over 30% detailed balance limiting efficiency, as well as to its earth-abundant and environment-benign constituents. [1-3] The increase in power conversion efficiency to a record of 12.6% in the last decade has demonstrated the huge potential of these materials. [4,5] However, as one of the most complicated compound semiconductors, kesterite has much more intricate defect chemistry than its counterparts, Cu(In,Ga)Se 2 (CIGS) and CdTe, [6-8] making the control of intrinsic defects a major challenge. Deep intrinsic defects like Sn Zn antisites and related [Cu Zn +Sn Zn ] clusters act as deep recombination centers, leading to the short carrier lifetime. [7,9,10] Additionally, the large population of defect clusters like [2Cu Zn +Sn Zn ] introduces considerable potential (i.e., band or electrostatic) fluctuation. [11] Consequently, the performance of CZTSSe solar cells are currently stagnated by the large open-circuit voltage (V OC) deficit. [12,13] To address the detrimental intrinsic defects and defect clusters in CZTSSe absorber, multiple strategies have been employed. As suggested by the first-principle calculations, the formation energy of intrinsic defects and Kesterite-based Cu 2 ZnSn(S,Se) 4 semiconductors are emerging as promising materials for low-cost, environment-benign, and high-efficiency thin-film photo voltaics. However, the current state-of-the-art Cu 2 ZnSn(S,Se) 4 devices suffer from cation-disordering defects and defect clusters, which generally result in severe potential fluctuation, low minority carrier lifetime, and ultimately unsatisfactory performance. Herein, critical growth conditions are reported for obtaining high-quality Cu 2 ZnSnSe 4 absorber layers with the formation of detrimental intrinsic defects largely suppressed. By controlling the oxidation states of cations and modifying the local chemical composition, the local chemical environment is essentially modified during the synthesis of kesterite phase, thereby effectively suppressing detrimental intrinsic defects and activating desirable shallow acceptor Cu vacancies. Consequently, a confirmed 12.5% efficiency is demonstrated with a high V OC of 491 mV, which is the new record efficiency of pure-selenide Cu 2 ZnSnSe 4 cells with lowest V OC deficit in the kesterite family by E g /q-Voc. These encouraging results demonstrate an essential route to overcome the long-standing challenge of defect control in kesterite semiconductors, which may also be generally applicable to other multinary compound semiconductors.

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We report systematic design and formation of plasmonic perovskite solar cells (PSCs) by integrating Au@TiO core-shell nanoparticles (NPs) into porous TiO and/or perovskite semiconductor capping layers. The plasmonic effects in the formed PSCs are examined. The most efficient configuration is obtained by incorporating Au@TiO NPs into both the porous TiO and the perovskite capping layers, which increases the power conversion efficiency (PCE) from 12.59% to 18.24%, demonstrating over 44% enhancement, compared with the reference device without the metal NPs. The PCE enhancement is mainly attributed to short-circuit current improvement. The plasmonic enhancement effects of Au@TiO core-shell nanosphere photovoltaic composites are explored based on the combination of UV-vis absorption spectroscopy, external quantum efficiency (EQE), photocurrent properties, and photoluminescence (PL). The addition of Au@TiO nanospheres increased the rate of exciton generation and the probability of exciton dissociation, enhancing charge separation/transfer, reducing the recombination rate, and facilitating carrier transport in the device. This study contributes to understanding of plasmonic effects in perovskite solar cells and also provides a promising approach for simultaneous photon energy and electron management.

Environmentally benign and potentially cost‐effective Sb 2 Se 3 solar cells have drawn much attention by continuously achieving new efficiency records. This article reports a compatible strategy to enhance the efficiency of planar n–i–p Sb 2 Se 3 solar cells through Sb 2 Se 3 surface modification and an architecture with oriented 1D van der Waals material, trigonal selenium (t‐Se). A seed layer assisted successive close spaced sublimation (CSS) is developed to fabricate highly crystalline Sb 2 Se 3 absorbers. It is found that the Sb 2 Se 3 absorber exhibits a Se‐deficient surface and negative surface band bending. Reactive Se is innovatively introduced to compensate the surface Se deficiency and form an (101) oriented 1D t‐Se interlayer. The p‐type t‐Se layer promotes a favored band alignment and band bending at the Sb 2 Se 3 /t‐Se interface, and functionally works as a surface passivation and hole transport material, which significantly suppresses interface recombination and enhances carrier extraction efficiency. An efficiency of 7.45% is obtained in a planar Sb 2 Se 3 solar cell in superstrate n–i–p configuration, which is the highest efficiency for planar Sb 2 Se 3 solar cells prepared by CSS. The all‐inorganic Sb 2 Se 3 solar cell with t‐Se shows superb stability, retaining ≈98% of the initial efficiency after 40 days storage in open air without encapsulation.