Conductive and Stable Magnesium Oxide Electron‐Selective Contacts for Efficient Silicon Solar Cells

A high Schottky barrier (>0.65 eV) for electrons is typically found on lightly doped n‐type crystalline (c‐Si) wafers for a variety of contact metals. This behavior is commonly attributed to the Fermi‐level pinning effect and has hindered the development of n‐type c‐Si solar cells, while its p‐type counterparts have been commercialized for several decades, typically utilizing aluminium alloys in full‐area, and more recently, partial‐area rear contact configurations. Here the authors demonstrate a highly conductive and thermally stable electrode composed of a magnesium oxide/aluminium (MgO_x/Al) contact, achieving moderately low resistivity Ohmic contacts on lightly doped n‐type c‐Si. The electrode, functionalized with nanoscale MgO_x films, significantly enhances the performance of n‐type c‐Si solar cells to a power conversion efficiency of 20%, advancing n‐type c‐Si solar cells with full‐area dopant‐free rear contacts to a point of competitiveness with the standard p‐type architecture. The low thermal budget of the cathode formation, its dopant‐free nature, and the simplicity of the device structure enabled by the MgO_x/Al contact open up new possibilities in designing and fabricating low‐cost optoelectronic devices, including solar cells, thin film transistors, or light emitting diodes.     

Dopant‐Free Partial Rear Contacts Enabling 23% Silicon Solar Cells

Over the past five years, there has been a significant increase in both the intensity of research and the performance of crystalline silicon devices which utilize metal compounds to form carrier‐selective heterocontacts. Such heterocontacts are less fundamentally limited and have the potential for lower costs compared to the current industry dominating heavily doped, directly metalized contacts. A low temperature (≤230 °C), TiO_x/LiF_x/Al electron heterocontact is presented here, which achieves mΩcm² scale contact resistivities ρ_c on lowly doped n‐type substrates. As an extreme demonstration of the potential of this heterocontact, it is trialed in a newly developed, high efficiency n‐type solar cell architecture as a partial rear contact (PRC). Despite only contacting ≈1% of the rear surface area, an efficiency of greater than 23% is achieved, setting a new benchmark for n‐type solar cells featuring undoped PRCs and confirming the unusually low ρ_c of the TiO_x/LiF_x/Al contact. Finally, in contrast to previous versions of the n‐type undoped PRC cell, the performance of this cell is maintained after annealing at 350–400 °C, suggesting its compatibility with conventional surface passivation activation and sintering steps.     

Temperature and Humidity Stable Alkali/Alkaline‐Earth Metal Carbonates as Electron Heterocontacts for Silicon Photovoltaics

Nanometer scale interfacial layers between the metal cathode and the n‐type semiconductor play a critical role in enhancing the transport of charge carriers in and out of optoelectronic devices. Here, a range of nanoscale alkali and alkaline earth metal carbonates (i.e., potassium, rubidium, caesium, calcium, strontium, and barium) are shown to function effectively as electron heterocontacts to lightly doped n‐type crystalline silicon (c‐Si), which is particularly challenging to contact with common metals. These carbonate interlayers are shown to enhance the performance of n‐type c‐Si proof‐of‐concept solar cells up to a power conversion efficiency of ≈19%. Furthermore, these devices are thermally stable up to 350 °C and both the caesium and barium carbonates pass a standard 1000 h damp heat test, with >95% of their initial performance maintained. The temperature and humidity stable electron heterocontacts based on alkali and alkaline earth metal carbonates show a high potential for industrial feasibility and longevity for deployment in the field.     

A Low Resistance Calcium/Reduced Titania Passivated Contact for High Efficiency Crystalline Silicon Solar Cells

Recent advances in the efficiency of crystalline silicon (c‐Si) solar cells have come through the implementation of passivated contacts that simultaneously reduce recombination and resistive losses within the contact structure. In this contribution, low resistivity passivated contacts are demonstrated based on reduced titania (TiO_x) contacted with the low work function metal, calcium (Ca). By using Ca as the overlying metal in the contact structure we are able to achieve a reduction in the contact resistivity of TiO_x passivated contacts of up to two orders of magnitude compared to previously reported data on Al/TiO_x contacts, allowing for the application of the Ca/TiO_x contact to n‐type c‐Si solar cells with partial rear contacts. Implementing this contact structure on the cell level results in a power conversion efficiency of 21.8% where the Ca/TiO_x contact comprises only ≈6% of the rear surface of the solar cell, an increase of 1.5% absolute compared to a similar device fabricated without the TiO_x interlayer.     

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.     

Four‐Terminal Perovskite/Silicon Multijunction Solar Modules

Multijunction solar cells employing perovskite and crystalline‐silicon (c‐Si) light absorbers bear the exciting potential to surpass the efficiency limit of market‐leading single‐junction c‐Si solar cells. However, scaling up this technology and maintaining high efficiency over large areas are challenging as evidenced by the small‐area perovskite/c‐Si multijunction solar cells reported so far. In this work, a scalable four‐terminal multijunction solar module design employing a 4 cm² semitransparent methylammonium lead triiodide perovskite solar module stacked on top of an interdigitated back contact c‐Si solar cell of identical area is demonstrated. With a combination of optimized transparent electrodes and efficient module design, the perovskite/c‐Si multijunction solar modules exhibit power conversion efficiencies of 22.6% on 0.13 cm² and 20.2% on 4 cm² aperture area. Furthermore, a detailed optoelectronic loss analysis along with strategies to enhance the performance is discussed.     

Dual Functional Electron‐Selective Contacts Based on Silicon Oxide/Magnesium: Tailoring Heterointerface Band Structures while Maintaining Surface Passivation

Silicon (Si)‐based dopant‐free heterojunction solar cells (SCs) featuring carrier‐selective contacts (CSCs) have attracted considerable interest due to the extreme simplifications in their device structure and manufacturing procedure. However, these SCs are limited by the unsatisfactory contact properties on both sides of the junction, and their efficiencies are not comparable with those of commercially available Si SCs. In this report, a high‐performance silicon‐oxide/magnesium (SiO_x/Mg) electron‐selective contact (ESC) design is described. Combining an ultrathin SiO_x and a low work function Mg layer, the novel ESC simultaneously yields low recombinative and resistive losses. In addition, deposition of Mg on SiO_x relaxes the restriction on the threshold thickness of the SiO_x for electron tunneling and therefore broadens the optimization space for rear‐sided passivation. Meanwhile, hole‐selective contact with boosted light harvesting and suppressed interfacial recombination is achieved by forming a fully conformal contact between the conducting poly(3,4‐ethylene dioxythiophene): poly(styrenesulfonate) (PEDOT: PSS) and periodic Si pyramid arrays. With the double‐sided carrier‐selective contact designs, PEDOT: PSS/Si/SiO_x/Mg SCs with efficiency of 15% are finally obtained via a totally dopant‐free processing. Subsequent calculations further indicate a pathway for the improvement of these contacts toward an efficiency that is competitive with conventionally diffused pn junction SCs.     

Overcoming Electrode‐Induced Losses in Organic Solar Cells by Tailoring a Quasi‐Ohmic Contact to Fullerenes via Solution‐Processed Alkali Hydroxide Layers

It is shown that the performance of inverted organic solar cells can be significantly improved by facilitating the formation of a quasi‐ohmic contact via solution‐processed alkali hydroxide (AOH) interlayers on top of n‐type metal oxide (aluminum zinc oxide, AZO, and zinc oxide, ZnO) layers. AOHs significantly reduce the work function of metal oxides, and are further proven to effectively passivate defect states in these metal oxides. The interfacial energetics of these electron collecting contacts with a prototypical electron acceptor (C₆₀) are investigated to reveal the presence of a large interface dipole and a new interface state between the Fermi energy and the C₆₀ highest occupied molecular orbital for AOH‐modified AZO contacts. These novel interfacial gap states are a result of ground‐state electron transfer from the metal hydroxide‐functionalized AZO contact to the adsorbed molecules, which are hypothesized to be electronically hybridized with the contact. These interface states tail all the way to the Fermi energy, providing for a highly n‐doped (metal‐like) interfacial molecular layer. Furthermore, the strong “light‐soaking” effect is no longer observed in devices with a AOH interface.     

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).     

Boosting the Performance of WO3/n‐Si Heterostructures for Photoelectrochemical Water Splitting: from the Role of Si to Interface Engineering

Metal oxide/Si heterostructures make up an exciting design route to high‐performance electrodes for photoelectrochemical (PEC) water splitting. By monochromatic light sources, contributions of the individual layers in WO₃/n‐Si heterostructures are untangled. It shows that band bending near the WO₃/n‐Si interface is instrumental in charge separation and transport, and in generating a photovoltage that drives the PEC process. A thin metal layer inserted at the WO₃/n‐Si interface helps in establishing the relation among the band bending depth, the photovoltage, and the PEC activity. This discovery breaks with the dominant Z‐scheme design idea, which focuses on increasing the conductivity of an interface layer to facilitate charge transport, but ignores the potential profile around the interface. Based on the analysis, a high‐work‐function metal is predicted to provide the best interface layer in WO₃/n‐Si heterojunctions. Indeed, the fabricated WO₃/Pt/n‐Si photoelectrodes exhibit a 2 times higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) and a 10 times enhancement at 1.6 V versus RHE compared to WO₃/n‐Si. Here, it is essential that the native SiO₂ layer at the interface between Si and the metal is kept in order to prevent Fermi level pinning in the Schottky contact between the Si and the metal.     

Design and Fabrication of a Precious Metal‐Free Tandem Core–Shell p+n Si/W‐Doped BiVO4 Photoanode for Unassisted Water Splitting

Tandem photoelectrochemical water splitting cells utilizing crystalline Si and metal oxide photoabsorbers are promising for low‐cost solar hydrogen production. This study presents a device design and a scalable fabrication scheme for a tandem heterostructure photoanode: p⁺n black silicon (Si)/SnO₂ interface/W‐doped bismuth vanadate (BiVO₄)/cobalt phosphate (CoPi) catalyst. The black‐Si not only provides a substantial photovoltage of 550 mV, but it also serves as a conductive scaffold to decrease charge transport pathlengths within the W‐doped BiVO₄ shell. When coupled with cobalt phosphide (CoP) nanoparticles as hydrogen evolution catalysts, the device demonstrates spontaneous water splitting without employing any precious metals, achieving an average solar‐to‐hydrogen efficiency of 0.45% over the course of an hour at pH 7. This fabrication scheme offers the modularity to optimize individual cell components, e.g., Si nanowire dimensions and metal oxide film thickness, involving steps that are compatible with fabricating monolithic devices. This design is general in nature and can be readily adapted to novel, higher performance semiconducting materials beyond BiVO₄ as they become available, which will accelerate the process of device realization.     

Light-Harvesting Properties of Embedded Tin Oxide Nanoparticles for Partial Rear Contact Silicon Solar Cells

In this paper, a novel method of preparation and systematic study of application of low-loss tin oxide (SnO₂) nanospheres located at the rear side of crystalline silicon solar cells having partial rear contact have been presented. The improvement in efficiency due to light harvesting through optical scattering of tin oxide nanospheres is significant for thin silicon solar cells. Finite-difference time-domain (FDTD) simulations reveal that embedding of the rear-located nanospheres is necessary for back scattering of light from the rear surface. An analytical electrical model has been developed utilizing the results of optical simulations to estimate the solar cell parameters and efficiency enhancement of solar cells. The model shows that an absolute efficiency enhancement of ～19% can be achieved for 16% efficient 10-μm thin silicon solar cell with partial rear contact. The enhancement is lower (～6%) for thicker (180 μm) partial rear contact cells. Experimentally, SnO₂ nanospheres have been synthesized and applied at the rear side of partial rear contact solar cell as a proof of experiment to validate the potential of this approach. A relative enhancement of short-circuit current by 2.3% and open-circuit voltage by 2.5% has been achieved experimentally for 180-μm silicon solar cells leading to 5.2% higher efficiency with respect to baseline efficiency validating this concept.     

MXene‐Contacted Silicon Solar Cells with 11.5% Efficiency

MXene, a new class of 2D materials, has gained significant attention owing to its attractive electrical conductivity, tunable work function, and metallic nature for wide range of applications. Herein, delaminated few layered Ti₃C₂T_x MXene contacted Si solar cells with a maximum power conversion efficiency (PCE) of ≈11.5% under AM1.5G illumination are demonstrated. The formation of an Ohmic junction of the metallic MXene to n⁺‐Si surface efficiently extracts the photogenerated electrons from n⁺np⁺‐Si, decreases the contact resistance, and suppresses the charge carrier recombination, giving rise to excellent open‐circuit voltage and short‐circuit current density. The rapid thermal annealing process further improves the electrical contact between Ti₃C₂T_x MXene and n⁺‐Si surface by reducing sheet resistance, increasing electrical conductivity, and decreasing cell series resistance, thus leading to a remarkable improvement in fill factor and overall PCE. The work demonstrated here can be extended to other MXene compositions as potential electrodes for developing highly performing solar cells.     

Scalable and Solid‐State Redox Functionalization of Transparent Single‐Walled Carbon Nanotube Films for Highly Efficient and Stable Solar Cells

This study reports a scalable and room‐temperature solid‐state redox functionalization process for single‐walled carbon nanotubes (SWNTs) with instant efficacy and high stability. By drop‐casting/spin‐coating CuCl₂/Cu(OH)₂ colloidal ethanol solution onto SWNT films, the sheet resistance of the SWNT films achieves 69.4 Ω sq^?1 at 90% transparency without noticeable increase for more than 12 months. The charge transfer mechanism between the redox and the SWNTs is revealed by Raman and X‐ray photoelectron spectroscopies. The SWNT/silicon solar cells are utilized as a benchmark to evaluate the effectiveness of the redox functionalization process and its compatibility for device integration. The power conversion efficiency of the SWNT/Si solar cell increases by 115% after redox functionalization, reaching the value of 14.09% without degradation in the ambient for over 12 months. Temperature‐dependent operation characteristics of the redox functionalized SWNT/Si solar cells demonstrate that the Fermi level unpinning and enhanced tunneling of the charge carriers contribute to the significant improvement of the photovoltage and fill factor. The CuCl₂/Cu(OH)₂ redox also serves as an antireflection layer, resulting in a 20% increase of the photocurrent. The proposed redox functionalized SWNTs are promising as multifunctional transparent conductive films for wide‐range solar cell applications.     

Doping‐Free Asymmetrical Silicon Heterocontact Achieved by Integrating Conjugated Molecules for High Efficient Solar Cell

Organic conjugated molecule/silicon (Si) heterojunction has been widely investigated to build up an asymmetrical heterocontact for efficient photovoltaics. However, it is still unclear how the organic molecular structures can affect their electronic coupling interaction with Si. Here, two widely explored electron acceptors of poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (N2200) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) are used to build up asymmetrical Si heterocontact to investigate their electronic coupling interaction. It is found that PCBM displays different electronic coupling with Si from N2200, which is ascribed to their various physical distance with Si based on a systematic and detailed density functional theory calculation. Organic layer incorporation not only suppresses the surface charge recombination velocity but also leads to an Ohmic contact between Si and Al. Therefore, a doping‐free organic/Si heterojunction photovoltaic with a power conversion efficiency of 14.9% is achieved with PCBM layer. This work discloses a key factor affecting organic/Si electronic coupling interaction, which helps build up high quality Si heterocontact for solar cells and other optoelectronic devices. Furthermore, the simplified heterocontact achieved by a low temperature, solution processed, and lithography‐free steps has a dramatic improvement on conventional diffusion doped‐silicon one at high temperature.     

Conductive Hole‐Selective Passivating Contacts for Crystalline Silicon Solar Cells

Defect state passivation and conductivity of materials are always in opposition; thus, it is unlikely for one material to possess both excellent carrier transport and defect state passivation simultaneously. As a result, the use of partial passivation and local contact strategies are required for silicon solar cells, which leads to fabrication processes with technical complexities. Thus, one material that possesses both a good passivation and conductivity is highly desirable in silicon photovoltaic (PV) cells. In this work, a passivation‐conductivity phase‐like diagram is presented and a conductive‐passivating‐carrier‐selective contact is achieved using PEDOT:Nafion composite thin films. A power conversion efficiency of 18.8% is reported for an industrial multicrystalline silicon solar cell with a back PEDOT:Nafion contact, demonstrating a solution‐processed organic passivating contact concept. This concept has the potential advantages of omitting the use of conventional dielectric passivation materials deposited by costly high‐vacuum equipment, energy‐intensive high‐temperature processes, and complex laser opening steps. This work also contributes an effective back‐surface field scheme and a new hole‐selective contact for p‐type and n‐type silicon solar cells, respectively, both for research purposes and as a low‐cost surface engineering strategy for future Si‐based PV technologies.     

Self‐Doped,n‐Type Perylene Diimide Derivatives as Electron Transporting Layers for High‐Efficiency Polymer Solar Cells

Perylene diimide (PDI) with high electron affinities are promising candidates for applications in polymer solar cells (PSCs). In addition, the strength of π‐deficient backbones and end‐groups in an n‐type self‐dopable system strongly affects the formed end‐group‐induced electronic interactions. Herein, a series of amine/ammonium functionalized PDIs with excellent alcohol solubility are synthesized and employed as electron transporting layers (ETLs) in PSCs. The electron transfer properties of the resulting PDIs are dramatically tuned by different end‐groups and π‐deficient backbones. Notably, electron transfer is observed directly in solution in self‐doped PDIs for the first time. A significantly enhanced power conversion efficiency of 10.06% is achieved, when applying the PDIs as ETLs in PTB7‐Th:PC₇₁BM‐based PSCs. These results demonstrate the potential of n‐type organic semiconductors with stable n‐type doping capability and facile solution processibility for future applications of energy transition devices.     

Achieving High Open‐Circuit Voltages up to 1.57 V in Hole‐Transport‐Material‐Free MAPbBr3 Solar Cells with Carbon Electrodes

An open‐circuit voltage (V_oc) of 1.57 V under simulated AM1.5 sunlight in planar MAPbBr₃ solar cells with carbon (graphite) electrodes is obtained. The hole‐transport‐material‐free MAPbBr₃ solar cells with the normal architecture (FTO/TiO₂/MAPbBr₃/carbon) show little hysteresis during current–voltage sweep under simulated AM1.5 sunlight. A solar‐to‐electricity power conversion efficiency of 8.70% is achieved with the champion device. Accordingly, it is proposed that the carbon electrodes are effective to extract photogenerated holes in MAPbBr₃ solar cells, and the industry‐applicable carbon electrodes will not limit the performance of bromide‐based perovskite solar cells. Based on the analysis of the band alignment, it is found that the voltage (energy) loss across the interface between MAPbBr₃ and carbon is very small compared to the offset between the valence band maximum of MAPbBr₃ and the work function of graphite. This finding implies either Fermi level pinning or highly doped region inside MAPbBr₃ layer exists. The band‐edge electroluminescence spectra of MAPbBr₃ from the solar cells further support no back‐transfer pathways of electrons across the MAPbBr₃/TiO₂ interface.     

High‐Efficiency Polymer Homo‐Tandem Solar Cells with Carbon Quantum‐Dot‐Doped Tunnel Junction Intermediate Layer

The tunnel junction (TJ) intermediate connection layer (ICL), which is the most critical component for high‐efficient tandem solar cell, generally consists of hole conducting layer and polyethyleneimine (PEI) polyelectrolyte. However, because of the nonconducting feature of pristine PEI, photocurrent is open‐restricted in ICL even with a little thick PEI layer. Here, high‐efficiency homo‐tandem solar cells are demonstrated with enhanced efficiency by introducing carbon quantum dot (CQD)‐doped PEI on TJ–ICL. The CQD‐doped PEI provides substantial dynamic advantages in the operation of both single‐junction solar cells and homo‐tandem solar cells. The inclusion of CQDs in the PEI layer leads to improved electron extraction property in single‐junction solar cells and better series connection in tandem solar cells. The highest efficient solar cell with CQD‐doped PEI layer in between indium tin oxide (ITO) and photoactive layer exhibits a maximum power conversion efficiency (PCE) of 9.49%, which represents a value nearly 10% higher than those of solar cells with pristine PEI layer. In the case of tandem solar cells, the highest performing tandem solar cell fabricated with C‐dot‐doped PEI layer in ICL yields a PCE of 12.13%; this value represents an ≈15% increase in the efficiency compared with tandem solar cells with a pristine PEI layer.     

Ti3C2Tx (MXene)‐Silicon Heterojunction for Efficient Photovoltaic Cells

A novel type of solar cell has been developed based on charge separation at the heterojunction formed by a transparent conducting MXene electrode and an n‐type silicon (n‐Si) wafer. A thin layer of the native silicon dioxide plays an important role in suppressing the recombination of charge carriers. A two‐step chemical treatment can increase the device efficiency by about 40%. Promisingly, an average power conversion efficiency of over 10% under simulated full sunlight is achieved for this novel class of solar cell with the application of an antireflection layer. The efficiencies of these novel solar cells based on a MXene‐Si heterojunction achieved in this work point to great promise in emerging photovoltaic technology. In addition to their high efficiency, the excellent reproducibility of such devices establishes a solid base for possible future commercialization.