All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

Transparent Ultrathin Oxygen‐Doped Silver Electrodes for Flexible Organic Solar Cells

An effective method for depositing highly transparent and conductive ultrathin silver (Ag) electrodes using minimal oxidation is reported. The minimal oxidation of Ag layers significantly improves the intrinsic optical and structural properties of Ag without any degradation of its electrical conductivity. Oxygen‐doped Ag (AgO_x) layers of thicknesses as low as 6 nm exhibit completely 2D and continuous morphologies on ZnO films, smaller optical reflections and absorbances, and smaller sheet resistances compared with those of discontinuous and granular‐type Ag layers of the same thickness. A ZnO/AgO_x/ZnO (ZAOZ) electrode using an AgO_x (O/Ag = 3.4 at%) layer deposited on polyethylene terephthalate substrates at room temperature shows an average transmittance of 91%, with a maximum transmittance of 95%, over spectral range 400?1000 nm and a sheet resistance of 20 Ω sq^?1. The average transmittance value is increased by about 18% on replacing a conventional ZnO/Ag/ZnO (ZAZ) electrode with the ZAOZ electrode. The ZAOZ electrode is a promising bottom transparent conducting electrode for highly flexible inverted organic solar cells (IOSCs), and it achieves a power conversion efficiency (PCE) of 6.34%, whereas an IOSC using the ZAZ electrode exhibits a much lower PCE of 5.65%.     

DC‐sputtered ZnO:Al as transparent conductive oxide for silicon heterojunction solar cells with µc‐Si:H emitter

Silicon heterojunction (SHJ) solar cells are highly interesting, because of their high efficiency and low cost fabrication. So far, the most applied transparent conductive oxide (TCO) is indium tin oxide (ITO). The replacement of ITO with cheaper, more abundant and environmental friendly material with texturing capability is a promising way to reduce the production cost of the future SHJ solar cells. Here, we report on the fabrication of the SHJ solar cells with direct current‐sputtered aluminum‐doped zinc oxide (ZnO:Al) as an alternative TCO. Furthermore, we address several important differences between ITO and the ZnO:Al layers including a high Schottky barrier at the emitter/ZnO:Al interface and a high intrinsic resistivity of the ZnO:Al layers. To overcome the high Schottky barrier, we suggest employing micro‐crystalline silicon (µc‐Si:H) emitter, which also improves temperature threshold and passivation of the solar cell precursor. In addition, we report on the extensive studies of the effect of the ZnO:Al deposition parameters including layer thickness, oxygen flow, power density and temperature on the electrical properties of the fabricated SHJ solar cells. Finally, the results of our study indicate that the ZnO:Al deposition parameters significantly affect the electrical properties of the obtained solar cell. By understanding and fine‐tuning all these parameters, a high conversion efficiency of 19.2% on flat wafer (small area (5 × 5 mm²) and without any front metal grid) is achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

Inkjet printed metallizations for Cu(In1−x Ga x )Se2 photovoltaic cells

This study reports the inkjet printing of Ag front contacts on Aluminum doped Zinc Oxide (AZO)/intrinsic Zinc Oxide (i‐ZnO)/CdS/Cu(In_1−xGa_x)Se₂ (CIGS)/Mo thin film photovoltaic cells. The printed Ag contacts are being developed to replace the currently employed evaporated Ni/Al bi‐layer contacts. Inkjet deposition conditions were optimized to reduce line resistivity and reduce contact resistance to the Al:ZnO layer. Ag lines printed at a substrate temperature of 200°C showed a line resistivity of 2.06 µΩ · cm and a contact resistance to Al:ZnO of 8.2 ± 0.2 mΩ · cm² compared to 6.93 ± 0.3 mΩ · cm² for thermally evaporated contacts. These deposition conditions were used to deposit front contacts onto high quality CIGS thin film photovoltaic cells. The heating required to print the Ag contacts caused the performance to degrade compared to similar devices with evaporated Ni/Al contacts that were not heated. Devices with inkjet printed contacts showed 11.4% conversion efficiency compared to 14.8% with evaporated contacts. Strategies to minimize heating, which is detrimental for efficiency, during inkjet printing are proposed. Copyright © 2011 John Wiley & Sons, Ltd.     

Improved micromorph solar cells by means of mixed‐phase n‐doped silicon oxide layers

A good light trapping scheme is necessary to improve the performance of amorphous/microcrystalline silicon tandem cells. This is generally achieved by using a highly reflective transparent conducting oxide/metal back contact plus an intermediate reflector between the component cells. In this work, the use of doped silicon oxide as alternative n‐layer in micromorph solar cells is proposed as a means to obtain high current values using a simple Ag back contact and no extra reflector between the component cells n‐doped silicon oxide layers with a wide range of optical and electrical properties have been prepared. The influence of different deposition regimes on the material properties has been studied. The main findings are the following: (i) when carbon dioxide is added to the gas mixture, sufficiently high hydrogen dilution is necessary to widen the transition region from highly conductive microcrystalline‐like films to amorphous material characterized by low electrical conductivity; (ii) lower refractive index values are found with lower deposition pressure. Optimal n‐doped silicon oxide layers have been used in both component cells of micromorph devices, adopting a simple Ag back contact. Higher current values for both cells are obtained in comparison with the values obtained using standard n‐doped microcrystalline silicon, whereas similar values of fill factor and open circuit voltage are measured. The current enhancement is particularly evident for the bottom cell, as revealed by the increased spectral response in the red/infrared region. The results prove the high potential of n‐doped silicon oxide as ideal reflector for thin‐film silicon solar cells. Copyright © 2011 John Wiley & Sons, Ltd.     

Improvement of the cell performance in the ZnS/Cu(In,Ga)Se2 solar cells by the sputter deposition of a bilayer ZnO : Al film

ZnS is a candidate to replace CdS as the buffer layer in Cu(In,Ga)Se₂ (CIGS) solar cells for Cd‐free commercial product. However, the resistance of ZnS is too large, and the photoconductivity is too small. Therefore, the thickness of the ZnS should be as thin as possible. However, a CIGS solar cell with a very thin ZnS buffer layer is vulnerable to the sputtering power of the ZnO : Al window layer deposition because of plasma damage. To improve the efficiency of CIGS solar cells with a chemical‐bath‐deposited ZnS buffer layer, the effect of the plasma damage by the sputter deposition of the ZnO : Al window layer should be understood. We have found that the efficiency of a CIGS solar cell consistently decreases with an increase in the sputtering power for the ZnO : Al window layer deposition onto the ZnS buffer layer because of plasma damage. To protect the ZnS/CIGS interface, a bilayer ZnO : Al film was developed. It consists of a 50‐nm‐thick ZnO : Al plasma protection layer deposited at a sputtering power of 50 W and a 100‐nm‐thick ZnO : Al conducting layer deposited at a sputtering power of 200 W. The introduction of a 50‐nm‐thick ZnO : Al layer deposited at 50 W prevented plasma damage by sputtering, resulting in a high open‐circuit voltage, a large fill factor, and shunt resistance. The ZnS/CIGS solar cell with the bilayer ZnO : Al film yielded a cell efficiency of 14.68%. Therefore, the application of bilayer ZnO : Al film to the window layer is suitable for CIGS solar cells with a ZnS buffer layer. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of metal-fingers/doped-ZnO transparent electrode on performance of GaN/InGaN solar cell

The effect of doped-ZnO transparent conductive oxide (TCO) with metal (Ag)-fingers contact on GaN/InGaN solar cell is investigated through numerical simulations. An optical and electrical analysis of different dopant elements (such as B, Al, Ga, In and Sn) with ZnO as a top TCO layer is studied. A comparative analysis of metal square pad electrode, metal grid pattern electrode and metal-finger/ZnO type electrodes are taken into consideration to ensure the effect of anti-reflectivity by ZnO. The effect of thickness of ZnO and i-InGaN layer on performance of solar cell is also studied in detail. The proposed solar cell structure with Ag-fingers/ZnO:Al as top contact electrode shows interesting device characteristics compared to other dopants and metal top electrodes. The device achieves open circuit voltage~2.525 V, short circuit current~4.256 mA/cm², fill factor~87.86% and efficiency~9.22% under 1 Sun, air mass 1.5 global illumination.     

Interdigitated back‐contact heterojunction solar cell concept for liquid phase crystallized thin‐film silicon on glass

We present an interdigitated back‐contact silicon heterojunction system designed for liquid‐phase crystallized thin‐film (~10 µm) silicon on glass. The preparation of the interdigitated emitter (a‐Si:H(p)) and absorber (a‐Si:H(n)) contact layers relies on the etch selectivity of doped amorphous silicon layers in alkaline solutions. The etch rates of a‐Si:H(n) and a‐Si:H(p) in 0.6% NaOH were determined and interdigitated back‐contact silicon heterojunction solar cells with two different metallizations, namely Al and ITO/Ag electrodes, were evaluated regarding electrical and optical properties. An additional random pyramid texture on the back side provides short‐circuit current density (j_SC) of up to 30.3 mA/cm² using the ITO/Ag metallization. The maximum efficiency of 10.5% is mainly limited by a low of fill factor of 57%. However, the high j_SC, as well as V_OC values of 633 mV and pseudo‐fill factors of 77%, underline the high potential of this approach. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhanced Omnidirectional Photovoltaic Performance of Solar Cells Using Multiple‐Discrete‐Layer Tailored‐ and Low‐Refractive Index Anti‐Reflection Coatings

An optimized four‐layer tailored‐ and low‐refractive index anti‐reflection (AR) coating on an inverted metamorphic (IMM) triple‐junction solar cell device is demonstrated. Due to an excellent refractive index matching with the ambient air by using tailored‐ and low‐refractive index nanoporous SiO₂ layers and owing to a multiple‐discrete‐layer design of the AR coating optimized by a genetic algorithm, such a four‐layer AR coating shows excellent broadband and omnidirectional AR characteristics and significantly enhances the omnidirectional photovoltaic performance of IMM solar cell devices. Comparing the photovoltaic performance of an IMM solar cell device with the four‐layer AR coating and an IMM solar cell with the conventional SiO₂/TiO₂ double layer AR coating, the four‐layer AR coating achieves an angle‐of‐incidence (AOI) averaged short‐circuit current density, J_SC, enhancement of 34.4%, whereas the conventional double layer AR coating only achieves an AOI‐averaged J_SC enhancement of 25.3%. The measured reflectance reduction and omnidirectional photovoltaic performance enhancement of the four‐layer AR coating are to our knowledge, the largest ever reported in the literature of solar cell devices.     

Silver versus white sheet as a back reflector for microcrystalline silicon solar cells deposited on LPCVD‐ZnO electrodes of various textures

We compare the performance of two back reflector designs on the optoelectrical properties of microcrystalline silicon solar cells. The first one consists of a 5‐µm‐thick low‐pressure chemical vapor deposition (LPCVD)‐ZnO electrode combined with a white sheet; the second one incorporates an Ag reflector deposited on a thin LPCVD‐ZnO layer (with thickness below 200 nm). For this latter design, the optical loss in the nano‐rough Ag reflector can be strongly reduced by smoothing the surface of the thin underlying ZnO layer, by means of an Ar‐plasma treatment. Because of its superior lateral conductivity, the thin‐ZnO/Ag back reflector design provides a higher fill factor than the dielectric back reflector design. When decreasing the roughness of the front electrode with respect to our standard front LPCVD‐ZnO layer, the electrical cell performance is improved; in addition, the implementation of the thin‐ZnO/Ag back reflector leads to a significant relative gain in light trapping. Applying this newly optimized combination of front and back electrodes, the conversion efficiency is improved from 8.9% up to 9.4%, for cells with an active‐layer thickness of only 1.1 µm. We thereby highlight the necessity to optimize simultaneously the front and back electrodes. Copyright © 2014 John Wiley & Sons, Ltd.     

Coral‐shaped ZnO nanostructures for dye‐sensitized solar cell photoanodes

A highly efficient ZnO photoanode for dye‐sensitized solar cells was successfully grown by a simple, low cost, and scalable method. A nanostructured coral‐shaped Zn layer was deposited by sputtering onto fluorine‐doped tin oxide/glass slices at room temperature and then thermally oxidized in ambient atmosphere. Stoichiometry, crystalline phase, quality, and morphology of the film were investigated, evidencing the formation of a highly porous branched nanostructure, with a pure wurtzite crystalline structure. ZnO‐based dye‐sensitized solar cells were fabricated with customized microfluidic architecture. Dye loading on the oxide surface was analyzed with ultraviolet‐visible spectroscopy, and the dependence of the cell efficiency on sensitizer incubation time and film thickness was studied by current‐voltage electrical characterization, incident photon‐to‐electron conversion efficiency, and impedance spectroscopy measurements, showing the promising properties of this material for the fabrication of dye‐sensitized solar cell photoanodes with a solar conversion efficiency up to 4.58%. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced Performance of I2‐Free Solid‐State Dye‐Sensitized Solar Cells with Conductive Polymer up to 6.8%

An iodine‐free solid‐state dye‐sensitized solar cell (ssDSSC) is reported here, with 6.8% energy conversion efficiency—one of the highest yet reported for N719 dye—as a result of enhanced light harvesting from the increased transmittance of an organized mesoporous TiO₂ interfacial layer and the good hole conductivity of the solid‐state‐polymerized material. The organized mesoporous TiO₂ (OM‐TiO₂) interfacial layer is prepared on large‐area substrates by a sol‐gel process, and is confirmed by scanning electron microscopy (SEM) and grazing incidence small‐angle X‐ray scattering (GISAXS). A 550‐nm‐thick OM‐TiO₂ film coated on fluorine‐doped tin oxide (FTO) glass is highly transparent, resulting in transmittance increases of 8 and 4% compared to those of the bare FTO and conventional compact TiO₂ film on FTO, respectively. The high cell performance is achieved through careful control of the electrode/hole transport material (HTM) and nanocrystalline TiO₂/conductive glass interfaces, which affect the interfacial resistance of the cell. Furthermore, the transparent OM‐TiO₂ film, with its high porosity and good connectivity, exhibits improved cell performance due to increased transmittance in the visible light region, decreased interfacial resistance ( Ω ), and enhanced electron lifetime ( τ ). The cell performance also depends on the conductivity of HTMs, which indicates that both highly conductive HTM and the transparent OM‐TiO₂ film interface are crucial for obtaining high‐energy conversion efficiencies in I₂‐free ssDSSCs.     

Ligand‐Free Synthesis of Aluminum‐Doped Zinc Oxide Nanocrystals and their Use as Optical Spacers in Color‐Tuned Highly Efficient Organic Solar Cells

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal‐oxide‐based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO₂ limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster‐free Al‐doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO‐based optical spacers. These AZO NCs also open new opportunities for the processing of high‐efficiency color tuned solar cells. For the first time, it is shown that applying solution‐processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors.     

Improved conversion efficiency of a‐Si:H/µc‐Si:H thin‐film solar cells by using annealed Al‐doped zinc oxide as front electrode material

In recent years, zinc oxide has been investigated as a front electrode material in hydrogenated amorphous silicon/hydrogenated microcrystalline silicon (a‐Si:H/µc‐Si:H) tandem solar cells. Such as for other transparent conducting oxide materials and applications, a proper balancing of transparency and conductivity is necessary. The latter is directly related to the density and the mobility of charge carriers. A high density of charge carriers increases conductivity but leads to a higher absorption of light in the near‐infrared part of the spectrum due to increased free‐carrier absorption. Hence, the only way to achieve high conductivity while keeping the transparency as high as possible relies on an increase of carrier mobility. The carrier density and the mobility of sputtered Al‐doped zinc oxide (ZnO:Al) can be tailored by a sequence of different annealing steps. In this work, we implemented such annealed ZnO:Al films as a front electrode in a‐Si:H/µc‐Si:H tandem solar cells and compared the results with those of reference cells grown on as‐deposited ZnO:Al. We observed an improvement of short‐circuit current density as well as open‐circuit voltage and fill factor. The gain in current density could be attributed to a reduction of both sub‐band‐gap absorption and free‐carrier absorption in the ZnO:Al. The higher open‐circuit voltage and fill factor are indicators of a better device quality of the silicon for cells grown on annealed ZnO:Al. Altogether, the annealing led to an improved initial conversion efficiency of 12.1%, which was a gain of +0.7% in absolute terms. Copyright © 2013 John Wiley & Sons, Ltd.     

Mitigating Plasmonic Absorption Losses at Rear Electrodes in High‐Efficiency Silicon Solar Cells Using Dopant‐Free Contact Stacks

Although charge‐carrier selectivity in conventional crystalline silicon (c‐Si) solar cells is usually realized by doping Si, the presence of dopants imposes inherent performance limitations due to parasitic absorption and carrier recombination. The development of alternative carrier‐selective contacts, using non‐Si electron and hole transport layers, has the potential to overcome such drawbacks and simultaneously reduce the cost and/or simplify the fabrication process of c‐Si solar cells. Nevertheless, devices relying on such non‐Si contacts with power conversion efficiencies (PCEs) that rival their classical counterparts are yet to be demonstrated. In this study, one key element is brought forward toward this demonstration by incorporating low‐pressure chemical vapor deposited ZnO as the electron transport layer in c‐Si solar cells. Placed at the rear of the device, it is found that rather thick (75 nm) ZnO film capped with LiF_x/Al simultaneously enables efficient electron selectivity and suppression of parasitic infrared absorption. Next, these electron‐selective contacts are integrated in c‐Si solar cells with MoO_x‐based hole‐collecting contacts at the device front to realize full‐area dopant‐free‐contact solar cells. In the proof‐of‐concept device, a PCE as high as 21.4% is demonstrated, which is a record for this novel device class and is at the level of conventional industrial solar cells.     

Metal versus dielectric back reflector for thin‐film Si solar cells with impact of front electrode surface texture

Thin‐film Si solar cells employ a back reflector (BR) for a more efficient use of the long wavelength light. Here, we have carried out a cross evaluation of metal (Ag‐based) and dielectric (white paint‐based) BR designs. Conclusive results have been reached regarding the most suitable BR type depending on the front electrode morphology, both with crater‐like and pyramidal texture. The ZnO/Ag BR is found to be optically more efficient because of improved light trapping, although the gain tends to vanish for rougher front electrodes. Thanks to non‐conventional Raman intensity measurements, this dependence on the front texture has been linked to the different weight of front and back interfaces in the light trapping process for the different morphologies. With rougher substrates, because the minor optical gain is accompanied by sputter‐induced electronic deterioration of the solar cell during the ZnO buffer layer deposition, the white paint‐based BR design is preferred. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10⁻³ Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al₂O₃ barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al₂O₃ films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrodeposited zinc grid as low‐cost solar cell front contact

This paper presents an innovative low‐cost electrodeposition process to grow metallic zinc grids as a front contact for Cu(In,Ga)(Se,S)₂ (CIGS) and silicon heterojunction solar cells as an alternative to complex and expensive monolithic integration and silver screen printing techniques respectively. Morphological and electrical properties of the grid have been investigated and compared with a reference evaporated one. High quality and conformal zinc grids have been deposited showing very high growth rates up to 3.3 µm min⁻¹. Zinc grid is successfully deposited as front electrode for CIGS solar cells that are fabricated by a variety of deposition processes. Efficiency (16.3%) is achieved without antireflection coating on a 0.5 cm² co‐evaporated absorber and 14.8% on an electrodeposited one. Using electrodeposition for the growth of the doped ZnO film as well, a 14.1% efficiency is demonstrated on an all‐wet solar cell only composed of layers deposited by atmospheric methods—from absorber to metallic grid. The process is then applied to a 4.2 cm² cell as a first step toward large‐scale application. Finally, a zinc grid is deposited on a 0.5 cm² silicon heterojunction showing a promising 17% efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

All‐Solution‐Processed Cu2ZnSnS4 Solar Cells with Self‐Depleted Na2S Back Contact Modification Layer

The thin‐film photovoltaic material Cu₂ZnSnS₄ (CZTS) has drawn worldwide attention in recent years due to its earth‐abundant, nontoxic element constitution, and remarkable photovoltaic performance. Although state‐of‐the‐art power conversion efficiency is achieved by hydrazine‐based methods, effort to fabricate such devices in a high throughput, environmental‐friendly way is still highlydesired. Here a hydrazine‐free all‐solution‐processed CZTS solar cell with Na₂S self‐depleted back contact modification layer for the first time is demonstrated, using a ball‐milled CZTS as light absorber, low‐temperature solution‐processed ZnO electron‐transport layer as well as silver‐nanowire transparent electrode. The inserting of Na₂S self‐depleted layer is proven to effectively stabilize the CZTS/Mo interface by eliminating a detrimental phase segregation reaction between CZTS and Mo‐coated soda lime glass, thus leading to a better crystallinity of CZTS light absorbing layer, enhanced carrier transportation at CZTS/Mo interface as well as a smaller series resistance. Furthermore, the self‐depletion feature of the Na₂S modification layer also averts hole‐transportation barrier within the devices. The results show the vital importance of interfacial engineering for these CZST devices and the Na₂S interface layer can be extended to other optoelectronic devices using Mo contact.