Modulating the Structure and Optoelectronic Properties of Solution-Processed Bismuth-Based Nanocrystals.

Bismuth-based chalcogenides have emerged as promising candidates for next-generation, solution-processable semiconductors, mainly benefiting from their facile fabrication, low cost, excellent stability, and tunable optoelectronic properties. Particularly, the recently developed AgBiS2 solar cells have shown striking power conversion efficiencies. High performance bismuth-based photodetectors have also been extensively studied in the past few years. However, the fundamental properties of these Bi-based semiconductors have not been sufficiently investigated, which is crucial for further improving the device performance. Here, we introduce multiple time-resolved and steady-state techniques to fully characterize the charge carrier dynamics and charge transport of solution-processed Bi-based nanocrystals. It was found that the Ag-Bi ratio plays a critical role in charge transport. For Ag-deficient samples, silver bismuth sulfide thin films behave as localized state induced hopping charge transport, and the Ag-excess samples present band-like charge transport. This finding is crucial for developing more efficient Bi-based semiconductors and optoelectronic devices.

Anion/Cation Co-Doping to Improve the Thermoelectric Performance of Sn-Enriched n-Type SnSe Polycrystals with Suppressed Lattice Thermal Conductivity.

Enhancing the thermoelectric performance of n-type polycrystalline SnSe is essential, addressing challenges posed by elevated thermal conductivity and compromised power factor inherent in its intrinsic p-type characteristics. This investigation utilized solid-state reactions and spark plasma sintering techniques for the synthesis of n-type SnSe. A significant improvement in the figure of merit (ZT) is achieved through strategic reduction in Se concentration and optimization of crystal orientation. The co-doping with Br and Ge further improves the material; Br amplifies carrier concentration, enhancing electrical conductivity, while Ge introduces effective phonon scattering centers. In the Br/Ge co-doped SnSe sample, thermal conductivity dropped to 0.38 Wm⁻¹K⁻¹, yielding a remarkable power factor of 662 µW mK- 2 at 773 K, culminating in a ZT of 1.34. This signifies a noteworthy 605% improvement over the pristine sample, underscoring the pivotal role of Ge doping in enhancing n-type material thermoelectric properties. The enhancement is attributed to Br doping introducing additional electronic states near the valence band, and Ge doping modifying the band structure, fostering resonant states near the conduction band. The Br/Ge co-doping further transforms the band structure, influencing electrical conductivity, Seebeck coefficient, and thermal conductivity, advancing the understanding and application of n-type SnSe materials for superior thermoelectric performance.

Suppressing Deep-Level Trap Toward Over 13% Efficient Solution-Processed Kesterite Solar Cell.

Cu2ZnSn (S,Se)4 (CZTSSe), a promising absorption material for thin-film solar cells, still falls short of reaching the balance limit efficiency due to the presence of various defects and high defect concentration in the thin film. During the high-temperature selenization process of CZTSSe, the diffusion of various elements and chemical reactions significantly influence defect formation. In this study, a NaOH-Se intermediate layer introduced at the back interface can optimize Cu2ZnSnS4 (CZTS)precursor films and subsequently adjust the Se and alkali metal content to favor grain growth during selenization. Through this back interface engineering, issues such as non-uniform grain arrangement on the surface, voids in bulk regions, and poor contact at the back interface of absorber layers are effectively addressed. This method not only optimizes morphology but also suppresses deep-level defect formation, thereby promoting carrier transport at both interfaces and bulk regions of the absorber layer. Consequently, CZTSSe devices with a NaOH-Se intermediate layer improved fill factor, open-circuit voltage, and efficiency by 13.3%. This work initiates from precursor thin films via back interface engineering to fabricate high-quality absorber layers while advancing the understanding regarding the role played by intermediate layers at the back interface of kesterite solar cells.

Electron Transport Layer Engineering Induced Carrier Dynamics Optimization for Efficient Cd-Free Sb2 Se3 Thin-Film Solar Cells.

Antimony selenide (Sb2 Se3 ) is a highly promising photovoltaic material thanks to its outstanding optoelectronic properties, as well as its cost-effective and eco-friendly merits. However, toxic CdS is widely used as an electron transport layer (ETL) in efficient Sb2 Se3 solar cells, which largely limit their development toward market commercialization. Herein, an effective green Cd-free ETL of SnOx is introduced and deposited by atomic layer deposition method. Additionally, an important post-annealing treatment is designed to further optimize the functional layers and the heterojunction interface properties. Such engineering strategy can optimize SnOx ETL with higher nano-crystallinity, higher carrier density, and less defect groups, modify Sb2 Se3 /SnOx heterojunction with better interface performance and much desirable "spike-like" band alignment, and also improve the Sb2 Se3 light absorber layer quality with passivated bulk defects and prolonged carrier lifetime, and therefore to enhance carrier separation and transport while suppressing non-radiative recombination. Finally, the as-fabricated Cd-free Mo/Sb2 Se3 /SnOx /ITO/Ag thin-film solar cell exhibits a stimulating efficiency of 7.39%, contributing a record value for Cd-free substrate structured Sb2 Se3 solar cells reported to date. This work provides a viable strategy for developing and broadening practical applications of environmental-friendly Sb2 Se3 photovoltaic devices.

(Bi,Sb)2 Se3 Alloy Thin Film for Short-Wavelength Infrared Photodetector and TFT Monolithic-Integrated Matrix Imaging.

Short-wavelength infrared photodetectors play a significant role in various fields such as autonomous driving, military security, and biological medicine. However, state-of-the-art short-wavelength infrared photodetectors, such as InGaAs, require high-temperature fabrication and heterogenous integration with complementary metal-oxide-semiconductor (CMOS) readout circuits (ROIC), resulting in a high cost and low imaging resolution. Herein, for the first time, a low-cost, high-performance, high-stable, and thin-film transistor (TFT) ROIC monolithic-integrated (Bi,Sb)2 Se3 alloy thin-film short-wavelength infrared photodetector is reported. The (Bi,Sb)2 Se3 alloy thin-film short-wavelength infrared photodetectors demonstrate a high external quantum efficiency (EQE) of 21.1% (light intensity of 0.76 µW cm-2 ) and a fast response time (3.24 µs). The highest EQE is about two magnitudes than that of the extrinsic photoconduction of Sb2 Se3 (0.051%). In addition, the unpackaged devices demonstrate high electric and thermal stability (almost no attenuation at 120 °C for 312 h), showing potential for in-vehicle applications that may experient such a high temperature. Finally, both the (Bi,Sb)2 Se3 alloy thin film and n-type CdSe buffer layer are directly deposited on the TFT ROIC (with a 64 × 64-pixel array) with a low-temperature process and the material identification and imaging applications are presented. This work is a significant breakthrough in ROIC monolithic-integrated short-wavelength infrared imaging chips.

A Deep Dive into Cu2ZnSnS4 (CZTS) Solar Cells: A Review of Exploring Roadblocks, Breakthroughs, and Shaping the Future.

Renewable energy is crucial for sustainable future, and Cu2ZnSnS4 (CZTS) based solar cells shine as a beacon of hope. CZTS, composed of abundant, low-cost, and non-toxic elements, shares similarities with Cu(In,Ga)Se2 (CIGS). However, despite its promise and appealing properties for solar cells, CZTS-based solar cells faces performance challenges owing to inherent issues with CZTS material, and conventional substrate structure complexities. This review critically examines these roadblocks, explores ongoing efforts and breakthroughs, providing insight into the evolving landscape of CZTS-based solar cells research. Furthermore, as an optimistic turn in the field, the review first highlights the crucial need to transition to a superstrate structure for CZTS-based single junction devices, and summarizes the substantial progress made in this direction. Subsequently, dive into the discussion about the fascinating realm of CZTS-based tandem devices, providing an overview of the existing literature as well as outlining the possible potential strategies for enhancing the efficiency of such devices. Finally, the review provides a useful outlook that outlines the priorities for future research and suggesting where efforts should concentrate to shape the future of CZTS-based solar cells.

Heterogeneous Nucleation Regulation Amends Unfavorable Crystallization Orientation and Defect Features of Antimony Selenosulfide Film for High-Efficient Planar Solar Cells.

Antimony selenosulfide (Sb2(S,Se)3) has obtained widespread concern for photovoltaic applications as a light absorber due to superior photoelectric features. Accordingly, various deposition technologies have been developed in recent years, especially hydrothermal deposition method, which has achieved a great success. However, device performances are limited with severe carrier recombination, relating to the quality of absorber and interfaces. Herein, bulk and interface defects are simultaneously suppressed by regulating heterogeneous nucleation kinetics with barium dibromide (BaBr2) introduction. In details, the Br adsorbs and dopes on the polar planes of cadmium sulfide (CdS) buffer layer, promoting the exposure of nonpolar planes of CdS, which facilitates the favorable growth of [hk1]-Sb2(S,Se)3 films possessing superior crystallinity and small interface defects. Additionally, the Se/S ratio is increased due to the replacement of S/Se by Br, causing a downshift of the Fermi levels with a benign band alignment and a shallow-level defect. Moreover, Ba2+ is located at grain boundaries by coordination with S and Se ions, passivating grain boundary defects. Consequently, the efficiency is increased from 7.70% to 10.12%. This work opens an avenue towards regulating the heterogeneous nucleation kinetics of Sb2(S,Se)3 film deposited via hydrothermal deposition approach to optimize its crystalline orientation and defect features.

Toward High Efficient Cu2 ZnSn(Sx ,Se1- x )4 Solar Cells: Break the Limitations of VOC and FF.

Increasing the fill factor (FF) and the open-circuit voltage (VOC ) simultaneously together with non-decreased short-circuit current density (JSC ) are a challenge for highly efficient Cu2 ZnSn(S,Se)4 (CZTSSe) solar cells. Aimed at such target in CZTSSe solar cells, a synergistic strategy to tailor the recombination in the bulk and at the heterojunction interface has been developed, consisting of atomic-layer deposited aluminum oxide (ALD-Al2 O3 ) and (NH4 )2 S treatment. With this strategy, deep-level CuZn defects are converted into shallower VCu defects and improved crystallinity, while the surface of the absorber is optimized by removing Zn- and Sn-related impurities and incorporating S. Consequently, the defects responsible for recombination in the bulk and at the heterojunction interface are effectively passivated, thereby prolonging the minority carrier lifetime and increasing the depletion region width, which promote carrier collection and reduce charge loss. As a consequence, the VOC deficit decreases from 0.607 to 0.547 V, and the average FF increases from 64.2% to 69.7%, especially, JSC does not decrease. Thus, the CZTSSe solar cell with the remarkable efficiency of 13.0% is fabricated. This study highlights the increased FF together with VOC simultaneously to promote the efficiency of CZTSSe solar cells, which could also be applied to other photoelectronic devices.

Large-Grain Spanning Monolayer Cu2 ZnSnSe4 Thin-Film Solar Cells Grown from Metal Precursor.

The persistent double layer structure whereby two layers with different properties form at the front and rear of absorbers is a critical challenge in the field of kesterite thin-film solar cells, which imposes additional nonradiative recombination in the quasi-neutral region and potential limitation to the transport of hole carriers. Herein, an effective model for growing monolayer CZTSe thin-films based on metal precursors with large grains spanning the whole film is developed. Voids and fine grain layer are avoided successfully by suppressing the formation of a Sn-rich liquid metal phase near Mo back contact during alloying, while grain coarsening is greatly promoted by enhancing mass transfer during grain growth. The desired morphology exhibits several encouraging features, including significantly reduced recombination in the quasi-neutral region that contributes to the large increase of short-circuit current, and a quasi-Ohmic back contact which is a prerequisite for high fill factor. Though this growth mode may introduce more interfacial defects which require further modification, the strategies demonstrated remove a primary obstacle toward higher efficiency kesterite solar cells, and can be applicable to morphology control with other emerging chalcogenide thin films.

Design and Implementation of 2.45 GHz Passive SAW Temperature Sensors with BPSK Coded RFID Configuration.

A surface acoustic wave based passive temperature sensor capable of multiple access is investigated. Binary Phase Shift Keying (BPSK) codes of eight chips were implemented using a reflective delay line scheme on a Y-Z LiNbO3 piezoelectric substrate. An accurate simulation based on the combined finite- and boundary element method (FEM/BEM) was performed in order to determine the optimum design parameters. The scaling factor 's' and time delay factor 'τ' were extracted using signal processing techniques based on the wavelet transform of the correlation function, and then evaluated at various ambient temperatures. The scaling factor 's' gave a more stable and reliable response to temperature than the time delay factor 'τ'. Preliminary results show that the sensor response is fast and consistent subject to ambient temperature and it exhibits good linearity of 0.9992 with temperature varying from 0 to 130 °C.

Effective Non-Radiative Interfacial Recombination Suppression Scenario Using Air Annealing for Antimony Triselenide Thin-Film Solar Cells.

Antimony triselenide (Sb2Se3) has become a very promising candidate for next-generation thin-film solar cells due to the merits of their low-cost, low-toxic and excellent optoelectronic properties. Despite Sb2Se3 thin-film photovoltaic technology having undergone rapid development over the past few years, insufficient doping concentration and severe recombination have been the most challenging limitations hindering further breakthroughs for the Sb2Se3 solar cells. Post-annealing treatment of the Sb2Se3/CdS heterojunction was demonstrated to be very helpful in improving the device performance previously. In this work, post-annealing treatments were applied to the Sb2Se3/CdS heterojunction under a vacuum and in the air, respectively. It was found that compared to the vacuum annealing scenario, the air-annealed device presented notable enhancements in open-circuit voltage. Ultimately a competitive power conversion efficiency of 7.62% was achieved for the champion device via air annealing. Key photovoltaic parameters of the Sb2Se3 solar cells were measured and the effects of post-annealing treatments using different scenarios on the devices were discussed.

Back Interface and Absorber Bulk Deep-Level Trap Optimization Enables Highly Efficient Flexible Antimony Triselenide Solar Cell.

The unique 1D crystal structure of Antimony Triselenide (Sb2Se3) offers notable potential for use in flexible, lightweight devices due to its excellent bending characteristics. However, fabricating high-efficiency flexible Sb2Se3 solar cells is challenging, primarily due to the suboptimal contact interface between the embedded Sb2Se3 layer and the molybdenum back-contact, compounded by complex intrinsic defects. This study introduces a novel Molybdenum Trioxide (MoO3) interlayer to address the back contact interface issues in flexible Sb2Se3 devices. Further investigations indicate that incorporating a MoO3 interlayer not only enhances the crystalline quality but also promotes a favorable [hk1] growth orientation in the Sb2Se3 absorber layer. It also reduces the barrier height at the back contact interface and effectively passivates harmful defects. As a result, the flexible Sb2Se3 solar cell, featuring a Mo-foil/Mo/MoO3/Sb2Se3/CdS/ITO/Ag substrate structure, demonstrates exceptional flexibility and durability, enduring large bending radii and multiple bending cycles while achieving an impressive efficiency of 8.23%. This research offers a straightforward approach to enhancing the performance of flexible Sb2Se3 devices, thereby expanding their application scope in the field of photovoltaics.

Analysis of Carrier Transport at Zn1-xSnxOy/Absorber Interface in Sb2(S,Se)3 Solar Cells.

This work explores the effect of a Zn1-xSnxOy (ZTO) layer as a potential replacement for CdS in Sb2(S,Se)3 devices. Through the use of Afors-het software v2.5, it was determined that the ZTO/Sb2(S,Se)3 interface exhibits a lower conduction band offset (CBO) value of 0.34 eV compared to the CdS/Sb2(S,Se)3 interface. Lower photo-generated carrier recombination can be obtained at the interface of the ZTO/Sb2(S,Se)3 heterojunction. In addition, the valence band offset (VBO) value at the ZTO/Sb2(S,Se)3 interface increases to 1.55 eV. The ZTO layer increases the efficiency of the device from 7.56% to 11.45%. To further investigate the beneficial effect of the ZTO layer on the efficiency of the device, this goal has been achieved by five methods: changing the S content of the absorber, changing the thickness of the absorber, changing the carrier concentration of ZTO, using various Sn/(Zn+Sn) ratios in ZTO, and altering the thickness of the ZTO layer. When the S content in Sb2(S,Se)3 is around 60% and the carrier concentration is about 1018 cm-3, the efficiency is optimal. The optimal thickness of the Sb2(S,Se)3 absorber layer is 260 nm. A ZTO/Sb2(S,Se)3 interface with a Sn/(Zn+Sn) ratio of 0.18 exhibits a better CBO value. It is also found that a ZTO thickness of 20 nm is needed for the best efficiency.

Optimization of Thermoelectric Properties and Physical Mechanisms of Cu2Se-Based Thin Films via Heat Treatment.

Cu2Se is an attractive thermoelectric material due to its layered structure, low cost, environmental compatibility, and non-toxicity. These traits make it a promising replacement for conventional thermoelectric materials in large-scale applications. This study focuses on preparing Cu2Se flexible thin films through in situ magnetron sputtering technology while carefully optimizing key preparation parameters, and explores the physical mechanism of thermoelectric property enhancement, especially the power factor. The films are deposited onto flexible polyimide substrates. Experimental findings demonstrate that films grown at a base temperature of 200 °C exhibit favorable performance. Furthermore, annealing heat treatment effectively regulates the Cu element content in the film samples, which reduces carrier concentration and enhances the Seebeck coefficient, ultimately improving the power factor of the materials. Compared to the unannealed samples, the sample annealed at 300 °C exhibited a significant increase in room temperature Seebeck coefficient, rising from 9.13 µVK-1 to 26.73 µVK-1. Concurrently, the power factor improved from 0.33 µWcm-1K-2 to 1.43 µWcm-1K-2.

Suppressing Buried Interface Nonradiative Recombination Losses Toward High-Efficiency Antimony Triselenide Solar Cells.

Antimony triselenide (Sb2 Se3 ) has possessed excellent optoelectronic properties and has gained interest as a light-harvesting material for photovoltaic technology over the past several years. However, the severe interfacial and bulk recombination obviously contribute to significant carrier transport loss thus leading to the deterioration of power conversion efficiency (PCE). In this work, buried interface and heterojunction engineering are synergistically employed to regulate the film growth kinetic and optimize the band alignment. Through this approach, the orientation of the precursor films is successfully controlled, promoting the preferred orientational growth of the (hk1) of the Sb2 Se3 films. Besides, interfacial trap-assisted nonradiative recombination loss and heterojunction band alignment are successfully minimized and optimized. As a result, the champion device presents a PCE of 9.24% with short-circuit density (JSC ) and fill factor (FF) of 29.47 mA cm-2 and 63.65%, respectively, representing the highest efficiency in sputtered-derived Sb2 Se3 solar cells. This work provides an insightful prescription for fabricating high-quality Sb2 Se3 thin film and enhancing the performance of Sb2 Se3 solar cells.

Segmented Control of Selenization Environment for High-Quality Cu2ZnSn(S,Se)4 Films Toward Efficient Kesterite Solar Cells.

High-crystalline-quality absorbers with fewer defects are crucial for further improvement of open-circuit voltage (VOC) and efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. However, the preparation of high-quality CZTSSe absorbers remains challenging due to the uncontrollability of the selenization reaction and the complexity of the required selenization environment for film growth. Herein, a novel segmented control strategy for the selenization environment, specifically targeting the evaporation area of Se, to regulate the selenization reactions and improve the absorber quality is proposed. The large evaporation area of Se in the initial stage of the selenization provides a great evaporation and diffusion flux for Se, which facilitates rapid phase transition reactions and enables the attainment of a single-layer thin film. The reduced evaporation area of Se in the later stage creates a soft-selenization environment for grain growth, effectively suppressing the loss of Sn and promoting element homogenization. Consequently, the mitigation of Sn-related deep-level defects on the surface and in the bulk induced by element imbalance is simultaneously achieved. This leads to a significant improvement in nonradiative recombination suppression and carrier collection enhancement, thereby enhancing the VOC. As a result, the CZTSSe device delivers an impressive efficiency of 13.77% with a low VOC deficit.

High-Performance Thermoelectric Flexible Ag2Se-Based Films with Wave-Shaped Buckling via a Thermal Diffusion Method.

Herein, an n-type Ag2Se thermoelectric flexible thin film has been fabricated on a polyimide (PI) substrate via a novel thermal diffusion method, and the thermoelectric performance is well-optimized by adjusting the pressure and temperature of thermal diffusion. All of the Ag2Se films are beneficial to grow (013) preferred orientations, which is conducive to performing a high Seebeck coefficient. By increasing the thermal diffusion temperature, the electrical conductivity can be rationally regulated while maintaining the independence of the Seebeck coefficient, which is mainly attributed to the increased electric mobility. As a result, the fabricated Ag2Se thin film achieves a high power factor of 18.25 µW cm-1 K-2 at room temperature and a maximum value of 21.7 µW cm-1 K-2 at 393 K. Additionally, the thermal diffusion method has resulted in a wave-shaped buckling, which is further verified as a promising structure to realize a larger temperature difference by the simulation results of finite element analysis (FEA). Additionally, this unique surface morphology of the Ag2Se thin film also exhibits outstanding mechanical properties, for which the elasticity modulus is only 0.42 GPa. Finally, a flexible round-shaped module assembled with Sb2Te3 has demonstrated an output power of 166 nW at a temperature difference of 50 K. This work not only introduces a new method of preparing Ag2Se thin films but also offers a convincing strategy of optimizing the microstructure to enhance low-grade heat utilization efficiency.

Charge Transport Enhancement in BiVO4 Photoanode for Efficient Solar Water Oxidation.

Photoelectrochemical (PEC) water splitting in a pH-neutral electrolyte has attracted more and more attention in the field of sustainable energy. Bismuth vanadate (BiVO4) is a highly promising photoanode material for PEC water splitting. Additionally, cobaltous phosphate (CoPi) is a material that can be synthesized from Earth's rich materials and operates stably in pH-neutral conditions. Herein, we propose a strategy to enhance the charge transport ability and improve PEC performance by electrodepositing the in situ synthesis of a CoPi layer on the BiVO4. With the CoPi co-catalyst, the water oxidation reaction can be accelerated and charge recombination centers are effectively passivated on BiVO4. The BiVO4/CoPi photoanode shows a significantly enhanced photocurrent density (Jph) and applied bias photon-to-current efficiency (ABPE), which are 1.8 and 3.2 times higher than those of a single BiVO4 layer, respectively. Finally, the FTO/BiVO4/CoPi photoanode displays a photocurrent density of 1.39 mA cm-2 at 1.23 VRHE, an onset potential (Von) of 0.30 VRHE, and an ABPE of 0.45%, paving a potential path for future hydrogen evolution by solar-driven water splitting.

Tellurium Doping Inducing Defect Passivation for Highly Effective Antimony Selenide Thin Film Solar Cell.

Antimony selenide (Sb2Se3) is emerging as a promising photovoltaic material owing to its excellent photoelectric property. However, the low carrier transport efficiency, and detrimental surface oxidation of the Sb2Se3 thin film greatly influenced the further improvement of the device efficiency. In this study, the introduction of tellurium (Te) can induce the benign growth orientation and the desirable Sb/Se atomic ratio in the Te-Sb2Se3 thin film. Under various characterizations, it found that the Te-doping tended to form Sb2Te3-doped Sb2Se3, instead of alloy-type Sb2(Se,Te)3. After Te doping, the mitigation of surface oxidation has been confirmed by the Raman spectra. High-quality Te-Sb2Se3 thin films with preferred [hk1] orientation, large grain size, and low defect density can be successfully prepared. Consequently, a 7.61% efficiency Sb2Se3 solar cell has been achieved with a VOC of 474 mV, a JSC of 25.88 mA/cm2, and an FF of 64.09%. This work can provide an effective strategy for optimizing the physical properties of the Sb2Se3 absorber, and therefore the further efficiency improvement of the Sb2Se3 solar cells.

Cadmium-Free Kesterite Thin-Film Solar Cells with High Efficiency Approaching 12.

Cadmium sulfide (CdS) buffer layer is commonly used in Kesterite Cu2 ZnSn(S,Se)4 (CZTSSe) thin film solar cells. However, the toxicity of Cadmium (Cd) and perilous waste, which is generated during the deposition process (chemical bath deposition), and the narrow bandgap (≈2.4 eV) of CdS restrict its large-scale future application. Herein, the atomic layer deposition (ALD) method is proposed to deposit zinc-tin-oxide (ZTO) as a buffer layer in Ag-doped CZTSSe solar cells. It is found that the ZTO buffer layer improves the band alignment at the Ag-CZTSSe/ZTO heterojunction interface. The smaller contact potential difference of the ZTO facilitates the extraction of charge carriers and promotes carrier transport. The better p-n junction quality helps to improve the open-circuit voltage (VOC ) and fill factor (FF). Meanwhile, the wider bandgap of ZTO assists to transfer more photons to the CZTSSe absorber, and more photocarriers are generated thus improving short-circuit current density (Jsc). Ultimately, Ag-CZTSSe/ZTO device with 10 nm thick ZTO layer and 5:1 (Zn:Sn) ratio, Sn/(Sn + Zn): 0.28 deliver a superior power conversion efficiency (PCE) of 11.8%. As far as it is known that 11.8% is the highest efficiency among Cd-free kesterite thin film solar cells.