Nanoscale Microstructure and Chemistry of Cu2ZnSnS4/CdS Interface in Kesterite Cu2ZnSnS4 Solar Cells

Sulfurization with various atmosphere and postheat treatments has been reported for earth abundant kesterite Cu₂ZnSnS₄ (CZTS) preparation as cost‐effective material for next‐generation solar cells. A full understanding of the nanoscale microstructure and chemistry of CZTS/CdS interface obtained from these different fabrication routes is currently lacking, yet is critical to developing optimal processing routes for high‐performance kesterite solar cells. Here, the first detailed investigation of the interfacial microstructure and chemistry of CdS/Cu₂ZnSnS₄ heterojunctions is presented. For CZTS obtained from sulfurization in a sulfur‐only atmosphere where highly defective surfaces are present, air annealing followed by etching in the initial stage of chemical bath deposition (CBD) process can effectively eliminate interfacial defects and allow the epitaxial growth of CBD‐CdS, improving the minority lifetime, open circuit voltage (V_OC), and fill factor (FF) of the devices, while blocking Cd diffusion and deteriorating short circuit current (J_sc). For CZTS from sulfurization in a combined sulfur and SnS atmosphere where CBD‐CdS can directly epitaxially grow on CZTS and Cd‐diffusion is clearly observed, associated devices show the longest lifetime and the highest efficiency of 8.76%. Epitaxial growth of CdS and Cd diffusion into CZTS are found to be two crucial features minimizing interfacial recombination and achieving high‐efficiency devices. This will not only enhance the understanding of the device structure and physics of kesterite based solar cells, but also provide an effective way for designing other chalcogenide heterojunction solar cells.     

Cation Substitution of Solution‐Processed Cu2ZnSnS4 Thin Film Solar Cell with over 9% Efficiency

To alleviate the limitations of pure sulfide Cu₂ZnSnS₄ (CZTS) thin film, such as band gaps adjustment, antisite defects, secondary phase and microstructure, Cadmium is introduced into CZTS thin film to replace Zn partially to form Cu₂Zn_1?xCd_xSnS₄ (CZCTS) thin film by low‐cost sol–gel method. It is demonstrated that the band gaps and crystal structure of CZCTS thin films are affected by the change in Zn/Cd ratio. In addition, the ZnS secondary phase can be decreased and the grain sizes can be improved to some degree by partial replacement of Zn with Cd in CZCTS thin film. The power conversion efficiency of CZTS solar cell device is enhanced significantly from 5.30% to 9.24% (active area efficiency 9.82%) with appropriate ratio of Zn/Cd. The variation of device parameter as a function of Zn/Cd ratio may be attributed to the change in electronic structure of the bulk CZCTS thin film (i.e., phase change from kesterite to stannite), which in turn affects the band alignment at the CZCTS/buffer interface and the charge separation at this interface.     

Targeting Ideal Dual‐Absorber Tandem Water Splitting Using Perovskite Photovoltaics and CuInxGa1‐xSe2 Photocathodes

Efficient sunlight‐driven water splitting devices can be achieved by pairing two absorbers of different optimized bandgaps in an optical tandem design. With tunable absorption ranges and cell voltages, organic–inorganic metal halide perovskite solar cells provide new opportunities for tailoring top absorbers for such devices. In this work, semitransparent perovskite solar cells are developed for use as the top cell in tandem with a smaller bandgap photocathode to enable panchromatic harvesting of the solar spectrum. A new CuIn_xGa_1‐xSe₂ multilayer photocathode is designed, exhibiting excellent performance for photoelectrochemical water reduction and representing a near‐ideal bottom absorber. When pairing it below a semitransparent CH₃NH₃PbBr₃‐based solar cell, a solar‐to‐hydrogen efficiency exceeding 6% is achieved, the highest value yet reported for a photovoltaic–photoelectrochemical device utilizing a single‐junction solar cell as the bias source under one sun illumination. The analysis shows that the efficiency can reach more than 20% through further optimization of the perovskite top absorber.     

Significant Efficiency Enhancement in Ultrathin CZTS Solar Cells by Combining Al Plasmonic Nanostructures Array and Antireflective Coatings

In the few past years, the economic and eco-friendly Cu₂ZnSnS₄ (CZTS) solar cells have caught lots of attentions. However, due to rather poor efficiency, identifying deficiencies and making improvements is necessary. In the present study, the performance improvement of ultrathin CZTS solar cells was achieved through (1) incorporation of anti-reflective coating (ARC) on the surface of cell and (2) embedding Al plasmonic nanostructures with different radius, periods, and vertical positions in the absorber layer. Various thicknesses of CZTS absorber layer were simulated optically and electrically using FDTD and DEVICE solver of Lumerical software. The reference solar cell consists of a 1.5-nm-thick CZTS absorber and exhibit an efficiency of up to 5.67%, short-circuit current density (Jsc) of 18.48 mA cm⁻² and open circuit voltage of 0.58 V. Result showed a remarkable performance enhancement of the solar cell in spite of a very thin absorber layer. For a 500-μm-thick CZTS solar cell with the assistance of ARC and embedding Al plasmonic nanostructures, the efficiency is increased to 7.45% due to an increase in Jsc to 22.62 mA cm⁻² with an open circuit voltage of 0.62 V.

     

The Role of Hydrogen from ALD‐Al2O3 in Kesterite Cu2ZnSnS4 Solar Cells: Grain Surface Passivation

In this research, a new route of surface passivation is reported by introducing hydrogen from the atomic layer deposited (ALD) Al₂O₃ layer into pure sulfide Cu₂ZnSnS₄ (CZTS) solar cells. Different amounts of hydrogen are incorporated into the Cu₂ZnSnS₄/CdS interface through controlling the thickness of the ALD‐Al₂O₃ layer. The device with three cycles of ALD‐Al₂O₃ yields the highest efficiency of 8.08% (without antireflection coating) with improved open‐circuit voltage of up to 70 mV. With closer examination on the passivation route of ALD‐Al₂O₃, it is revealed by the surface chemisty study that the Al₂O₃ can be etched away by ammonium hydroxide in the CdS buffer deposition process. Instead, the hydrogen is detected within a shallow depth from the CZTS surface, and makes a significant difference in the measured distribution of contact potential difference and device performance. This may be interpreted by the effect of hydrogen passivation of the CZTS surface by curing dangling bonds at the surface of CZTS grains. This work may provide a new direction of further improving the performance of kesterite solar cells.     

Electron‐Beam‐Evaporated Nickel Oxide Hole Transport Layers for Perovskite‐Based Photovoltaics

High‐quality charge carrier transport materials are of key importance for stable and efficient perovskite‐based photovoltaics. This work reports on electron‐beam‐evaporated nickel oxide (NiO_x) layers, resulting in stable power conversion efficiencies (PCEs) of up to 18.5% when integrated into solar cells employing inkjet‐printed perovskite absorbers. By adding oxygen as a process gas and optimizing the layer thickness, transparent and efficient NiO_x hole transport layers (HTLs) are fabricated, exhibiting an average absorptance of only 1%. The versatility of the material is demonstrated for different absorber compositions and deposition techniques. As another highlight of this work, all‐evaporated perovskite solar cells employing an inorganic NiO_x HTL are presented, achieving stable PCEs of up to 15.4%. Along with good PCEs, devices with electron‐beam‐evaporated NiO_x show improved stability under realistic operating conditions with negligible degradation after 40 h of maximum power point tracking at 75 °C. Additionally, a strong improvement in device stability under ultraviolet radiation is found if compared to conventional perovskite solar cell architectures employing other metal oxide charge transport layers (e.g., titanium dioxide). Finally, an all‐evaporated perovskite solar mini‐module with a NiO_x HTL is presented, reaching a PCE of 12.4% on an active device area of 2.3 cm².     

Cesium Doped NiOx as an Efficient Hole Extraction Layer for Inverted Planar Perovskite Solar Cells

Organic–inorganic hybrid perovskite solar cells have resulted in tremendous interest in developing next generation photovoltaics due to high record efficiency exceeding 22%. For inverted structure perovskite solar cells, the hole extraction layers play a significant role in achieving efficient and stable perovskite solar cell by modifying charge extraction, interfacial recombination losses, and band alignment. Here, cesium doped NiO_x is selected as a hole extraction layer to study the impact of Cs dopant on the optoelectronic properties of NiO_x and the photovoltaic performance. Cs doped NiO_x films are prepared by a simple solution‐based method. Both doped and undoped NiO_x films are smooth and highly transparent, while the Cs doped NiO_x exhibits better electron conductivity and higher work function. Therefore, Cs doping results in a significant improvement in the performance of NiO_x‐based inverted planar perovskite solar cells. The best efficiency of Cs doped NiO_x devices is 19.35%, and those devices show high stability as well. The improved efficiency in devices with Cs:NiO_x is attributed to a significant improvement in the hole extraction and better band alignment compared to undoped NiO_x. This work reveals that Cs doped NiO_x is very promising hole extraction material for high and stable inverted perovskite solar cells.     

Aging Effect of a Cu(In,Ga)(S,Se)2 Absorber on the Photovoltaic Performance of Its Cd‐Free Solar Cell Fabricated by an All‐Dry Process: Its Carrier Recombination Analysis

Cd‐free Cu(In,Ga)(S,Se)₂ (CIGSSe) solar cells are fabricated by an all‐dry process (a Cd‐free and all‐dry process CIGSSe solar cell) with aged CIGSSe thin film absorbers. The aged CIGSSe thin films are kept in a desiccator cabinet under partial pressure of oxygen of ≈200 Pa for aging time up to 10 months. It is reported for the first time that aged CIGSSe thin film with increased aging time results in significant enhancement of photovoltaic performance of Cd‐free and all‐dry process CIGSSe solar cells, regardless of the alkali treatment. Based on carrier recombination analysis, carrier recombination rates at the interface and in the depletion region of the Cd‐free and all‐dry process CIGSSe solar cells are reduced owing to avoidance of sputtering damage on CIGSSe absorber surface, which is consistent with the strong electron beam‐induced current signal near CIGSSe surface after the increased aging time. It is implied that the interface and near‐surface qualities are clearly improved through the increased aging time, which is attributable to the self‐forming of In_x(O,S)_y near CIGSSe surface, which acts as a buffer layer. Ultimately, the 22.0%‐efficient Cd‐free CIGSSe solar cell fabricated by all‐dry process is achieved with the aged Cs‐treated CIGSSe absorber with the aging time of 10 months.     

Oxygenated CdS Buffer Layers Enabling High Open‐Circuit Voltages in Earth‐Abundant Cu2BaSnS4 Thin‐Film Solar Cells

Earth‐abundant Cu₂BaSnS₄ (CBTS) thin films exhibit a wide bandgap of 2.04–2.07 eV, a high absorption coefficient > 10⁴ cm^?1, and a p‐type conductivity, suitable as a top‐cell absorber in tandem solar cell devices. In this work, sputtered oxygenated CdS (CdS:O) buffer layers are demonstrated to create a good p–n diode with CBTS and enable high open‐circuit voltages of 0.9–1.1 V by minimizing interface recombination. The best power conversion efficiency of 2.03% is reached under AM 1.5G illumination based on the configuration of fluorine‐doped SnO₂ (back contact)/CBTS/CdS:O/CdS/ZnO/aluminum‐doped ZnO (front contact).     

Photovoltaic Materials and Devices Based on the Alloyed Kesterite Absorber (AgxCu1–x)2ZnSnSe4

The photovoltaic absorber Cu₂ZnSn(S_xSe_1–x)₄ (CZTSSe) has attracted interest in recent years due to the earth‐abundance of its constituents and the realization of high performance (12.6% efficiency). The open‐circuit voltage in CZTSSe devices is believed to be limited by absorber band tailing caused by the exceptionally high density of Cu/Zn antisites. By replacing Cu in CZTSSe with Ag, whose covalent radius is ≈15% larger than that of Cu and Zn, the density of I–II antisite defects is predicted to drop. The fundamental properties of the mixed Ag‐Cu kesterite compound are reported as a function of the Ag/(Ag + Cu) ratio. The extent of band tailing is shown to decrease with increasing Ag. This is verified by comparing the optical band gap extrapolated from transmission data with the position of the room‐temperature photoluminescence peak; these values converge for the pure‐Ag compound. Additionally, the pinning of the Fermi level in CZTSSe, attributed to heavy defect compensation and band tailing, is not observed in the pure‐Ag compound, offering further evidence of improved electronic structure. Finally, a device efficiency of 10.2% is reported for a device containing 10% Ag (no antireflection coating); this compares to ≈9% (avg) efficiency for the baseline pure‐Cu CZTSe.     

Rear Surface Passivation for Ink-Based,Submicron CuIn(S,Se)2 Solar Cells

A N, N-dimethylformamide and thiourea-based route is developed to fabricate submicron (0.55 and 0.75 µm) thick CuIn(S,Se)₂ (CISSe) thin films for photovoltaic applications, addressing challenges of material usage, throughput, and manufacturing costs. However, reducing the absorber film thickness below 1 µm in a regular CISSe solar cell decreases the device efficiency due to losses at the highly-recombinative, and mediocre-reflective Mo/CISSe rear interface. For the first time, to mitigate the rear recombination losses, a novel rear contacting structure involving a surface passivation layer and point contact openings is developed for solution processed CISSe films and demonstrated in tangible devices. An atomic layer deposited Al₂O₃ film is employed to passivate the Mo/CISSe rear surface while precipitates formed via chemical bath deposition of CdS are used to generate nanosized point openings. Consequently, Al₂O₃ passivated CISSe solar cells show an increase in the open-circuit voltage (V_OC) and short-circuit current density when compared to reference cells with equivalent absorber thicknesses. Notably, a V_OC increase of 59 mV contributes to active area efficiencies of 14.2% for rear passivated devices with 0.75 µm thick absorber layers, the highest reported value for submicron-based solution processed, low bandgap CISSe solar cells.     

Geogrid‐Inspired Nanostructure to Reinforce a CuxZnySnzS Nanowall Electrode for High‐Stability Electrochemical Energy Conversion Devices

Inspired by geogrids commonly applied in construction engineering to reinforce side slopes and retaining walls, the use of a “nano‐geogrid” to reinforce a Cu_x Zn_y Sn_z S (CZTS) nanowall electrode for application in electrochemical reactions is demonstrated. The CZTS nanowall electrode reinforced by the nano‐geogrid (denoted as NWD) shows not only remarkable mechanical and electrochemical stability but also considerable electrochemical performances. The NWD demonstrated as a counter electrode in a dye‐sensitized solar cell shows a power conversion efficiency of 7.44 ± 0.04%, comparable with the device using Pt as electrode, and also significantly improves device stability as compared with that afforded by an electrode comprising a CZTS nanowall without the nano‐geogrid (denoted as NOD). In addition, applying the NWD electrode as a cathode in photo‐electrochemical hydrogen evolution reactions (HERs) yields a photocurrent density of ?10 mA cm^?2 at ?0.162 V (vs RHE) under AM 1.5 illumination. Moreover, when HERs are conducted under extreme conditions, the NWD electrode remains intact, whereas the NOD electrode is completely peeled off after 10 min of reaction. Therefore, the concept of using a mimetic rational nanostructure could pave the way for the possibility of improving the performance and stability of various devices.     

Ultra-thin Semiconductor/Metal Resonant Superabsorbers

The design of thin-film semiconductor absorbers is a long-sought-after goal of crucial importance for optoelectronic devices. We propose a new strategy that achieves multi-band optical absorption in an ultra-thin semiconductor-insulator-metal nanostructure. The whole thickness of the absorber is just 60 nm, which is less than λ/12. The ultra-thin semiconductor resonators are used as the photonic coupling elements. The plasmonic metal layer with the thickness about 15 nm simultaneously acts as the transmission cancel layer and the plasmon source for resonant coupling with the optical near-field energy. The combined semiconductor resonators and the thin metal film produce strong electromagnetic field coupling and confinement effects, which mainly contribute to the efficient light trapping for the multi-band strong light absorption. The semiconductors such as Si, GaAs, and Ge are confirmed with the capability to show high light absorption via this simple hybrid metal-semiconductor resonant system. These features pave new insight on ultra-thin semiconductor absorbers and hold potential applications for optoelectronics such as nonlinear optics, hot-electron excitation and extraction, and the related devices.

     

Advanced Alkali Treatments for High‐Efficiency Cu(In,Ga)Se2 Solar Cells on Flexible Substrates

Flexible, lightweight Cu(In,Ga)Se₂ (CIGS) solar cells grown on polymer substrates are a promising technology with fast growing market prospects. However, power conversion efficiencies of solar cells grown at low temperatures (≈450 °C) remain below the efficiencies of cells grown at high temperature on glass substrates. This contribution discusses the impact on cell efficiency of process improvements of low‐temperature CIGS deposition on flexible polyimide and glass substrates. Different strategies for incorporation of alkali elements into CIGS are evaluated based on a large number of depositions. Postdeposition treatment with heavy alkali (here RbF) enables a thickness reduction of the CdS buffer layer and increases the open‐circuit voltage. Na supply during 3rd stage CIGS deposition positively impacts the cell performance. Coevaporation of heavy alkali (e.g., RbF) during capping layer deposition mitigates the adverse shunting associated with high Cu contents, yielding highest efficiencies with near‐stoichiometric absorber compositions. Furthermore, optimization of the deposition sequence results in absorbers with a 1 µm wide notch region with nearly constant bandgap minimum. The improved processes result in a record cell efficiency of 20.8% for CIGS on flexible substrate.     

Hole Transporting Bilayers for Efficient Micrometer-Thick Perovskite Solar Cells

Achieving high efficiencies in halide perovskite solar cells with thicknesses >1 µm is necessary for developing perovskite-Si tandem cells based on small pyramidal structures. To achieve this goal, not only is the perovskite layer quality to be optimized but also the properties of the charge-transport layers must be tuned to reduce charge-collection losses. The transport layers provide a non-ohmic resistance that modulates the Fermi-level splitting inside the perovskite absorber. The finite conductivity of the transport layers can lead to losses in the fill factor (FF) and short-circuit current, even at infinite charge-carrier mobility in the absorber layer. These losses notably scale with the absorber layer thickness, which implies that higher-conductivity transport layers are required for thicker perovskite absorbers. One strategy to improve charge collection and thereby FFs in thick inverted perovskite solar cells is to use bilayers of hole-transport layers. In this study, the combination of poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] with self-assembled monolayers provides the best photovoltaic performance in single-junction devices.     

Back Contact Engineering for Increased Performance in Kesterite Solar Cells

The thin‐film photovoltaic absorber Cu₂ZnSn(S,Se)₄ (CZTSSe) holds considerable promise for large scale conversion of sunlight into electricity. CZTSSe is composed of Earth‐abundant elements that exhibit low‐toxicities, but improvements in device efficiency have been hampered by difficulties in increasing open circuit voltages (V_OC) due, at least in part, to disorder induced band tailing. We present a method to increase V_OC through direct modification of the back contact; our approach involves the separation of fully functioning devices from their Mo/glass substrate to reveal the back CZTSSe surface. Formation of a new back contact consisting of a thermally deposited high work function material (MoO₃), together with a higly reflective (Au) capping layer, creates an electrostatic field that drives electrons to the front p‐n junction and leads to a decrease in electron‐hole recombination. Model simulations indicating an increase in V_OC with decreasing absorber thickness are borne out by experiments with devices of varying thicknesses (0.7–2.0 μm). We report V_OC increases of up to 49 mV for a 1 μm thick absorber, with even greater increases up to 61 mV when the back CZTSSe surface is etched with bromine‐methanol.     

Ultrasmall Nanoplatelets: The Ultimate Tuning of Optoelectronic Properties

2D semiconducting nanoplatelets (NPLs) are an emerging class of photoactive materials. They can be used as building blocks in optoelectronic devices thanks to their large absorption coefficient, high carrier mobility, and unique thickness‐dependent optical transitions. The main drawback of NPLs is their large lateral size, which results in unfavorable band energy levels and low quantum yield (QY). Here, ultrasmall lead chalcogenide PbSe_1–x S_x NPLs are prepared, which exhibit an unprecedented QY of ≈60%, the highest ever reported for this structure. The NPLs are applied as light absorber in a photoelectrochemical system, leading to a saturated photocurrent density of ≈5.0 mA cm^?2 (44 mL cm^?2 d^?1), which is a record for NPL‐based photoelectrodes in solar‐driven hydrogen generation. Ultrasmall NPLs hold the potential for breakthrough developments in the field of optically active nanomaterials.     

High‐Performance Planar Perovskite Solar Cells Using Low Temperature,Solution–Combustion‐Based Nickel Oxide Hole Transporting Layer with Efficiency Exceeding 20%

NiO_x hole transporting layer has been extensively studied in optoelectronic devices. In this paper, the low temperature, solution–combustion‐based method is employed to prepare the NiO_x hole transporting layer. The resulting NiO_x thin films show better quality and preferable energy alignment with perovskite thin film compared to high temperature sol–gel‐processed NiO_x. With this, high‐performance perovskite solar cells are fabricated successfully with power conversion efficiency exceeding 20% using a modified two‐step prepared MA_1?yFA_yPbI_3?xCl_x perovskite. This efficiency value is among the highest values for NiO_x‐based devices. Various characterizations and analyses provide evidence of better film quality, enhanced charge transport and extraction, and suppressed charge recombination. Meanwhile, the device exhibits much better device stability compared to sol–gel‐processed NiO_x and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)‐based devices.     

Chemical Consequences of Alkali Inhomogeneity in Cu2ZnSnS4 Thin‐Film Solar Cells

This study offers new insight into the role of Na in Cu₂ZnSnS₄ (CZTS) thin film solar cells by studying samples with a spatially varying alkali distribution. This is achieved by omitting a diffusion barrier between the soda‐lime glass substrate and the Mo back contact, where compositional variations of the glass inherently result in non‐uniform alkali distributions in the CZTS. By correlating light beam induced current (LBIC) maps with secondary ion mass spectrometry composition maps, it is shown that samples containing regions of higher Na concentration (“hot spots”) have corresponding LBIC hot spots on comparable length scales. Samples containing an alkali diffusion barrier have lower LBIC dispersion; thus, LBIC can be used to evaluate non‐uniformity in CZTS devices, where a common cause is Na inhomogeneity. Moreover, it is shown that the Na hot spots are strongly correlated with other compositional variations in the device, including increased Cu in‐diffusion with the underlying MoS₂ layer and decreased diffusion of Cd to the back contact. Neither of these effects are well understood in CZTS devices, and neither have previously been correlated with the presence or absence of Na.     

Tantalum Nitride Electron‐Selective Contact for Crystalline Silicon Solar Cells

Minimizing carrier recombination at contact regions by using carrier‐selective contact materials, instead of heavily doping the silicon, has attracted considerable attention for high‐efficiency, low‐cost crystalline silicon (c‐Si) solar cells. A novel electron‐selective, passivating contact for c‐Si solar cells is presented. Tantalum nitride (TaN _x ) thin films deposited by atomic layer deposition are demonstrated to provide excellent electron‐transporting and hole‐blocking properties to the silicon surface, due to their small conduction band offset and large valence band offset. Thin TaN_x interlayers provide moderate passivation of the silicon surfaces while simultaneously allowing a low contact resistivity to n‐type silicon. A power conversion efficiency (PCE) of over 20% is demonstrated with c‐Si solar cells featuring a simple full‐area electron‐selective TaN_x contact, which significantly improves the fill factor and the open circuit voltage (V_oc) and hence provides the higher PCE. The work opens up the possibility of using metal nitrides, instead of metal oxides, as carrier‐selective contacts or electron transport layers for photovoltaic devices.