Combining electron‐ and hole‐selective materials in one crystalline silicon (Si) solar cell, thereby avoiding any dopants, is not considered for application to photovoltaic industry until only comparable efficiency and stable performance are achievable. Here, it is demonstrated how a conventionally unstable electron‐selective contact (ESC) is optimized with huge boost in stability as well as improved electron transport. With the introduction of a Ti thin film between a‐Si:H( i )/LiF and Al electrode, high‐level passivation ( S eff = 4.6 cm s –1 ) from a‐Si:H( i ) and preferential band alignment ( ρ C = 7.9 mΩ cm 2 ) from low work function stack of LiF/Ti/Al are both stably retained in the newly constructed n ‐Si/a‐Si:H( i )/LiF/Ti/Al ESC. A detailed interfacial elements analysis reveals that the efficiently blocked inward diffusion of Al from electrode by the Ti protecting layer balances transport and recombination losses in general. This excellent electron‐selective properties in combination with large process tolerance that enable remarkable device performance, particularly high efficiencies of 22.12% and 23.61%, respectively, are successfully approached by heterojunction solar cells with dopant‐free ESC and dopant‐free contacts for both polarities.

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 (SiOx/Mg) electron‐selective contact (ESC) design is described. Combining an ultrathin SiOx and a low work function Mg layer, the novel ESC simultaneously yields low recombinative and resistive losses. In addition, deposition of Mg on SiOx relaxes the restriction on the threshold thickness of the SiOx 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/SiOx/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.

Surface nanotexturing with excellent light-trapping property is expected to significantly increase the conversion efficiency of solar cells. However, limited by the serious surface recombination arising from the greatly enlarged surface area, the silicon (Si) nanotexturing-based solar cells cannot yet achieve satisfactory high efficiency, which is more prominent in organic/Si hybrid solar cells (HSCs) where a uniform polymer layer can rarely be conformably coated on nanotextured substrate. Here, the HSCs featuring advanced surface texture of periodic upright nanopyramid (UNP) arrays and hole-conductive conjugated polymers, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), are investigated. The tetramethylammonium hydroxide etching is used to smooth the surface morphologies of the Si-UNPs, leading to reduced surface defect states. The uniform Si-UNPs together with silane chemical-incorporated PEDOT:PSS solution enable the simultaneous realization of excellent broadband light absorption as well as enhanced electrical contact between the textured Si and the conducting polymer. The resulting PEDOT:PSS/Si HSCs textured with UNP arrays show a promising power conversion efficiency of 13.8%, significantly higher than 12.1% of the cells based on the-state-of-the-art surface texture with random pyramids. These results provide a viable route toward shape-controlled nanotexturing-based high-performance organic/Si HSCs.

Research on photovoltaic devices with a high performance-to-cost ratio requires efforts not only on efficiency improvement but also on manufacturing cost reduction. Recently, a record efficiency of 26.6% on crystalline silicon solar cells (SCs) has been achieved by combining the heterojunctions (HJs) with a device structure of interdigitated back contacts. However, the technology that integrates the interdigital p- and n-type amorphous silicon (a-Si:H) layers on the rear surface of the Si substrate is challenging. This issue has motivated researchers to search dopant-free carrier-selective contacts with alternative materials to completely replace doped a-Si:H layers. Transition metal oxides, graphene, and poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), all having high work functions and hole conducting properties, can play the role of hole-selective layers (HSLs). In this review, we focus on the latest advances and the future trends in these HSLs and their applications in silicon HJ SCs. The main issues and challenges encountered are discussed.

Surface-texture with silicon (Si) nanopyramid arrays has been considered as a promising choice for extremely high performance solar cells due to their excellent anti-reflective effects and inherent low parasitic surface areas. However, the current techniques of fabricating Si nanopyramid arrays are always complicated and cost-ineffective. Here, a high throughput nanosphere patterning method is developed to form periodic upright nanopyramid (UNP) arrays in wafer-scale. A direct comparison with the state-of-the-art texture of random pyramids is demonstrated in optical and electronic properties. In combination with the antireflection effect of a SiN_x coating layer, the periodic UNP arrays help to provide a remarkable improvement in short-wavelength response over the random pyramids, attributing to a short-current density gain of 1.35 mA/cm². The advanced texture of periodic UNP arrays provided in this work shows a huge potential to be integrated into the mass production of high-efficiency Si solar cells.

The organic/silicon (Si) hybrid heterojunction solar cells (HHSCs) have attracted considerable attention due to their potential advantages in high efficiency and low cost. However, as a newly arisen photovoltaic device, its current efficiency is still much worse than commercially available Si solar cells. Therefore, a comprehensive and systematical optoelectronic evaluation and loss analysis on this HHSC is therefore highly necessary to fully explore its efficiency potential. Here, a thoroughly optoelectronic simulation is provided on a typical planar polymer poly (3,4-ethylenedioxy thiophene):polystyrenesulfonate (PEDOT:PSS)/Si HHSC. The calculated spectra of reflection and external quantum efficiency (EQE) match well with the experimental results in a full-wavelength range. The losses in current density, which are contributed by both optical losses (i.e., reflection, electrode shield, and parasitic absorption) and electrical recombination (i.e., the bulk and surface recombination), are predicted via carefully addressing the electromagnetic and carrier-transport processes. In addition, the effects of Si doping concentrations and rear surface recombination velocities on the device performance are fully investigated. The results drawn in this study are beneficial to the guidance of designing high-performance PEDOT:PSS/Si HHSCs.

Carrier recombination and light management of the dopant-free silicon/organic heterojunction solar cells (HSCs) based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are the critical factors in developing high-efficiency photovoltaic devices. However, the traditional passivation technologies can hardly provide efficient surface passivation on the front surface of Si. In this study, a photoinduced electric field was induced in a bilayer antireflective coating (ARC) of polydimethylsiloxane (PDMS) and titanium oxide (TiO) films, due to formation of an accumulation layer of negative carriers (O species) under UV (sunlight) illumination. This photoinduced field not only suppressed the silicon surface recombination but also enhanced the built-in potential of HSCs with 84 mV increment. In addition, this photoactive ARC also displayed the outstanding light-trapping capability. The front PEDOT:PSS/Si HSC with the saturated O received a champion PCE of 15.51% under AM 1.5 simulated sunlight illumination. It was clearly demonstrated that the photoinduced electric field was a simple, efficient, and low-cost method for the surface passivation and contributed to achieve a high efficiency when applied in the Si/PEDOT:PSS HSCs.

Recently, silicon single nanowire solar cells (SNSCs) serving as the sustainable self-power sources have been integrated into optoelectronic nanodevices under the driver of technology and economy. However, conventional SNSC cannot provide the minimum energy consumption for the operation of nanodevices due to its low power conversion efficiency (PCE). Here, we propose an innovative approach to combine the n-type silicon nanowires (SiNWs) with p-type poly(3,4-ethylthiophene):poly(styrenesulfonate) (PEDOT:PSS) to form the p + n heterojunction, which shows superior opto-electric performances. Besides, PEDOT:PSS also acts as a natural anti-reflection coating (ARC) with an excellent light-trapping capability, especially in the short-wavelength range. Importantly, the photovoltaic performances of Si/PEDOT:PSS SNSC can be well maintained even in large surface recombination velocity, due to the efficient field-effect passivation of PEDOT:PSS. The minority carrier concentration at outer surface of shallow p + n heterojunction is greatly reduced by the electric field, drastically suppressing the surface recombination compared to the conventional p-i-n homojunction SNSC. Furthermore, larger junction area of p + n heterojunction facilitates the separation of photo-generated charge carriers. These results demonstrate that the Si/PEDOT:PSS SNSC is a promising alternative for micro power application.