly define the concept of "Cu-based materials", and further present a comprehensive review on the materials (design and fabrication), devices (assembly and performances), and charge carrier dynamics of Cu-based thin-film semiconductor materials, including perovskites, oxides, chalcogenides (binary, ternary, quaternary and quinary) and perovskite-like iodides. In addition, the current challenges and prospects in this topic are critically concluded. Particularly, this review may help researchers focused on investigating thin-film solar cells.

Palladium as a Superior Cocatalyst to Platinum for Hydrogen Evolution Using Covalent Triazine Frameworks as a Support.

Abundant pyridinic nitrogen in the triazine units of covalent triazine frameworks (CTFs) is very useful in various heterogeneous catalysis reactions. Herein, a tunable CTF platform with the same porous structure was designed and synthesized to study the interaction between palladium/platinum (Pd/Pt) and pyridinic nitrogen of CTFs. The smaller Pd nanoparticles were formed because of the stronger interaction between Pd and pyridinic nitrogen atoms of CTFs, which is more beneficial for the separation of photogenerated electron-hole pairs. Moreover, the stronger interaction between the Pd nanoparticles and CTFs is also beneficial for photoelectron transfer. Under the same conditions, the hydrogen evolution rate of 1 wt % Pd@CTF-HC6 is up to 11 times more than that of 1 wt % Pt@CTF-HC6. The hydrogen evolution rate of 1 wt % Pd@CTF-N approaches 10 556 µmol h-1 g-1 and is about 5 times more than that of 1 wt % Pt@CTF-N.

Controlling Monomer Feeding Rate to Achieve Highly Crystalline Covalent Triazine Frameworks.

The synthesis of highly crystalline covalent triazine frameworks (CTFs) with ultrastrong covalent bonds (aromatic CN) from the triazine linkage presents a great challenge to synthetic chemists. Herein, the synthesis of highly crystalline CTFs via directly controlling the monomer feeding rate is reported. By tuning the feeding rate of monomers, the crystallization process can be readily governed in a controlled manner in an open system. The sample of CTF-HUST-HC1 with abundant exposed {001} crystal facets has the better crystallinity and thus is selected to study the effect of high crystallinity on photoelectric properties. Owing to the better separation of photogenerated electron-hole pairs and charge transfer, the obtained highly ordered CTF-HUST-HC1 has superior performance in the photocatalytic removal of nitric oxide (NO) than its lesser crystalline counterparts and g-C3 N4 .

Crystalline Covalent Triazine Frameworks by In†Situ Oxidation of Alcohols to Aldehyde Monomers.

Covalent triazine frameworks (CTFs) with aromatic triazine linkages have recently received increasing interest for various applications because of their rich nitrogen content and high chemical stability. Owing to the strong aromatic C=N bond and high chemical stability, only a few CTFs are crystalline, and most CTFs are amorphous. Herein we report a new general strategy to give highly crystalline CTFs by in situ formation of aldehyde monomers through the controlled oxidation of alcohols. This general strategy allows a series of crystalline CTFs with different monomers to be prepared, which are shown to have higher thermal stability and enhanced performance in photocatalysis as compared with the less crystalline or amorphous CTFs. This open-system approach is very simple and convenient, which presents a potential pathway to large-scale industrial production of crystalline CTFs.