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.     

Lithium Fluoride Based Electron Contacts for High Efficiency n‐Type Crystalline Silicon Solar Cells

Low‐resistance contact to lightly doped n‐type crystalline silicon (c‐Si) has long been recognized as technologically challenging due to the pervasive Fermi‐level pinning effect. This has hindered the development of certain devices such as n‐type c‐Si solar cells made with partial rear contacts (PRC) directly to the lowly doped c‐Si wafer. Here, a simple and robust process is demonstrated for achieving mΩ cm² scale contact resistivities on lightly doped n‐type c‐Si via a lithium fluoride/aluminum contact. The realization of this low‐resistance contact enables the fabrication of a first‐of‐its‐kind high‐efficiency n‐type PRC solar cell. The electron contact of this cell is made to less than 1% of the rear surface area, reducing the impact of contact recombination and optical losses, permitting a power conversion efficiency of greater than 20% in the initial proof‐of‐concept stage. The implementation of the LiF_x/Al contact mitigates the need for the costly high‐temperature phosphorus diffusion, typically implemented in such a cell design to nullify the issue of Fermi level pinning at the electron contact. The timing of this demonstration is significant, given the ongoing transition from p‐type to n‐type c‐Si solar cell architectures, together with the increased adoption of advanced PRC device structures within the c‐Si photovoltaic industry.     

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.     

Rationalizing the Molecular Design of Hole‐Selective Contacts to Improve Charge Extraction in Perovskite Solar Cells

Two new hole selective materials (HSMs) based on dangling methylsulfanyl groups connected to the C‐9 position of the fluorene core are synthesized and applied in perovskite solar cells. Being structurally similar to a half of Spiro‐OMeTAD molecule, these HSMs (referred as FS and DFS) share similar redox potentials but are endowed with slightly higher hole mobility, due to the planarity and large extension of their structure. Competitive power conversion efficiency (up to 18.6%) is achieved by using the new HSMs in suitable perovskite solar cells. Time‐resolved photoluminescence decay measurements and electrochemical impedance spectroscopy show more efficient charge extraction at the HSM/perovskite interface with respect to Spiro‐OMeTAD, which is reflected in higher photocurrents exhibited by DFS/FS‐integrated perovskite solar cells. Density functional theory simulations reveal that the interactions of methylammonium with methylsulfanyl groups in DFS/FS strengthen their electrostatic attraction with the perovskite surface, providing an additional path for hole extraction compared to the sole presence of methoxy groups in Spiro‐OMeTAD. Importantly, the low‐cost synthesis of FS makes it significantly attractive for the future commercialization of perovskite solar cells.     

A Dopant‐Free Polymeric Hole‐Transporting Material Enabled High Fill Factor Over 81% for Highly Efficient Perovskite Solar Cells

Although perovskite solar cells (PVSCs) have achieved rapid progress in the past few years, most of the high‐performance device results are based on the doped small molecule hole‐transporting material (HTM), spiro‐OMeTAD, which affects their long‐term stability. In addition, some defects from under‐coordinated Pb atoms on the surface of perovskite films can also result in nonradiative recombination to affect device performance. To alleviate these problems, a dopant‐free HTM based on a donor‐acceptor polymer, PBT1‐C, synthesized from the copolymerization between the benzodithiophene and 1,3‐bis(4‐(2‐ethylhexyl)thiophen‐2‐yl)‐5,7‐bis(2‐alkyl)benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione units is introduced. PBT1‐C not only possesses excellent hole mobility, but is also able to passivate the surface traps of the perovskite films. The derived PVSC shows a high power conversion efficiency of 19.06% with a very high fill factor of 81.22%, which is the highest reported for dopant‐free polymeric HTMs. The results from photoluminescence and trap density of states measurements validate that PBT1‐C can effectively passivate both surface and grain boundary traps of the perovskite.     

Efficient Silicon Solar Cells through Organic Self-Assembled Monolayers as Electron Selective Contacts

Effective charge carrier-selective contacts are a crucial component of high-performance crystalline silicon (c-Si) solar cells. Organic materials deposited via self-assembly on the c-Si surface are promising candidates for simplified, scalable, and cost-effective processing of charge extraction layers. This study investigates the application of nPACz self-assembled monolayers (SAMs), based on carbazole and phosphonic acid groups, where n (= 2, 4, or 6) is the aliphatic chain length, to facilitate electron extraction in c-Si solar cells by tuning the work function of aluminum (Al) at the rear contact. So far, these SAM molecules are mainly applied as the hole-selective layer in state-of-the-art perovskite and organic solar cells, via anchoring on a metal oxide electrode. Here, by inserting 2PACz between amorphous silicon passivated c-Si and Al, an electron-selective contact with a contact resistivity of 65 mΩ cm² is achieved and a power conversion efficiency of 21.4% with an open-circuit voltage of 725 mV and a fill factor of 79.2% is demonstrated. Although the 2PACz displays some instability in this study, its initial performance is comparable to those achieved with conventionally used n-type amorphous silicon. This study highlights the potential of solution-processable organic SAMs in forming carrier-selective contacts for c-Si heterojunction solar cells.     

Carbon Nanotube‐Silicon Solar Cells

Due to the high cost of silicon photovoltaics there is currently great interest in finding alternative semiconductor materials for light harvesting devices. Single‐walled carbon nanotubes are an allotrope of carbon with unique electrical and optical properties and are promising as future photovoltaic materials. It is thus important to investigate the methods of exploiting their properties in photovoltaic devices. In addition to already extensive research using carbon nanotubes in organic photovoltaics and photoelectrochemical cells, another way to do this is to combine them with a relatively well understood model semiconductor such as silicon. Nanotube‐silicon heterojunction solar cells are a recent photovoltaic architecture with demonstrated power conversion efficiencies of up to ～14% that may in part exploit the photoactivity of carbon nanotubes.     

Multifunctional Effect of p‐Doping,Antireflection, and Encapsulation by Polymeric Acid for High Efficiency and Stable Carbon Nanotube‐Based Silicon Solar Cells

Silicon solar cells among different types of solar energy harvesters have entered the commercial market owing to their high power conversion efficiency and stability. By replacing the electrode and the p‐type layer by a single layer of carbon nanotubes, the device can be further simplified. This greatly augments the attractiveness of silicon solar cells in the light of raw material shortages and the solar payback period, as well as lowering the fabrication costs. However, carbon nanotube‐based silicon solar cells still lack device efficiency and stability. These can be improved by chemical doping, antireflection coating, and encapsulation. In this work, the multifunctional effects of p‐doping, antireflection, and encapsulation are observed simultaneously, by applying a polymeric acid. This method increases the power conversion efficiency of single‐walled carbon nanotube‐based silicon solar cells from 9.5% to 14.4% and leads to unprecedented device stability of more than 120 d under severe conditions. In addition, the polymeric acid‐applied carbon nanotube‐based silicon solar cells show excellent chemical and mechanical robustness. The obtained stable efficiency stands the highest among the reported carbon nanotube‐based silicon solar cells.     

Di‐Spiro‐Based Hole‐Transporting Materials for Highly Efficient Perovskite Solar Cells

Hole‐transporting materials (HTMs) are essential for enabling highly efficient perovskite solar cells (PVSCs) to extract and transport the hole carriers. Among numerous HTMs that are studied so far, the single‐spiro‐based compounds are the most frequently used HTMs for achieving highly efficient PVSCs. In fact, all the new spiro‐based HTMs reported so far that render PVSCs over 20% are based on spiro[fluorene‐9,9′‐xanthene] or spiro [cyclopenta [2,1‐b:3,4b′]dithiophene‐4,9′‐fluorene] cores; therefore, there is a need to diversify the design of their structures for further improving their function and performance. In addition, the fundamental understanding of structure–performance relationships for the spiro‐based HTMs is still lagging, for example, how molecular configuration, spiro numbers, and heteroatoms in spiro‐rings impact the efficacy of HTMs. To address these needs, two novel H‐shaped HTMs, G1 and G2 based on the di‐spiro‐rings as the cores are designed and synthesized. The combined good film‐forming properties, better interactions with perovskite, slightly deeper highest occupied molecular orbital, higher mobility and conductivity, as well as more efficient charge transfer for G2 help devices reach a very impressive power conversion efficiency of 20.2% and good stability. This is the first report of demonstrating the feasibility of using di‐spiro‐based HTMs for highly efficient PVSCs.     

Solution‐Based Silicon in Thin‐Film Solar Cells

Solution‐based semiconductors give rise to the next generation of thin‐film electronics. Solution‐based silicon as a starting material is of particular interest because of its favorable properties, which are already vastly used in conventional electronics. Here, the application of a silicon precursor based on neopentasilane for the preparation of thin‐film solar cells is reported for the first time, and, for the first time, a performance similar to conventional fabrication methods is demonstrated. Because three different functional layers, n‐type contact layer, intrinsic absorber, and p‐type contact layer, have to be stacked on top of each other, such a device is a very demanding benchmark test of performance of solution‐based semiconductors. Complete amorphous silicon n‐i‐p solar cells with an efficiency of 3.5% are demonstrated, which significantly exceeds previously reported values.     

Recent Progress on Hole‐Transporting Materials for Emerging Organometal Halide Perovskite Solar Cells

In less than three years, the photovoltaic community has witnessed a rapid emergence of a new class of solid‐state heterojunction solar cells based on solution‐processable organometal halide perovskite absorbers. The energy conversion efficiency of solid‐state perovskite solar cells (PSCs) has been quickly increased to a certified value of 20.1% by the end of 2014 because of their unique characteristics, such as a broad spectral absorption range, large absorption coefficient, high charge carrier mobility and diffusion length. Here, the focus is specifically on recent developments of hole‐transporting materials (HTMs) in PSCs, which are essential components for achieving high solar cell efficiencies. Some fundamentals with regard to PSCs are first presented, including the history of PSCs, device architectures and general operational principles of PSCs as well as various techniques developed for the fabrications of uniform and dense perovskite complexes. A broad range of the state‐of‐the‐art HTMs being used in PSCs are then discussed in detail. Finally, an outlook on the design of more efficient HTMs for highly efficient PSCs is addressed.     

Overcoming Efficiency Limitations of SnS‐Based Solar Cells

Thin‐film solar cells are made by vapor deposition of Earth‐abundant materials: tin, zinc, oxygen and sulfur. These solar cells had previously achieved an efficiency of about 2%, less than 1/10 of their theoretical potential. Loss mechanisms are systematically investigated and mitigated in solar cells based on p‐type tin monosulfide, SnS, absorber layers combined with n‐type zinc oxysulfide, Zn(O,S) layers that selectively transmit electrons, but block holes. Recombination at grain boundaries is reduced by annealing the SnS films in H₂S to form larger grains with fewer grain boundaries. Recombination near the p‐SnS/n‐Zn(O,S) junction is reduced by inserting a few monolayers of SnO₂ between these layers. Recombination at the junction is also reduced by adjusting the conduction band offset by tuning the composition of the Zn(O,S), and by reducing its free electron concentration with nitrogen doping. The resulting cells have an efficiency over 4.4%, which is more than twice as large as the highest efficiency obtained previously by solar cells using SnS absorber layers.     

Spontaneous Interface Ion Exchange: Passivating Surface Defects of Perovskite Solar Cells with Enhanced Photovoltage

Interface engineering is of great concern in photovoltaic devices. For the solution‐processed perovskite solar cells, the modification of the bottom surface of the perovskite layer is a challenge due to solvent incompatibility. Herein, a Cl‐containing tin‐based electron transport layer; SnO_x‐Cl, is designed to realize an in situ, spontaneous ion‐exchange reaction at the interface of SnO_x‐Cl/MAPbI₃. The interfacial ion rearrangement not only effectively passivates the physical contact defects, but, at the same time, the diffusion of Cl ions in the perovskite film also causes longitudinal grain growth and further reduces the grain boundary density. As a result, an efficiency of 20.32% is achieved with an extremely high open‐circuit voltage of 1.19 V. This versatile design of the underlying carrier transport layer provides a new way to improve the performance of perovskite solar cells and other optoelectronic devices.     

High‐Efficiency Large‐Area Carbon Nanotube‐Silicon Solar Cells

Currently studied carbon nanotube‐silicon (CNT‐Si) solar cells are based on relatively small active areas (typically <0.15 cm²); increasing the active area generally leads to reduced power conversion efficiencies. This study reports CNT‐Si solar cells with active areas of more than 2 cm² for single cells, yet still achieving cell efficiencies of about 10%, which is the first time for CNT‐Si solar cells with an active area more than 1 cm² to reach the level for real applications. In this work, a controlled number of flattened highly conductive CNT strips is added, in simple arrangement, to form a CNT‐Si solar cell with CNT strips in which the middle film makes heterojunctions with Si while the top strips act as self‐similar top electrodes, like conventional metal grids. The CNT strips, directly condensed from as‐grown CNT films, not only improve the CNT‐Si junctions, but also enhance the conductivity of top electrodes without introducing contact barrier when the CNT strips are added onto the film. This property may facilitate the development of large‐area high‐performance CNT or graphene‐Si solar cells.