Modifying Surface Termination by Bidentate Chelating Strategy Enables 13.77% Efficient Kesterite Solar Cells.

Surfaces display discontinuities in the kesterite-based polycrystalline films can produce large defect densities, including strained and dangling bonds. These physical defects tend to introduce electronic defects and surface states, which can greatly promote nonradiative recombination of electron-hole pairs and damage device performance. Here, an effective chelation strategy is reported to suppress these harmful physical defects related to unterminated Cu, Zn, and Sn sites by modifying the surface of Cu2ZnSn(S,Se)4 (CZTSSe) films with sodium diethyldithiocarbamate (NaDDTC). The conjoint theoretical calculations and experimental results reveal that the NaDDTC molecules can be coordinate to surface metal sites of CZTSSe films via robust bidentate chelating interactions, effectively reducing surface undercoordinated defects and passivating the electron trap states. Consequently, the solar cell efficiency of the NaDDTC-treated device is increased to as high as 13.77% under 100 mW cm-2 illumination, with significant improvement in fill factor and open-circuit voltage. This surface chelation strategy provides strong surface termination and defect passivation for further development and application of kesterite-based photovoltaics.

Passivating Grain Boundaries via Graphene Additive for Efficient Kesterite Solar Cells.

Grain boundaries (GBs)-triggered severe non-radiative recombination is recently recognized as the main culprits for carrier loss in polycrystalline kesterite photovoltaic devices. Accordingly, further optimization of kesterite-based thin film solar cells critically depends on passivating the grain interfaces of polycrystalline Cu2 ZnSn(S,Se)4 (CZTSSe) thin films. Herein, 2D material of graphene is first chosen as a passivator to improve the detrimental GBs. By adding graphene dispersion to the CZTSSe precursor solution, single-layer graphene is successfully introduced into the GBs of CZTSSe absorber. Due to the high carrier mobility and electrical conductivity of graphene, GBs in the CZTSSe films are transforming into electrically benign and do not act as high recombination sites for carrier. Consequently, benefitting from the significant passivation effect of GBs, the use of 0.05 wt% graphene additives increases the efficiency of CZTSSe solar cells from 10.40% to 12.90%, one of the highest for this type of cells. These results demonstrate a new route to further increase kesterite-based solar cell efficiency by additive engineering.

2D Ti3C2-MXene Serving as Intermediate Layer between Absorber and Back Contact for Efficient CZTSSe Solar Cells.

Kesterite Cu2ZnSn(S,Se)4 (CZTSSe) has been considered as the most promising absorber material for inorganic thin-film solar cells. Among the three main interfaces in CZTSSe-based solar cells, the CZTSSe/Mo back interface plays an essential role in hole extraction as well as device performance. During the selenization process, the reaction between CZTSSe and Mo is one of the main reasons that lead to a large open circuit voltage (VOC) deficit, low short circuit current (Jsc), and fill factor. In this study, 2D Ti3C2-MXene was introduced as an intermediate layer to optimize the interface between the CZTSSe absorber layer and Mo back contact. Benefiting from the 2D Ti3C2-MXene intermediate layer, the reaction between CZTSSe and Mo was effectually suppressed, thus, significantly reducing the thickness of the detrimental Mo(S,Se)2 layer as well as interface recombination at the CZTSSe/Mo back interface. As a result, the power conversion efficiency of the champion device fabricated with the 2D Ti3C2-MXene intermediate layer was improved from 10.89 to 13.14% (active-area efficiency). This study demonstrates the potential use of the 2D Ti3C2-MXene intermediate layer for efficient CZTSSe solar cells and promotes a deeper understanding of the back interface in CZTSSe solar cells.

Ordered and Fast Ion Transport of Quasi-solid-state Electrolyte with Regulated Coordination Strength for Lithium Metal Batteries.

Polymer based quasi-solid-state electrolyte (QSE) has attracted great attention due to its assurance for high safety of rechargeable batteries including lithium metal batteries (LMB). However, it faces the issue of low ionic conductivity of electrolyte and solid-electrolyte-interface (SEI) layer between QSE and lithium anode. Herein, we firstly demonstrate that the ordered and fast transport of lithium ion (Li+ ) can be realized in QSE. Due to the higher coordination strength of Li+ on tertiary amine (-NR3 ) group of polymer network than that on carbonyl (-C=O) group of ester solvent, Li+ can diffuse orderly and quickly on -NR3 of polymer, significantly increasing the ionic conductivity of QSE to 3.69 mS cm-1 . Moreover, -NR3 of polymer can induce in situ and uniform generation of Li3 N and LiNx Oy in SEI. As a result, the Li||NCM811 batteries (50 µm Li foil) with this QSE show an excellent stability of 220 cycles at ≈1.5 mA cm-2 , 5 times to those with conventional QSE. LMBs with LiFePO4 can stably run for ≈8300 h. This work demonstrates an attractive concept for improving ionic conductivity of QSE, and also provides an important step for developing advanced LMB with high cycle stability and safety.

Progress and prospectives of solution-processed kesterite absorbers for photovoltaic applications.

Solar cells based on emerging kesterite Cu2ZnSn(S,Se)4 (CZTSSe) materials have reached certified power conversion efficiency (PCE) as high as 13.6%, showing great potential in the next generation of photovoltaic technologies because of their earth-abundant, tunable direct bandgap, high optical absorption coefficient, environment-friendly, and low-cost properties. The predecessor of CZTSSe is Cu(In,Ga) Se2 (CIGS), and the highest PCE of CIGS fabricated by the vacuum method is 23.35%. However, the recorded PCE of CZTSSe devices are fabricated by a low-cost solution method. The characteristics of the solvent play a key role in determining the crystallization kinetics, crystal growth quality, and optoelectronic properties of the CZTSSe thin films in the solution method. It is still challenging to improve the efficiency of CZTSSe solar cells for future commercialization and applications. This review describes the current status of CZTSSe solar cell absorbers fabricated by protic solvents with NH (hydrazine), protic solvents with SH (amine-thiol), aprotic solvents (DMSO and DMF), ethylene glycol methyl ether-based precursor solution method (EGME), and thioglycolic acid (TGA)-ammonia solution (NH3H2O) deposition methods. Furthermore, the performances of vacuum-deposited devices and solution-based processed devices are compared. Finally, the challenges and outlooks of CZTSSe solar cells are discussed for further performance improvement.

Hypoxia-responsive Immunostimulatory Nanomedicines Synergize with Checkpoint Blockade Immunotherapy for Potentiating Cancer Immunotherapy.

Inducing cell death while simultaneously enhancing antitumor immune responses is a promising therapeutic approach for multiple cancers. Celastrol (Cel) and 7-ethyl-10-hydroxycamptothecin (SN38) have contrasting physicochemical properties, but strong synergy in immunogenic cell death induction and anticancer activity. Herein, a hypoxia-sensitive nanosystem (CS@TAP) was designed to demonstrate effective immunotherapy for colorectal cancer by systemic delivery of an immunostimulatory chemotherapy combination. Furthermore, the combination of CS@TAP with anti-PD-L1 mAb (αPD-L1) exhibited a significant therapeutic benefit of delaying tumor growth and increased local doses of immunogenic signaling and T-cell infiltration, ultimately extending survival. We conclude that CS@TAP is an effective inducer of immunogenic cell death (ICD) in cancer immunotherapy. Therefore, this study provides an encouraging strategy to synergistically induce immunogenic cell death to enhance tumor cytotoxic T lymphocytes (CTLs) infiltration for anticancer immunotherapy.

Suppressing interface recombination in CZTSSe solar cells by simple selenization with synchronous interface gradient doping.

The main bottleneck in the development of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells is their very low VOC due to severe carrier recombination. Specifically, due to the poor defect environment and unfavorable band structure, carrier recombination at the front interface is considered to be one of the most serious issues. Thus, to reduce the interface recombination and VOC deficit, we propose a convenient and effective strategy for Cd gradient doping near the front interface during selenization. The formed Cd gradient significantly reduced the CuZn defects and related [2CuZn + SnZn] defect clusters near the CZTSSe-CdS heterojunction, thus significantly suppressing the interface recombination near the heterojunction. Benefitting from the formed Cd gradient, a champion device with 12.14% PCE was achieved with the VOC significantly improved from 432 mV to 486 mV. The proposed element gradient doping strategy can offer a new idea for selenization and element gradient doping in other photoelectric devices.

Over 16% Efficient Solution-Processed Cu(In,Ga)Se2 Solar Cells via Incorporation of Copper-Rich Precursor Film.

Solution processing of Cu(In,Ga)Se2 (CIGS) absorber is a highly promising strategy for a cost-effective CIGS photovoltaic device. However, the device performance of solution-processed CIGS solar cells is still hindered by the severe non-radiative recombination resulting from deep defects and poor crystal quality. Here, a simple and effective precursor film engineering strategy is reported, where Cu-rich (CGI >1) CIGS layer is incorporated into the bottom of the CIGS precursor film. It has been discovered that the incorporation of the Cu-rich CIGS layer greatly improves the absorber crystallinity and reduces the trap state density. Accordingly, more efficient charge generation and charge transfer are realized. As a result of systematic processing optimization, the champion solution-processed CIGS device delivers an improved open-circuit voltage of 656 mV, current density of 33.15 mA cm-2 , and fill factor of 73.78%, leading to the high efficiency of 16.05%.

Synergetic Effects of Zn Alloying and Defect Engineering on Improving the CdS Buffer Layer of Cu2ZnSnS4 Solar Cells.

The inferior electrical properties at the interface of the Cu2ZnSnS4/CdS (CZTS/CdS) heterojunction resulting in the severe loss of open-circuit voltage (Voc) highly restrict the photovoltaic efficiency of CZTS solar cell devices. Here, first-principles calculations show that the Zn-alloyed CdS buffer layer reverses the unfavorable cliff-like conduction band offset (CBO) of CZTS/CdS to the desirable spike-like CBO of CZTS/Zn0.25Cd0.75S, which suppresses carrier nonradiative recombination and blocks electron backflow. In addition, the weakened n-type conductivity of Zn0.25Cd0.75S can be enhanced by In, Ga, and Cl doping without the introduction of detrimental deep-level defects and severe band-tail states, which improves the Voc of CZTS solar cells by promoting strong band bending and large quasi-Fermi-level splitting at the absorber side of the CZTS/Zn0.25Cd0.75S heterojunction. This study finds that the synergetic effects of Zn alloying and defect engineering on the CdS buffer layer are promising for overcoming the long-standing issue of the Voc deficit in CZTS solar cells, and understanding the optimized interfacial electrical properties provides theoretical guidance for improving the efficiency of semiconductor devices.

Visible-Light-Induced Cascade Cyclization of N-Propargyl Aromatic Amines and Acyl Oxime Esters: Rapid Access to 3-Acylated Quinolines.

Visible-light-induced radical cascade acylation/cyclization/aromatization of N-propargyl aromatic amines and acyl oxime esters for the construction of 3-acylated quinolines is developed. This approach uses acyl oxime esters as the precursor of acyl radicals as well as acylation reagents, Eosin Y as the photocatalyst, and acetonitrile as the solvent, providing a convenient route toward 3-acylated quinolines via the C-C bond cleavage of acyl oxime esters.

Plasmonic Local Electric Field-Enhanced Interface toward High-Efficiency Cu2ZnSn(S,Se)4 Thin-Film Solar Cells.

The kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells have shown a continuous rise in power conversion efficiencies in the past years. However, the encountered interfacial problems with respect to charge recombination and extraction losses at the CdS/CZTSSe heterojunction still hinder their further development. In this work, an additional plasmonic local electric field is imposed into the CdS/CZTSSe interface through the electrostatic assembly of a two-dimensional (2D) ordered Au@SiO2 NP array onto an aminosilane-modified surface absorber. The interfacial electric properties are tuned by controlling the coverage particle distance, and the finite-difference time domain (FDTD) simulation demonstrates that the strong near-field enhancement mainly occurs near the p-n junction interface. It is shown that the imposed local electric field leads to interfacial electrostatic potential (Velec) augmentation and improves the charge extraction and recombination processes. These electric benefits enable remarkable improvements in open-circuit voltage (Voc) and short-circuit current (Jsc), leading to the cell efficiency being increased from 10.19 to 11.50%. This work highlights the dramatic role of the plasmonic local electric field and the use of the 2D Au@SiO2 NP array to modify a surface absorber instead of the extensively used ion passivation, providing a new strategy for p-n junction engineering in kesterite photovoltaics.

DMF-Based Large-Grain Spanning Cu2 ZnSn(Sx ,Se1- x )4 Device with a PCE of 11.76.

A main concern of the promising DMF-based Cu2 ZnSn(Sx ,Se1- x )4 (CZTSSe) solar cells lies in the absence of a large-grain spanning structure, which is a key factor for high open-circuit voltage (Voc ) and power conversion efficiency (PCE). A new strategy to achieve CZTSSe large-grain spanning monolayer is proposed, by taking advantage of the synergistic optimization with a Cu2+ plus Sn2+ redox system and pre-annealing temperatures. A series of structural, morphological, electrical, and photoelectric characterizations are employed to study the effects of the pre-annealing temperatures on absorber qualities, and an optimized temperature of 430 â„ƒ is determined. The growth mechanism of the large-grain spanning monolayer and the effect of redox reaction rate are carefully investigated. Three types of absorber growth mechanisms and a concept of critical temperature are proposed. The devices based on this large-grain spanning monolayer suppress the recombination of carriers at crystal boundaries and interfaces. The champion device exhibits a high Voc (>500 mV) and PCE of 11.76%, which are both the maximum values among DMF-based solar cells at the current stage.

Interface Engineering for High-Efficiency Solution-Processed Cu(In,Ga)(S,Se)2 Solar Cells via a Novel Indium-Doped CdS Strategy.

Indium doping of cadmium sulfide (CdS) by chemical bath deposition (CBD) can be an efficient strategy to boost the CIGSSe efficiency. However, limited by the extremely low solubility of In2S3, it is difficult to increase the In doping contents and inhibit the band energy-level regulation for CdS through the traditional CBD process. In this work, we perform a novel CBD method to prepare an indium-doped CdS (In:CdS) buffer, in which the indium source is sequentially slowly added in the growing aqueous solution. In this process, the In ion concentration involved in the real-time deposition is significantly reduced. Thus, compact and uniform In:CdS with higher indium doping content is obtained. Indium doping can elevate the CdS conduction band edge and construct a more favorable spike band alignment with a CIGSSe absorber. Moreover, it introduces efficient carrier transport and reduced interface defect density. As a result, improved CIGSSe heterojunction quality is realized by utilizing In:CdS. Also, the solution-processed CIGSSe device with In:CdS as a buffer yields a high efficiency of 16.4%, with a high VOC of 670 mV and an FF of 75.3%.

Palladium-catalyzed radical cascade cyanoalkylsulfonylation/cyclization of 3-arylethynyl-[1,1'-biphenyl]-2-carbonitriles with cyclobutanone oxime esters and DABSO.

A palladium-catalyzed radical cascade cyanoalkylsulfonylation/cyclization of 3-arylethynyl-[1,1'-biphenyl]-2-carbonitriles with DABCO·(SO2)2 and cyclobutanone oxime esters via cleavage of a C-C single bond and insertion of SO2 was described. A series of cyanoalkylsulfone-containing cyclopenta[gh]phenanthridines were obtained in moderate-to-good yields, thus featuring mild reaction conditions, a broad substrate scope, and a high functional group tolerance.

Visible-Light-Induced Multicomponent Cascade Cycloaddition of N-Propargyl Aromatic Amines, Cyclobutanone Oxime Esters, and K2S2O5: Access to Cyanoalkylsulfonylated Quinolines.

A visible-light-induced cascade cyanoalkylsulfonylation/cyclization/aromatization of N-propargyl aromatic amines with K2S2O5 and cyclobutanone oxime esters for the construction of cyanoalkylsulfonylated quinolines is developed. This cascade transformation features mild reaction conditions, a broad substrate scope, and excellent functional group compatibility, providing a convenient route toward cyanoalkylsulfonylated quinolines via the formation of a C-C bond and two C-S bonds in one step.

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.

Ni-Catalyzed radical cyclization of vinyl azides with cyclobutanone oxime esters to access cyanoalkyl containing quinoxalin-2(1H)-ones.

A nickel-catalyzed cascade addition/cyclization of 2-azido-N-arylacrylamides and cyclobutanone oxime esters for the construction of 3-cyanoalkylated quinoxalin-2(1H)-ones is developed. This reaction proceeds under mild conditions with good functional group tolerance and broad substrate scope. A preliminary mechanistic experiment indicated that the cyanoalkyl radical might be involved in this transformation.

Local Cu Component Engineering to Achieve Continuous Carrier Transport for Enhanced Kesterite Solar Cells.

Although the traditional Cu-poor architecture addresses many limitations for Cu2ZnSn(S,Se)4 solar cells, its further development still encounters a bottleneck in terms of efficiency, primarily arising from the inferior charge transport within the quasineutral region and enlarged recombination at back contact. On the contrary, the electrical benign kesterite compound with higher Cu content may compensate for these shortages, but it will degrade device performance more pronouncedly at front contact because of the Fermi level pinning and more electric shunts. Based on the electric disparities on their independent side, in this work, we propose a new status of Cu component by exploring a large grain/fine grain/large grain trilayer architecture with higher Cu content near back contact and lower Cu content near front contact. The benefits of this bottom Cu-higher strategy are that it imposes a concentration gradient to drive carrier diffusion toward front contact and decreases the valence band edge offset in the rear of the device to aid in hole extraction. Also, it maintains the Cu-poor architecture at the near surface to facilitate hole quasi-Fermi level splitting. In return, the local Cu component engineering-mediated electric advances contribute to the highest efficiency of 12.54% for kesterite solar cells using amine-thiol solution systems so far.

Enhancing Grain Growth for Efficient Solution-Processed (Cu,Ag)2ZnSn(S,Se)4 Solar Cells Based on Acetate Precursor.

Material crystallinity is the overriding factor in the determination of the photoelectric properties of absorber materials and the overall performance of the photovoltaic device. Nevertheless, in the Cu2ZnSn(S,Se)4 (CZTSSe) photovoltaic device, the bilayer or trilayer structure for the absorber has been broadly observed, which is generally harmful to the cell performance because the probability of photogenerated carrier recombination at grain boundaries significantly increased. Herein, our experiment reveals that the application of anions to a new family of (Cu,Ag)2ZnSn(S,Se)4 (CAZTSSe) materials leads to an increase in grain size and crystallinity. It is inspiring that using acetate starting materials in the precursor solution, a uniform, compact, and pinhole-free CAZTS precursor film was obtained, and the smoothness of the films surpassed that of films fabricated from the oxide route. More importantly, the crystallization of the CAZTSSe film has been considerably enhanced after selenization, and large grains going through the entire absorber layer was successfully obtained. Additionally, it is observed that the Voc accompanied by excellent crystallinity improved significantly due to the pronouncedly reduced carrier recombination loss at grain boundaries. As a consequence, the power conversion efficiency (PCE) of the CAZTSSe photovoltaic device is successfully increased from 10.35% (oxide route) to 11.32% (acetate route). Importantly, our work attests to the feasibility of tuning the crystallization of the CZTSSe film by simple chemistry.

High Efficiency CIGS Solar Cells by Bulk Defect Passivation through Ag Substituting Strategy.

Cu(In,Ga)Se2 (CIGS) is considered a promising photovoltaics material due to its excellent properties and high efficiency. However, the complicated deep defects (such as InCu or GaCu) in the CIGS layer hamper the development of polycrystalline CIGS solar cells. Numerous efforts have been employed to passivate these defects which distributed in the grain boundary and the CIGS/CdS interface. In this work, we implemented an effective Ag substituting approach to passivate bulk defects in CIGS absorber. The composition and phase characterizations revealed that Ag was successfully incorporated in the CIGS lattice. The substituting of Ag could boost the crystallization without obviously changing the band gap. The C-V and EIS results demonstrated that the device showed enlarged Wd and beneficial carrier transport dynamics after Ag incorporation. The DLTS result revealed that the deep InCu defect density was dramatically decreased after Ag substituting for Cu. A champion Ag-substituted CIGS device exhibited a remarkable efficiency of 15.82%, with improved VOC of 630 mV, JSC of 34.44 mA/cm2, and FF of 72.90%. Comparing with the efficiency of an unsubstituted CIGS device (12.18%), a Ag-substituted CIGS device exhibited 30% enhancement.