Sb2Se3 Films Research Articles

Rapid Thermal-Driven Crystal Growth and Defect Suppression in Antimony Selenide Thin Film for Efficient Solar Cells.

Antimony selenide (Sb2Se3) has demonstrated considerable potential and advancement as a light-absorbing material for thin-film solar cells owing to its exceptional optoelectronic characteristics. However, challenges persist in the crystal growth, particularly regarding the nucleation mechanism during pre-selenization process for Sb2Se3. The defects originating from this process significantly impact the quality of the absorber layer, leading to the degradation in the power conversion efficiency (PCE) of the device. Herein, the evolution of pre-selenization using rapid thermal processing (RTP) on the crystallization quality of Sb2Se3 film is systematically investigated. By optimizing the initial nucleation process during pre-selenization, resulting in a reduction of grain boundaries and nucleation centers, the Sb2Se3 thin films demonstrate enhanced crystallinity and pinholes-free morphology. It is found that the improved quality of the grain interior and interfaces of the Sb2Se3 absorber can mitigate intrinsic defects within the bulk layer, and passivate interfacial defect recombination. As a result, the short circuit current density (JSC) is elevated to 28.97mA cm-2, and a competitive efficiency of 9.03% is achieved in Sb2Se3 device. This study provides comprehensive insight into the process of crystal growth and the mechanism for defect suppression, which holds guiding significance for advancing photovoltaic performance.

Suppressing Se Vacancies in Sb2Se3 Photocathode by In Situ Annealing with Moderate Se Vapor Pressure for Efficient Photoelectrochemical Water Splitting.

Sb2Se3 emerges as a promising material for solar energy conversion devices. Unfortunately, the common deep-level defect VSe (selenium vacancy) in Sb2Se3 results in a low solar conversion efficiency. The post selenization process has been widely adopted for suppressing VSe. However, the effect of selenization on suppressing VSe is often compromised and even more VSe are induced due to defect-correlation. Herein, high-quality Sb2Se3 films are prepared using an unconventional selenization process, with precisely regulating in situ annealing Se vapor pressure. It is found that moderate Se vapor pressure annealing can efficiently suppress VSe by overcoming defect-correlation, as well as promotes grain growth and forms a better heterojunction band alignment. Consequently, the Sb2Se3 photocathode shows a high-level photocurrent of 19.5 mA cm-2 at 0 VRHE, an onset potential of 0.40 VRHE and a half-cell solar-to-hydrogen conversion efficiency of 1.9%, owing to the inhibited charge recombination, excellent charge transport and interface charge extraction. This work provides a significant insight to suppress deep-level defect VSe by adjusting Se vapor pressure for efficient Sb2Se3 photocathode.

Investigation of thermally induced surface composition and morphology variation of magnetron sputtered Sb2Se3 absorber layer for thin film solar cells

One of the most promising semiconductor materials for the development of sustainable thin-film solar cell technology is antimony selenide (Sb2Se3). Its excellent optical and electrical properties have drawn attention lately for potential application in thin-film solar cells. In this study, Sb2Se3 films deposited using the direct current (DC) magnetron sputtering technique have been subjected to a post-annealing process without an extra selenium supply at temperatures between 150 and 450 °C. Without an extra selenium supply, the impact of post-annealing temperature on the surface composition as well as the physical properties of the fabricated films was investigated. The overall evaluations revealed that the post-annealing temperature is highly efficient in altering the physical properties of the Sb2Se3 absorber thin films. We further observed that the post-annealing process improved the crystallization and the heat treatment temperature quite affected preferential orientation. The surface morphology of films exhibited structural deformation at high post-annealing temperatures (> 350 °C). According to optical and electrical characterizations, respectively, the optical energy gap and the resistivity of Sb2Se3 films reduced with an increment in the post-annealing temperature. Based on the XPS result, the variation in temperature of post-annealing led to a change in the surface composition of the films. The findings on the growth of Sb2Se3 thin films indicate the existence of an intermediate growth temperature that permits the growth of Sb2Se3 films to be optimized. The study’s conclusions can serve as a guide to the growth of Sb2Se3 thin films with the desired crystallinity, surface morphology, and composition for thin film solar cell applications.

Study on the effect of annealing temperature on the optical characteristics and microstructure of Sb2Se3 thin films

To achieve high conversion efficiency in Sb2Se3 thin films, the effects of different annealing temperatures on the optical properties and microstructure were investigated. The experiment shows that annealing improves Sb2Se3 films' refractive index, absorptivity, and reduces the optical band gap. The first-principle theoretical analysis reveals that defects in the films such as SbSe2, SbSe3, VSe2, and VSe3 significantly affect their optical band gap. Based on the XRD (X-ray diffraction) patterns, the half-height widths, average grain sizes, microstrains and dislocation densities of the diffraction peaks have been calculated. The results show that the optimal annealing temperature is 325 °C. Finally, EDS (Energy Dispersive Spectrometer) and Raman spectroscopy were used to explain the reasons for the changes in the optical properties and internal structure of the film with the annealing temperature from the perspectives of the changes in the film components and the bonding properties between the atoms.

Efficiency improvement of antimony selenide solar cells based on S-doped SnO2 buffer layer

Antimony Selenide (Sb2Se3) exhibits potential as a solar energy material owing to its optimal bandgap, lack of toxicity, and abundance of earth abundant elements. Currently, cadmium sulfide (CdS) serves as the predominant buffer layer for Sb2Se3 solar cells. However, the use of CdS hinders environmentally friendly advancement due to the toxic properties of the element cadmium. Hence, the quest for non-toxic buffer layers poses a significant challenge to the further advancement of Sb2Se3 solar cells. In prior research, tin oxide (SnO2) has been explored as a buffer layer. Nonetheless, the efficiency of SnO2/Sb2Se3 solar cells was hampered by the rough surface of SnO2 films and the poor crystallinity of Sb2Se3 films. In this investigation, we enhanced device efficiency by improving the uniformity of the SnO2 surface and enhancing the crystallinity of Sb2Se3 through spin-coating sulfur (S) onto the SnO2 film. Detailed examinations were conducted on the structure, optical, and electrical properties of the respective SnO2 and Sb2Se3 thin films. Ultimately, an efficiency of 3.38% was achieved using the spin-coated S:SnO2 film, marking an 85% enhancement compared to the baseline device.

A novel Se-diffused selenization strategy to suppress bulk and interfacial defects in Sb2Se3 thin film solar cell

In recent years, vacuum-based deposition of antimony selenide (Sb2Se3) thin films has garnered significant attention owing to its easy and impurity-free fabrication, along with exceptional power conversion efficiency (PCE). However, the necessary post-selenization process comes with a shortcoming of instigating buried Sb2Se3/molybdenum (Mo) back-contact interface defects. This study introduces a novel Se-diffusion post-selenization technique to precisely regulate the selenium reaction atmosphere, preventing void formation on the Sb2Se3 thin film surface and maintaining film quality for enhanced device efficiency. An optimized selenization condition with a precise Se precursor film thickness led to obtaining highly crystalline, preferentially (hk1) oriented, and large-grained Sb2Se3 films. Furthermore, a meticulous Se diffusion in Sb2Se3 film reduced the inevitable MoSe2 layer thickness at the Mo surface, thereby enhancing the quality of the back contact interface. The Sb2Se3 solar cell that was selenized to optimal level showed significant enhancements, raising the fill factor from 40.06 % to 45.12 % and improving the device efficiency from 2.89 % to 3.57 %. Our newly developed selenization strategy establishes a successful approach to regulate the Sb2Se3 film quality by addressing a crucial challenge in improving the efficiency of antimony chalcogenide solar cells.

Selenization-induced [001]-oriented Sb2Se3 film formation and its photo-sensing characteristics

Antimony selenide (Sb2Se3) is emerging as a promising material for optoelectronic applications owing to its exceptional properties. Achieving c-axis oriented [001] Sb2Se3 films, which is crucial for optimizing charge carrier transport has consistently been challenging. In this work, a facile route involving reactive selenization of antimony films deposited on glass substrates via thermal evaporation was employed to obtain [001] oriented Sb2Se3 thin films. The resultant films were comprehensively characterized using X-ray diffraction, field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy to confirm phase purity and compositional homogeneity, elucidating the role of selenization temperature in the formation of Sb2Se3 through this method. XPS analysis was carried out to confirm the oxidation states of Sb and Se. Optical analysis revealed a high absorption coefficient of ∼1.75 × 105 cm−1 with the desired direct band gap values in the range of 1.23 eV–1.20 eV. All these favourable properties, steered to observe a photocurrent of 143 nA at a 5V applied bias in 375°C selenized films under AM1.5 G illumination conditions. An n-Si/Sb2Se3 heterojunction was fabricated and a photocurrent of 2.8 μA was observed with responsivity and detectivity values of 8.18 × 10−5 A/W and 4.26 × 109 Jones respectively at zero applied bias and AM1.5 illumination conditions, showing the favourable prospects of Sb2Se3 thin films prepared via the selenization of antimony films in optoelectronic applications.

Crystalline Antimony Selenide Thin Films for Optoelectronics through Photonic Curing.

Thermal annealing is the most common postdeposition technique used to crystallize antimony selenide (Sb2Se3) thin films. However, due to slow processing speeds and a high energy cost, it is incompatible with the upscaling and commercialization of Sb2Se3 for future photovoltaics. Herein, for the first time, a fast-annealing technique that uses millisecond light pulses to deliver energy to the sample is adapted to cure thermally evaporated Sb2Se3 films. This study demonstrates how photonic curing (PC) conditions affect the outcome of Sb2Se3 phase conversion from amorphous to crystalline by evaluating the films' crystalline, morphological, and optical properties. We show that Sb2Se3 is readily converted under a variety of different conditions, but the zone where suitable films for optoelectronic applications are obtained is a small region of the parameter space. Sb2Se3 annealing with short pulses (<3 ms) shows significant damage to the sample, while using longer pulses (>5 ms) and a 4-5 J cm-2 radiant energy produces (211)- and (221)-oriented crystalline Sb2Se3 with minimal to no damage to the sample. A proof-of-concept photonically cured Sb2Se3 photovoltaic device is demonstrated. PC is a promising annealing method for large-area, high-throughput annealing of Sb2Se3 with various potential applications in Sb2Se3 photovoltaics.

Active Passivation of Anion Vacancies in Antimony Selenide Film for Efficient Solar Cells.

Binary antimony selenide (Sb2Se3) is a promising inorganic light-harvesting material with high stability, nontoxicity, and wide light harvesting capability. In this photovoltaic material, it has been recognized that deep energy level defects with large carrier capture cross section, such as VSe (selenium vacancy), lead to serious open-circuit voltage (VOC) deficit and in turn limit the achievable power conversion efficiency (PCE) of Sb2Se3 solar cells. Understanding the nature of deep-level defects and establishing effective method to eliminate the defects are vital to improving VOC. In this study, a novel directed defect passivation strategy is proposed to suppress the formation of VSe and maintain the composition and morphology of Sb2Se3 film. In particular, through systematic study on the evolution of defect properties, the pathway of defect passivation reaction is revealed. Owing to the inhibition of defect-assisted recombination, the VOC increases, resulting in an improvement of PCE from 7.69% to 8.90%, which is the highest efficiency of Sb2Se3 solar cells prepared by thermal evaporation method with superstrate device configuration. This study proposes a new understanding of the nature of deep-level defects and enlightens the fabrication of high quality Sb2Se3 thin film for solar cell applications.

Photoresponse in sequentially stacked antimony selenide thin films

Antimony selenide (Sb2Se3), a binary semiconducting compound has widespread research attention due to its excellent optoelectronic properties in the visible region and usefulness in applications such as solar cells, photosensors and photoelectrodes. The presented study explores the thickness dependent photoresponse in Sb2Se3 thin films, prepared by reactive selenization of antimony films having thickness values of ∼938 nm and ∼1879 nm when stacked second time. Growth orientation along [001] direction was achieved through carefully optimized selenization conditions to enable favourable charge transport in anisotropic Sb2Se3. Predominant Sb2Se3 formation was inferred from x-ray diffraction, Raman spectroscopy, secondary electron microscopy and energy-dispersive X-ray analyses. High optical absorption coefficient values of about 1 × 105 cm−1 and 5.7 × 104 cm−1 were observed for ∼938 nm and ∼1879 nm thick Sb2Se3 thin films. Further, the optoelectronic properties were elucidated through current–voltage and transient photoresponse measurements under dark and illumination conditions. The measurements were done under zero and different bias voltages. Sb2Se3 films having∼ 938 nm thickness exhibited self-driven photoresponse with a responsivity of 4.3×10−8 A W−1 and detectivity of 3.5 × 106 jones respectively, under AM 1.5 G illumination conditions.

Effect of Energy-driven Molecular Precursor Decomposition on the Crystal Orientation of Antimony Selenide Film and Solar Cell Efficiency.

Antimony selenide (Sb2Se3) consists of 1D (Sb4Se6)n ribbons, along which the carriers exhibit high transport efficiency. By adjusting the deposition parameters of vacuum-deposited methods, such as evaporation temperature, chamber pressure, and vapor concentration, it is possible to grow the (Sb4Se6)n ribbons vertically or highly inclined towards the substrate, resulting in films with [hk1] orientation. However, the specific mechanisms by which these deposition parameters affect the orientation of thin films require a deeper understanding. Herein, a molecular beam epitaxy technique is developed for the preparation of highly [hk1]-oriented Sb2Se3 films, and the effect of evaporation parameters on the film orientation is investigated. It is found that the evaporation temperature can affect the decomposition degree of Sb2Se3, which in turn determines the vapor composition and film orientation. Additionally, the decomposition of Sb2Se3 related to evaporation temperature leads to significant changes in the elemental composition of the film, thereby passivating deep-level defects under Se-rich conditions. Consequently, the Sb2Se3 films with highly [hk1] orientation achieve a power conversion efficiency of 8.42% for the solar cells. This study provides new insights into the control of orientation in antimony-based chalcogenide films and points out new directions for improving the photovoltaic performance of solar cells.

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.

Ultrafast Electron and Hole Transfer and Efficient Charge Separation in a Sb2Se3/CdS Thin Film p-n Heterojunction.

Harvesting solar energy for different applications requires the continuous development of new semiconducting materials to exploit a broad part of the solar spectrum. In this direction, antimony selenide (Sb2Se3) has attracted a tremendous amount of attention over the past few years as a light-harvesting material for photovoltaic device applications owing to its phase stability, high absorption coefficient, earth abundance, and low toxicity. Here, we have fabricated a high-quality heterojunction of a p-type Sb2Se3 film and an n-type CdS film using the thermal evaporation technique. The photocurrent of the heterosystem was significantly higher than that of the pristine materials. This optoelectronic response was investigated using femtosecond transient absorption (TA) spectroscopy. TA study reveals the existence of an instantaneous electron transfer from Sb2Se3 to CdS, accompanied by a substantial charge separation at the heterojunction. Our study deals with the investigation of a well-designed p-n device, paving the way for the fabrication of highly efficient photovoltaic devices.

Cu-Doped Sb2Se3 Thin-Film Solar Cells Based on Hybrid Pulsed Electron Deposition/Radio Frequency Magnetron Sputtering Growth Techniques

In recent years, research attention has increasingly focused on thin-film photovoltaics utilizing Sb2Se3 as an ideal absorber layer. This compound is favored due to its abundance, non-toxic nature, long-term stability, and the potential to employ various cost-effective and scalable vapor deposition (PVD) routes. On the other hand, improving passivation, surface treatment and p-type carrier concentration is essential for developing high-performance and commercially viable Sb2Se3 solar cells. In this study, Cu-doped Sb2Se3 solar devices were fabricated using two distinct PVD techniques, pulsed electron deposition (PED) and radio frequency magnetron sputtering (RFMS). Furthermore, 5%Cu:Sb2Se3 films grown via PED exhibited high open-circuit voltages (VOC) of around 400 mV but very low short-circuit current densities (JSC). Conversely, RFMS-grown Sb2Se3 films resulted in low VOC values of around 300 mV and higher JSC. To enhance the photocurrent, we employed strategies involving a thin NaF layer to introduce controlled local doping at the back interface and a bilayer p-doped region grown sequentially using PED and RFMS. The optimized Sb2Se3 bilayer solar cell achieved a maximum efficiency of 5.25%.

In situ crystallization of amorphous Sb2Se3 films at electron beam irradiation

Amorphous films of Sb2Se3 were studied for crystallization under the action of electron irradiation. Electron microscopy studies demonstrated, that phase transformation is the island polymorphous crystallization mode with the relative length δ0≈ 183 for a film with a thickness 25 nm and δ0≈ 489 for a film with a thickness 40 nm. The dependence of the fraction of the crystalline phase on time has an exponential character, described by the JMAK formula. For films of both thicknesses numerical value of Avrami exponent nearest integer = 2.

Thickness-dependent nonlinear optical absorption of Sb2Se3 films grown by physical vapor deposition

Both experimental and theoretical works have demonstrated that two-dimensional materials exhibit strong thickness-dependent electronic and linear optical properties. However, the nonlinear optical (NLO) effect with respect to the thickness still needs to be further investigated, which is of great significance to design different photonic devices. Herein, we develop the physical vapor deposition technique to prepare a series of antimony selenide (Sb2Se[Formula: see text] films. The relationship between the thickness of Sb2Se3 film and the NLO absorption was investigated by a [Formula: see text]-scan system under 35[Formula: see text]fs, 800[Formula: see text]nm laser excitation. The result shows the thicker Sb2Se3 film ([Formula: see text]50[Formula: see text]nm) performs a larger third-order NLO susceptibility (Im[Formula: see text] approximately [Formula: see text] esu, which can be interpreted by the stronger photon absorption, lower saturable intensity, and larger absorption cross-section of ground-state. More importantly, the Im[Formula: see text] absolute value of thick Sb2Se3 film is also far larger than those of graphene, black phosphorus, transition metal dichalcogenide, MXenes, and heterostructure. This work demonstrates that Sb2Se3 film is an excellent saturable absorber and provides a promising application in nonlinear photonics.

Solution-processed Sb2Se3 photocathodes under Se-rich conditions and their photoelectrochemical properties.

In this study, selenium (Se)-rich antimony selenide (Sb2Se3) films were fabricated by applying a solution process with the solvents ethylenediamine and 2-mercaptoethanol to optimize the photoelectrochemical (PEC) performance of the Sb2Se3 photocathode. Various antimony (Sb)-Se precursor solutions with different molar ratios of Sb and Se (Sb : Se = 1 : 1.5, 1 : 3, 1 : 4.5, 1 : 7.5, and 1 : 9) were prepared to attain Se-rich fabrication conditions. As a result, the Se-rich Sb2Se3 films fabricated using the Sb-Se precursor solution with a molar ratio of Sb : Se = 1 : 7.5 exhibited an improved PEC performance, compared to the stoichiometric Sb2Se3 film. The charge transport was improved by the abundant Se element and thin selenium oxide (Se2O3) layer in the Se-rich Sb2Se3 film, resulting in a decrease in Se vacancies and substitutional defects. Moreover, the light utilization in the long wavelength region above 800 nm was enhanced by the light-trapping effect because of the nanowire structure in the Se-rich Sb2Se3 film. Hence, the optimal Se-rich Sb2Se3 photocathodes showed an improved photocurrent density of -0.24 mA cm-2 at the hydrogen evolution reaction potential that was three times higher than that of the stoichiometric Sb2Se3 photocathodes (-0.08 mA cm-2).

Controlled Epitaxial Growth of (hk1)-Sb2Se3 Film on Cu9S5 Single Crystal via Post-Annealing Treatment for Photodetection Application.

Antimony selenide (Sb2Se3) is a promising semiconductor for photodetector applications due to its unique photovoltaic properties. Achieving optimal carrier transport in (001)-Sb2Se3 by the material of contacting substrate requires in-depth study. In this paper, the induced growth of Sb2Se3 films from (hk0) to (hk1) planes is achieved on digenite (Cu9S5) films by post-annealing treatment. The flake-like and flower-like morphologies on the surface of Sb2Se3 films are caused by different thicknesses of the Cu9S5 films, which are related to the (hk0) and (hk1) planes of Sb2Se3 surface. The epitaxial growth of Sb2Se3 films on (105)-Cu9S5 surfaces exhibits thickness dependence. The results inform research into the controlled induced growth of low-dimensional materials. The device of Sb2Se3/Cu9S5/Si has good broadband response (visible to near-infrared), self-powered characteristics, and stability. As the crystalline quality of the Sb2Se3 film increases along the (hk1) plane, the carrier transport is enhanced correspondingly. Under the 980nm light irradiation, the device has an excellent switching ratio of 2×104 at 0 bias, with responsivity, detectivity, and response time up to 17µAW-1, 1.48×107 Jones, and 355/490µs, respectively. This suggests that Sb2Se3 is suitable for self-powered photodetectors and related optical and optoelectronic devices.

Suppressing Buried Interface Nonradiative Recombination Losses Toward High-Efficiency Antimony Triselenide Solar Cells.

Antimony triselenide (Sb2 Se3 ) has possessed excellent optoelectronic properties and has gained interest as a light-harvesting material for photovoltaic technology over the past several years. However, the severe interfacial and bulk recombination obviously contribute to significant carrier transport loss thus leading to the deterioration of power conversion efficiency (PCE). In this work, buried interface and heterojunction engineering are synergistically employed to regulate the film growth kinetic and optimize the band alignment. Through this approach, the orientation of the precursor films is successfully controlled, promoting the preferred orientational growth of the (hk1) of the Sb2 Se3 films. Besides, interfacial trap-assisted nonradiative recombination loss and heterojunction band alignment are successfully minimized and optimized. As a result, the champion device presents a PCE of 9.24% with short-circuit density (JSC ) and fill factor (FF) of 29.47mA cm-2 and 63.65%, respectively, representing the highest efficiency in sputtered-derived Sb2 Se3 solar cells. This work provides an insightful prescription for fabricating high-quality Sb2 Se3 thin film and enhancing the performance of Sb2 Se3 solar cells.

Regulating Deposition Pressures During Rapid Thermal Evaporation Processes to Enable Efficient Sb2 Se3 Solar Cells.

Sb2 Se3 solar cells deposited by rapid thermal evaporation (RTE) have drawn extensive attention owing to their compatibility with the commercial production line of CdTe solar cells and can be used to fabricate high-quality Sb2 Se3 films with high reproducibility. However, the deposition pressure during the RTE process has not been clearly explored, although it has a significant effect on the Sb2 Se3 film quality. A novel two-step deposition strategy is proposed that finely regulates the deposition pressure to improve the quality of Sb2 Se3 absorber layers, thereby improving the device performance of Sb2 Se3 solar cells. This novel method includes a rapid deposition process under a low pressure (5 mTorr) and an in situ annealing process under a relatively high pressure (200Torr). The maximum power conversion efficiency (PCE) of Sb2 Se3 solar cells fabricated by two-step deposited approach is up to 8.12%. The PCE enhancement is attributed to the increased grain size, reduced grain boundaries, modified surface Fermi level gradient of the absorber layer, and improved defect performance. This innovative deposition technique is expected to benefit other low-melting-point metal sulfoselenides for solar cell applications.