Carrier Collection Efficiency Research Articles

Highly Efficient Organic/Silicon Hybrid Solar Cells with a MoO3 Capping Layer

Organic/Si hybrid solar cells have attracted considerable attention for their uncomplicated fabrication process and superior device efficiency, making them a promising candidate for sustainable energy applications. However, the efficient collection and separation of charge carriers at the organic/Si heterojunction interface are primarily hindered by the inadequate work function of poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS). Here, the application of a high-work-function MoO3 film onto the n-Si/PEDOT:PSS surface leads to a notable enhancement in the device’s built-in potential. This enhancement results in the creation of an inversion layer near the n-Si surface and facilitates charge separation at the interface. Simultaneously, it inhibits charge recombination at the heterojunction interface. As a result, the champion PEDOT:PSS/Si solar cell, which incorporates a MoO3 interface layer, demonstrates an efficiency of 16.0% and achieves a high fill factor of 80.8%. These findings provide a straightforward and promising strategy for promoting the collection and transmission of charge carriers at the interface of photovoltaic devices.

Interlayer Charge Transition and Broadband Polarization Photodetection and Imaging Based on In2Se3/ReS2 van der Waals Heterostructure

Abstract2D van der Waal (vdWs) heterostructures present unique optoelectronic characteristics, making them favorable layer structures for constructing promising optoelectronic devices with multifunctional applications. Nevertheless, as a result of significant interface recombination of the photogenerated electron‐hole pairs and the presence of various absorption edges within constituent layers, they are prone to experiencing low carrier collection efficiency. In this work, a combined theoretical and experimental investigation are presented on the In2Se3/ReS2 vdWs heterostructure, aimed at developing high‐performance and broadband photodetector with multifunctionalities. In theoretical investigations, it is observed that, by adjusting the polarization states (+P to −P) in the In2Se3 layer, band alignment can be effectively tuned from type‐I to type‐II, providing a narrow bandgap of ≈0.65 eV, which is beyond that of their individual constituents. As a photodetector, the device shows broadband photoresponse ranging from 532 to 1550 nm with ultrahigh responsivity (99.36 AW−1), detectivity (3.5 × 1013 Jones), and external quantum efficiency (34195%). Additionally, competitive polarization sensitivity across the broad spectrum and imagining capability are observed with In2Se3/ReS2 vdWs heterostructure. This study demonstrates that In2Se3/ReS2 vdWs heterostructure device provides a promising technique for developing high‐performance 2D optoelectronic devices with multifunctionalities.

Covalent Heteroepitaxy of Large‐Area Vertical Hexagonal Boron Nitride for High‐Temperature VUV Photodetectors

AbstractHexagonal boron nitride (h‐BN) is a van der Waals (vdW) ultrawide bandgap semiconductor with high band‐edge absorption coefficient and chemical/thermal resistance, demonstrating great potential for vacuum ultraviolet (VUV) and UV‐C detection. Hitherto, most of their prevailing applications have exploited epitaxial films and multilayers either grown on substrates or transferred, which tend to form energy‐favorable noncovalent vdW epitaxy. Here, an alternative heteroepitaxy of 2‐inch h‐BN is reported with desirable thickness and vertically aligned vdW layers covalently bonded to sapphire, enabled by activating the inert substrate surface using ion impingement during deposition and the dislocation‐mediated epitaxial transition. The fabricated photodetectors allow efficient photon absorption and carrier collection using a simple planar device design, showing excellent VUV/UV‐C detection performance with ultrafast response of 270 ns/60 µs (rise/decay) and remarkable operating stability until 500 °C. This covalent heteroepitaxy of wafer‐scale h‐BN opens new avenues for optoelectronics and electronics significant to harsh environment applications.

Luminescence efficiency and carrier dynamics for InGaAs/GaAs surface quantum dots in coupled heterostructures

InGaAs/GaAs surface quantum dot (SQD) heterostructures have long been viewed as having great potential for realizing environmental gas detection devices. The research has recently been steered into discovering ways to inject carriers into the available SQD energy states to facilitate readable devices. In the present research, carrier injection from buried QDs (BQDs) to SQDs was controlled by changing the interlayer coupling. Photoluminescence (PL) measurements show that, by increasing the stacking period of BQDs, the carrier collection efficiency and subsequently the luminescence intensity for SQDs can be effectively improved. A rate equation simulation of the carrier recombination process is used to quantitatively describe the luminescent quantum efficiency (IQE) for the SQDs, indicating an increase with additional BQD layers due to an increase in carrier injection. The PL spectra along with the rate equation simulations further indicated that for these SQD hybrid structures nonradiative recombination dominates, with Auger recombination becoming significant at high excitation intensities. These results may help to understand the carrier dynamics in coupled SQDs hybrid structures. In addition, they provide a path to manipulating the properties of InGaAs SQDs for the development of gas sensors.

Simultaneous Band Alignment Modulation and Carrier Dynamics Optimization Enable Highest Efficiency in Cd‐Free Sb2Se3 Solar Cells

AbstractAntimony selenide (Sb2Se3) has developed as an eco‐friendly photovoltaic candidate owing to its non‐toxic composition and exceptional optoelectronic properties. However, the toxic and parasitic light‐absorbing CdS are widely used as electron transport layer (ETL) in Sb2Se3 solar cells, which severely limits its development. Herein, an alternative, zinc tin oxide (ZTO) ETL with varying composition‐dependent energy structure is deposited by atomic layer deposition (ALD) technique and used for constructing Cd‐free Sb2Se3 solar cells. It has been found that the ZTO ETL possessing an appropriate Zn/Sn ratio can alter the Sb2Se3/ZTO heterojunction band alignment to an ideal “spike‐like” arrangement. It not only suppresses the accumulation and recombination of charge carriers at the interface, but also effectively enhances carrier transport. In addition, thanks to the formation of passivated Sb2O3 ultra‐thin layer upon ALD process, the non‐radiative recombination within bulk Sb2Se3 can be effectively suppressed, and therefore enhancing carrier lifetime, extraction efficiency, and collection efficiency. Consequently, the as‐fabricated Mo/Sb2Se3/ZTO/ITO/Ag thin‐film solar cell demonstrates an impressive efficiency of 8.63%. This accomplishment establishes it as the most efficient Cd‐free Sb2Se3 solar cell to date, underscoring the significant advantages of incorporating ZTO ETL in the development of Sb2Se3 photovoltaic scenarios.

Cu2ZnSn(S,Se)4 solar cells with over 10% power conversion efficiency enabled by dual passivation strategy

Interfaces quality have always been considered the key factors in the fabrication of efficient Cu2ZnSn(S,Se)4 (CZTSSe) solar cells, and harmful defects at the interface can significantly reduce the performance of the device. Here, we propose a dual passivation strategy by adding Na to the surface of the absorber layer (CZTSSe) to passivate the CZTSSe/CdS interface and treating the buffer layer (CdS) using ultraviolet (UV) irradiation to passivate the CdS/ZnO interface. Due to the Na doping passivation, the absorber surface conductivity increases while the roughness decreases and detrimental defects that can lead to nonradiative recombination are reduced. The power conversion efficiency (PCE) of the cell is improved by about 1 percentage point by Na passivation. The contributions of open-circuit voltage (Voc), short-circuit current density (Jsc), and fill factor (FF) to the improvement of PCE have been quantified as 50.64%, −5.58%, and 54.94%, indicating that Na doping can significantly boost Voc and FF. UV-ozone passivation reduces residual carbon organics in the CdS buffer layer, weakens carrier recombination, allows for more light absorption, and widens the depletion region, which favors efficient carrier collection. The estimated contribution of Voc, Jsc, and FF to the PCE of the device is 8.78%, 119.59%, and −28.37%, respectively, demonstrating that UV-ozone passivation can significantly improve the Jsc of the device. The two passivation strategies complement each other's advantages and achieve a synergistic effect. Our prepared champion device exhibits a PCE of 10.69% and remarkable long-term stability.

Enhancing carrier collection in CsPbBr3 solar cells through crystal orientation and defect passivation

All-inorganic carbon-based CsPbBr3 perovskite solar cells (PSCs) have gained growing interest for their remarkable stability. However, compared to their organic–inorganic hybrid counterparts, there is still substantial room for improving their performance primarily due to the inferior photogenerated carrier collection efficiency. Here, we employ area-dependent transient photocurrent to assess the carrier transit time in CsPbBr3 PSCs, revealing that an extended carrier transit time relative to the lifetime significantly contributes to their low carrier collection efficiency. To address this challenge, we narrow the gap between carrier transit time and lifetime by introducing a dual-functional additive, serving to facilitate both crystallization orientation and defect passivation. Consequently, we achieve enhanced short-circuit current and efficiency in CsPbBr3 PSCs.

Suppressing interface recombination via element diffusion regulation towards high-efficiency Cd-free Cu(In,Ga)Se2 solar cells

Magnetron-sputtered Zn1-xMgxO (ZMO) films suffer from severe elemental diffusion to Cu(In,Ga)Se2 (CIGS), which limits the further improvement of device performance. Herein, we introduced Zn(O,S) (ZOS) as a barrier layer, and we controlled the diffusion of Zn within an appropriate range by adjusting the annealing temperature of ZOS. The results indicate that Zn can occupy copper vacancies (VCu) in CIGS and easily diffuse through VCu. A moderate amount of Zn at the interface acts as a charge compensator, reducing the band tailing effect and promoting the carrier collection efficiency of photovoltaic (PV) devices. However, excessive Zn doping induces additional defects dominated by ZnCu, ZnGa and ZnIn, leading to severe nonradiative recombination. Consequently, the Cd-free CIGS solar cell produced based on these insights exhibited a 49.4-mV reduction in the Voc deficit (Voc,def) as well as a notable increase in the power conversion efficiency (PCE) to 18.0 %. This study is the first to reveal the mechanism of defects caused by Zn diffusion, and these findings provide theoretical support for the study of Cd-free thin-film solar cells.

Optical design and bandgap engineering in ultrathin multiple quantum well solar cell featuring photonic nanocavity

AbstractUltrathin solar cells are efficient and captivating devices with unique technological and scientific features in terms of minimal material consumption, fast fabrication processes, and good compatibility with semi‐transparent applications. Such photovoltaic (PV) technologies can enable effective synergy between optical and electronic confinements with large tuning capabilities of all the optoelectronic characteristics. In this work, the implications of the optical design and the bandgap engineering in ultrathin hydrogenated amorphous Si/Ge multiple quantum well (MQW) solar cells featuring photonic nanocavity are analyzed based on experimental measurements and optoelectronic modelling. By changing the period thicknesses and the positions of QWs inside the deep‐subwavelength nanophotonic resonator, the spatial and spectral distributions of the optical field and the local absorption are strongly affected. This leads to a modulation of the absorption resonance condition, the absorption edge and the resulting photocurrent outputs. Because of quantum confinement effect, the change of MQW configurations with different individual QW periods while keeping similar total thickness of about 20 nm alters both the bandgap energy and the band offset at the QW/barrier heterojunctions. This in turn controls the photovoltage as well as the carrier collection efficiency in solar cells. The highest open circuit voltage and fill factor values are achieved by employing MQW device configuration with 2.5 nm‐thin QWs. A record efficiency above 5.5% is reached for such emerging ultrathin Si/Ge MQW solar cell technology using thinner QWs with sufficient number, because of the optimum trade‐off between all the optoelectronic characteristic outputs. The presented design rules for opaque ultrathin solar cells with quantum‐confined nanostructures integrated in a photonic nanocavity can be generalized for the engineering of relevant multifunctional semitransparent PV devices.

Ultrasensitive Near-Infrared Polarization Photodetectors with Violet Phosphorus/InSe van der Waals Heterostructures.

Near-infrared (NIR) polarization photodetectors with two-dimensional (2D) semiconductors and their van der Waals (vdW) heterostructures have presented great impact for the development of a wide range of technologies, such as in the optoelectronics and communication fields. Nevertheless, the lack of a photogenerated charge carrier at the device's interface leads to a poor charge carrier collection efficiency and a low linear dichroism ratio, hindering the achievement of high-performance optoelectronic devices with multifunctionalities. Herein, we present a type-II violet phosphorus (VP)/InSe vdW heterostructure that is predicted via density functional theory calculation and confirmed by Kelvin probe force microscopy. Benefiting from the type-II band alignment, the VP/InSe vdW heterostructure-based photodetector achieves excellent photodetection performance such as a responsivity (R) of 182.8 A/W, a detectivity (D*) of 7.86 × 1012 Jones, and an external quantum efficiency (EQE) of 11,939% under a 1064 nm photon excitation. Furthermore, the photodetection performance can be enhanced by manipulating the device geometry by inserting a few layers of graphene between the VP and InSe (VP/Gr/InSe). Remarkably, the VP/Gr/InSe vdW heterostructure shows a competitive polarization sensitivity of 2.59 at 1064 nm and can be integrated as an image sensor. This work demonstrates that VP/InSe and VP/Gr/InSe vdW heterostructures will be effective for promising integrated NIR optoelectronics.

Modeling the current-voltage characteristics of Sb2Se3 thin film solar cells through Sah-Noyce-Shockley recombination model

This study investigates the impact of various material parameters, such as film resistivity, the thickness of the absorber layer, uncompensated acceptor density, and carrier lifetime, on the carrier transport and device characteristics of emerging CdS/Sb2Se3 thin-film solar cells. The modeling approach is based on the rigorous Sah-Noyce-Shockley recombination model at the PN-junction, which is based on drift and diffusion collection efficiencies for total current-density calculations. The current-density and voltage have been optimized against the Sb2Se3 thickness and the depletion width at the CdS/Sb2Se3 junction. It has been determined that the lower efficiency of the cell is primarily due to the relatively short electron lifetime and the uncompensated acceptor density, which can widen or narrow the depletion width. The resistivity of the Sb2Se3 film can effectively control the voltage of the cell, however, the carrier lifetime can control this impact even to a higher extent. Therefore, the carrier lifetime and uncompensated acceptor densities are the two interdependent parameters that significantly control the current, voltage, and efficiency of the Sb2Se3 solar cells. This research provides valuable insights for the design and optimization of Sb2Se3 thin-film solar cells shedding light on carrier transport and charge collection mechanism in these emerging materials.

Universal growth of perovskite thin monocrystals from high solute flux for sensitive self-driven X-ray detection

Metal-halide perovskite thin monocrystals featuring efficient carrier collection and transport capabilities are well suited for radiation detectors, yet their growth in a generic, well-controlled manner remains challenging. Here, we reveal that mass transfer is one major limiting factor during solution growth of perovskite thin monocrystals. A general approach is developed to overcome synthetic limitation by using a high solute flux system, in which mass diffusion coefficient is improved from 1.7×10–10 to 5.4×10–10 m2 s–1 by suppressing monomer aggregation. The generality of this approach is validated by the synthesis of 29 types of perovskite thin monocrystals at 40–90 °C with the growth velocity up to 27.2 μm min–1. The as-grown perovskite monocrystals deliver a high X-ray sensitivity of 1.74×105 µC Gy−1 cm−2 without applied bias. The findings regarding limited mass transfer and high-flux crystallization are crucial towards advancing the preparation and application of perovskite thin monocrystals.

Metamaterial Engineering for Superior HgTe cQD Photodetector Performance

AbstractHighly responsive, low noise, and inexpensive photodetectors that operate in the mid‐infrared (MIR) wavelength regime are in high demand for applications ranging from fundamental science to large scale industries. However, simultaneously achieving all this in one device architecture is very challenging. In this work, mercury telluride (HgTe) colloidal quantum dot (cQD) based photodetectors are systematically improved by the introduction of new metamaterial designs. The new designs are found by utilizing simulations. Thereby the structures are optimized to increase the responsivity and simultaneously decrease the noise spectral current density. This is achieved by focusing on improving the photogenerated charge carrier collection efficiency while reducing the active material volume without altering the near unity absorption. A standard metamaterial perfect absorber architecture based on disc resonators is used as a starting point for the optimization process. By optimizing the carrier extraction through contact engineering, resulting in a narrow slot metamaterial, an overall ≈13‐fold responsivity and ≈345‐fold detectivity increase is achieved. The final metamaterial design reaches a responsivity of 16.2 A W−1 and detectivity of 6×108 Jones at a wavelength of 2710 nm. The analysis therefore provides a route to improve the responsivity and noise characteristics of mid‐infrared photodetectors based on cost‐efficient colloidal quantum dots.

Improved carrier collection efficiency in CZTS solar cells by Li‐enhanced liquid‐phase‐assisted grain growth

AbstractThe liquid‐phase‐assisted grain growth (LGG) process is a promising strategy to fabricate large‐grain pure sulfide Cu2ZnSnS4 (CZTS) layers that span the absorber thickness and improve the carrier collection efficiency in photovoltaic devices. Li doping is an effective route to promote such LGG process of Cu2ZnSn(S,Se)4 (CZTSSe) as it can provide liquid Li‐Se phase facilitating the growth of large‐grain CZTSSe. However, the detailed function of the added Li in grain growth has rarely been investigated in both CZTS and CZTSSe, as the reported in situ, and pre‐deposition doping strategies usually suffer from substantial Li losses during the spin‐coating process and/or the high‐temperature sulfurization process. Herein, by monitoring the temperature‐dependent Li loss during the sulfurization process, we demonstrate that a small proportion of the added Li can remain at the CZTS film from the early sulfurization stage and provide Li‐S flux to promote the LGG process. An encouraging efficiency of 10.53%, with a remarkably high short‐circuit current density of 22.6 mA/cm2 and open‐circuit voltage of 0.744 V, is achieved by a significantly enlarged grain size of 3 μm with Li addition. This work could enhance the knowledge of employing Li‐S as flux for growing large‐grain chalcogenide absorbers for high performance devices with better carrier transport.

Long-Range Hot-Carrier Transport in Topologically Connected HgTe Quantum Dots.

The utilization of hot carriers as a means to surpass the Shockley-Queasier limit represents a promising strategy for advancing highly efficient photovoltaic devices. Quantum dots, owing to their discrete energy states and limited multi-phonon cooling process, are regarded as one of the most promising materials. However, in practical implementations, the presence of numerous defects and discontinuities in colloidal quantum dot (CQD) films significantly curtails the transport distance of hot carriers. In this study, the harnessing of excess energies from hot-carriers is successfully demonstrated and a world-record carrier diffusion length of 15µm is observed for the first time in colloidal systems, surpassing existing hot-carrier materials by more than tenfold. The observed phenomenon is attributed to the specifically designed honeycomb-like topological structures in a HgTe CQD superlattice, with its long-range periodicity confirmed by High-Resolution Transmission Electron Microscopy(HR-TEM), Selected Area Electron Diffraction(SAED) patterns, and low-angle X-ray diffraction (XRD). In such a superlattice, nonlocal hot carrier transport is supported by three unique physical properties: the wavelength-independent responsivity, linear output characteristics and microsecond fast photoresponse. These findings underscore the potential of HgTe CQD superlattices as a feasible approach for efficient hot carrier collection, thereby paving the way for practical applications in highly sensitive photodetection and solar energy harvesting.

Multifunctional chemical anchors achieve a boosted fill factor and mitigate ion migration of high-stability perovskite solar cells.

To date, it is urgent to produce perovskite films with comparative or even better morphologies in an open-air environment. Unfortunately, a substantial number of trap states on the grain surface, especially the grain boundaries (GBs) of a perovskite layer, can bring about significant deterioration in the performance of PSCs. Trap-induced carrier recombination directly exerts a detrimental influence on the carrier collection efficiency and electronic properties of a perovskite active film. Herein, 4(5)-iodoimidazole (4II), a small organic molecule agent, was introduced to passivate the surface and bulk traps of the active film, which resulted in a controlled morphology, improved carrier extraction and suppressed ion migration for the devices fabricated in a relatively humid and O2-containing environment. Conductive atomic force microscopy (C-AFM) and Kelvin probe force microscopy (KPFM) measurements were applied to study trap passivation and suppression of ion migration across the GBs of perovskite films. The results manifest that the -CN group preferably bonds with the less-coordinated Pb2+ and the -NH- group favorably forms hydrogen bonds with the uncoordinated I-. As a result, the champion device delivered a significantly boosted power conversion efficiency from 17.22% to 20.95%, with an improved fill factor (FF) from 70.54% to 80.40%, and improved ambient stability of the unencapsulated device. This study may probe research insight into the design of passivators with synergistic effects for morphology control and reduction of carrier recombination loss for equally efficient perovskite photovoltaics fabricated in ambient air.

Carrier mobility in doped Sb<sub>2</sub>Se<sub>3</sub> based on deformation potential theory

Antimony selenide (Sb<sub>2</sub>Se<sub>3</sub>) is an element-rich, cost-effective, and non-toxic material used as an absorber layer in solar cells. The performance of solar cells is significantly influenced by the transport characteristics of charge carriers. However, these characteristics in Sb<sub>2</sub>Se<sub>3</sub> have not been well understood. In this work, through density functional theory and deformation potential theory, we investigate the hole transport properties of pure Sb<sub>2</sub>Se<sub>3</sub> and As-, Bi-doped Sb<sub>2</sub>Se<sub>3</sub>. The incorporation of as element and Bi element does not introduce additional impurity levels within the band gap. However, the band gaps are reduced in both As-Sb<sub>2</sub>Se3 and Bi-Sb<sub>2</sub>Se<sub>3</sub> due to the band shifts of energy levels. This phenomenon is primarily attributed to the interactions between the unoccupied 4p and 6p states of the doping atoms and the unoccupied 4p states of Se atoms, as well as the unoccupied 5p states of Sb atoms. In this study, we calculate and analyze three key parameters affecting mobility: effective mass, deformation potential, and elastic constants. The results indicate that effective mass has the greatest influence on mobility, with Bi-Sb<sub>2</sub>Se<sub>3</sub> exhibiting the highest average mobility. The average effective mass is highest in As-Sb<sub>2</sub>Se<sub>3</sub> and lowest in Bi-Sb<sub>2</sub>Se<sub>3</sub>. The elastic constants of the As- and Bi-doped Sb<sub>2</sub>Se<sub>3</sub> structures show minimal differences compared with that of the intrinsic Sb<sub>2</sub>Se<sub>3</sub> structure. By comparing the intrinsic, As-doped, and Bi-doped Sb<sub>2</sub>Se<sub>3</sub>, it is evident that doping has a minor influence on deformation potential energy along various directions. The study reveals that the hole mobility in Sb<sub>2</sub>Se<sub>3</sub> displays significant anisotropy, with higher mobilities observed in the <i>x</i>-direction and the <i>y</i>-direction than in the <i>z</i>-direction. This discrepancy is attributed to stronger covalent bonding primarily in the <i>x</i>- and <i>y</i>-direction, while in the <i>z</i>-direction weaker van der Waals forces is dominant. The directions with enhanced charge carrier transport capability contribute to efficient transfer and collection of photo-generated charge carriers. Therefore, our research theoretically underscores the significance of controlling the growth of antimony selenide along specific directions.

Cu2O/ZnO heterojunction self-powered photodetector performance regulation

Self-powered photodetectors, requiring no external bias, offer distinct advantages that render them ideal for a broad spectrum of applications. Efficient carrier separation and collection stand as foundational elements in the operation of these photodetectors. In this study, we delve into the refinement of Cu2O/ZnO heterojunction photodetectors. By varying the thickness of the ZnO layer, we controlled the separation and capture of carriers at the heterojunction, thus achieving adjustable photodetector performance. Our experimental findings reveal pronounced performance trends related to different wavelength bands, with particular significance in the ultraviolet and visible exploration. We observe a distinctive pattern marked by an initial performance increase followed by a subsequent decline. This intriguing phenomenon implies that meticulous control over carrier separation and collection within the heterojunction can be realized by fine-tuning the transmission distance, ultimately allowing us to adjust the photodetector’s responsivity.

Interface and Structural Engineering of Cr Doped Zinc Oxide/Graphene Photoanode with Enhanced Photoelectrochemical Water Splitting

The low-cost hydrogen (H2) generation from solar energy is one of the attractive and promising methods for clean and sustainable energy. It is challenging to boost global, renewable H2 energy mission. Until now, no catalytic system has been realized with viable efficiency and stability with reasonable manufacturing cost. Herein, we demonstrate a facile synthesis of chromium doped zinc oxide/graphene (Cr-doped ZnO@Graphene) as multicomponent photoanode using simple, inexpensive hydrothermal method. We investigated that graphene layer beneath ZnO can act in a different way, while salient features of controllable graphene concentration and appropriate Cr doping clearly displayed profound influence on photoelectrochemical water splitting reaction which is due to promoted electron transfer at interface. The detailed computational study was done by density functional theory (DFT) calculations. A photoelectrochemical cell was assembled with optimized photoanode displayed 4-fold increase in photocurrent density as compared to pristine ZnO. The improved PEC performance is attributed to the synergistic effects, where the presence of Cr dopant improves the charge carrier density and enhanced electronic conductivity, and graphene has increased the carrier transport and collection efficiency. Overall, this study provides valuable insights into the development of (Cr-doped ZnO@Graphene) as a highly efficient and stable photoelectrode for practical applications in solar water splitting and renewable energy conversion.

Engineering the Inhomogeneity of Metal-Insulator-Semiconductor Junctions for Photoelectrochemical Methanol Oxidation.

Si-based inhomogeneous metal-insulator-semiconductor (MIS) junctions with a discontinuous metal nanostructure on the Si/insulator layer are expected to be efficient photoelectrodes for solar energy conversion. However, the formation of a metal nanostructure with an optimized arrangement on semiconductors for efficient charge carrier collection is still a big challenge. Herein, we report a method for the in situ formation of an n-Si inhomogeneous MIS junction with well-dispersed metal nanocontacts through a self-assembly process during photoelectrochemical (PEC) methanol oxidation. The photovoltage shows a strong dependence on the inhomogeneity of the n-Si MIS junction, which can be precisely tuned by the applied electrode potential and operation time. The appropriate inhomogeneity of the Schottky junction as well as the high barrier regions induced by the metal oxide/(oxy)hydroxide layer synergistically produces a large photovoltage of 500 mV for the n-Si inhomogeneous MIS junction. Finally, the n-Si-based photoanode is coupled with a CO2-to-formate reaction to realize the production of formate at both electrodes, resulting in a high faradic efficiency (FE) of 86 and 93% for anode and cathode reactions at an operational current of 30 mA/cm2, respectively. These findings provide important insights into the design of highly efficient inhomogeneous MIS junctions through an in situ self-assembly route for solar energy conversion and storage.