Chen Weijie

Organic–inorganic perovskites are well suited for optoelectronic applications. In particular, perovskite single and perovskite tandem solar cells with silicon are close to their market entry. Despite their swift rise in efficiency to more than 21%, solar cell lifetimes are way below the needed 25 years. In fact, comparison of the time when the device performance has degraded to 80% of its initial value (T₈₀ lifetime) of numerous solar cells throughout the literature reveals a strongly reduced stability under illumination. Herein, the various detrimental effects are discussed. Most notably, moisture- and heat-related degradation can be mitigated easily by now. Recently, however, several photoinduced degradation mechanisms have been observed. Under illumination, mixed perovskites tend to phase segregate, while, further, oxygen catalyzes deprotonation of the organic cations. Additionally, during illumination photogenerated charge can be trapped in the NH antibonding orbitals causing dissociation of the organic cation. On the other hand, organic–inorganic perovskites exhibit a high radiation hardness that is superior to crystalline silicon. Here, the proposed degradation mechanisms reported in the literature are thoroughly reviewed and the microscopic mechanisms and their implications for solar cells are discussed.

T₈₀ lifetimes of organic–inorganic perovskite solar cells are strongly reduced under illumination. Various degradation mechanisms are therefore discussed throughout the literature. Degradation by moisture or heat is well understood and mitigation possible. Photoinduced phase segregation and photoinduced dissociation of the organic cation, however, remain unsolved. Recent observations enlighten the underlying microscopic mechanisms and may pave the way for stable perovskites.

A series of PBDB-TTn random donor copolymers is synthesized, consisting of an electron-deficient benzo[1,2-c:4,5-c′]dithiophene-4,8-dione (BDD) unit and different ratios of two electron-rich benzo[1,2-b:4,5-b′]dithiophene (BDT) and thieno[3,2-b]thiophene (TT) units, with intention to modulate the intrachain and/or interchain interactions and ultimately bulk-heterojunction morphology evolution. A comparative study using 4 × 2 polymer solar cell (PSC) performance maps and each of the [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) and the fused-aromatic-ring-based molecule (m-ITIC) acceptors are carried out. Given the similarities in their absorption ranges and energy levels, the PBDB-TTn copolymers clearly reveal a change in the absorption coefficients upon optimization of the BDT to TT ratio in the backbone. Among the given acceptor combination sets, superior performances are observed in the case of PBDB-TT5 blended with PC₇₁BM (8.34 ± 0.10%) or m-ITIC (11.10 ± 0.08%), and the dominant factors causing power conversion efficiency differences in them are found to be distinctly different. For example, the performances of PC₇₁BM-based PSCs are governed by size and population of face-on crystallites, while intermixed morphology without the formation of large phase-separated aggregates is the key factor for achieving high-performance m-ITIC-based PSCs. This study presents a new sketch of structure–morphology–performance relationships for fullerene- versus nonfullerene-based PSCs.

BDD-based four copolymers PBDD-TTn which contained BDT, TT, and BDD are synthesized and operated with two acceptors, PC₇₁BM and m-ITIC. Two systems have different operating mechanisms, and simultaneously high-performances 8.44% for PC₇₁BM and 11.18% for m-ITIC are obtained.

Extremely high power conversion efficiencies (PCEs) of ≈20–22% are realized through intensive research and development of 1.5–1.6 eV bandgap perovskite absorbers. However, development of ideal bandgap (1.3–1.4 eV) absorbers is pivotal to further improve PCE of single junction perovskite solar cells (PVSCs) because of a better balance between absorption loss of sub-bandgap photons and thermalization loss of above-bandgap photons as demonstrated by the Shockley–Queisser detailed balanced calculation. Ideal bandgap PVSCs are currently hindered by the poor optoelectronic quality of perovskite absorbers and their PCEs have stagnated at <15%. In this work, through systematic photoluminescence and photovoltaic analysis, a new ideal bandgap (1.35 eV) absorber composition (MAPb_0.5Sn_0.5(I_0.8Br_0.2)₃) is rationally designed and developed, which possesses lower nonradiative recombination states, band edge disorder, and Urbach energy coupled with a higher absorption coefficient, which yields a reduced V_oc,loss (0.45 V) and improved PCE (as high as 17.63%) for the derived PVSCs. This work provides a promising platform for unleashing the complete potential of ideal bandgap PVSCs and prospects for further improvement.

An ideal-bandgap (1.35 eV) perovskite (MAPb_0.5Sn_0.5(I_0.8Br_0.2)₃) is developed with lower non-radiative recombination states, band edge disorder, and Urbach energy coupled with a higher absorption coefficient, yielding a reduced open-circuit voltage loss of 0.45 V and improved efficiency of 17.63%. This work provides a promising platform for unleashing the complete potential of ideal-bandgap perovskite solar cells.

In article number 1703451, direct evidence of bromine migration in CH₃NH₃PbBr₃ single crystals under electric-field cycles is reported by David P. Fenning and co-workers, using nanoprobe X-ray fluorescence. Photoluminescence mapping reveals that the crystal has higher emission in regions with higher local bromine concentration. This link between ion migration and optoelectronic quality reveals the importance of controlling the nanoscale material chemistry to optimize performance in hybrid perovskite optoelectronic materials.

Employing a layer of bulk-heterojunction (BHJ) organic semiconductors on top of perovskite to further extend its photoresponse is considered as a simple and promising way to enhance the efficiency of perovskite-based solar cells, instead of using tandem devices or near infrared (NIR)-absorbing Sn-containing perovskites. However, the progress made from this approach is quite limited because very few such hybrid solar cells can simultaneously show high short-circuit current (J_SC) and fill factor (FF). To find an appropriate NIR-absorbing BHJ is essential for highly efficient, organic, photovoltaics (OPV)/perovskite hybrid solar cells. The materials involved in the BHJ layer not only need to have broad photoresponse to increase J_SC, but also possess suitable energy levels and high mobility to afford high V_OC and FF. In this work, a new porphyrin is synthesized and blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) to function as an efficient BHJ for OPV/perovskite hybrid solar cells. The extended photoresponse, well-matched energy levels, and high hole mobility from optimized BHJ morphology afford a very high power conversion efficiency (PCE) (19.02%) with high V_oc, J_SC, and FF achieved simultaneously. This is the highest value reported so far for such hybrid devices, which demonstrates the feasibility of further improving the efficiency of perovskite devices.

A highly efficient organic photovoltaics/perovskite hybrid solar cell is demonstrated by blending a new conjugated porphyrin-based small molecule with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) to function as an efficient bulk-heterojunction layer. The extended photoresponse, matched energy levels, and high hole mobility derived from the optimized bulk-heterojunction morphology contribute to the record-high efficiency of 19.02% in these hybrid devices.

A novel small-molecule acceptor, (2,2′-((5E,5′E)-5,5′-((5,5′-(4,4,9,9-tetrakis(5-hexylthiophen-2-yl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b′]dithiophene-2,7-diyl)bis(4-(2-ethylhexyl)thiophene-5,2-diyl))bis(methanylylidene)) bis(3-hexyl-4-oxothiazolidine-5,2-diylidene))dimalononitrile (ITCN), end-capped with electron-deficient 2-(3-hexyl-4-oxothiazolidin-2-ylidene)malononitrile groups, is designed, synthesized, and used as the third component in fullerene-free ternary polymer solar cells (PSCs). The cascaded energy-level structure enabled by the newly designed acceptor is beneficial to the carrier transport and separation. Meanwhile, the three materials show a complementary absorption in the visible region, resulting in efficient light harvesting. Hence, the PBDB-T:ITCN:IT-M ternary PSCs possess a high short-circuit current density (J_sc) under an optimal weight ratio of donors and acceptors. Moreover, the open-circuit voltage (V_oc) of the ternary PSCs is enhanced with an increase of the third acceptor ITCN content, which is attributed to the higher lowest unoccupied molecular orbital energy level of ITCN than that of IT-M, thus exhibits a higher V_oc in PBDB-T:ITCN binary system. Ultimately, the ternary PSCs achieve a power conversion efficiency of 12.16%, which is higher than the PBDB-T:ITM-based PSCs (10.89%) and PBDB-T:ITCN-based ones (2.21%). This work provides an effective strategy to improve the photovoltaic performance of PSCs.

Fullerene-free ternary polymer solar cells with a high efficiency of 12.16% are fabricated by adding a novel small-molecule acceptor to form a cascaded energy-level structure.