Inorganic Thin Film Solar Cells Research Articles

Recent Advances and Prospects of Solution‐Processed Efficient Sb2S3 Solar Cells

AbstractSolar cells comprising earth‐abundant and non‐toxic elements with applicable bandgaps and high absorption coefficients have attracted considerable interest over the past several decades and are important devices for addressing the future demand for clean and renewable energy. Antimony sulfide (Sb2S3) crystal material effectively meets these requirements owing to its suitable bandgap, high absorption coefficient, high electron and hole mobilities, earth abundance, and excellent stability. Solution‐processed Sb2S3 films are essential to facilitate the fabrication of low‐cost, large‐scale, and high‐efficiency photovoltaic devices, but suffer from several shortcomings of large intrinsic defects, high interfacial barrier, and atomic mismatch, uncontrollable film thickness, and crystal orientation. In this review, a systematic overview of the fundamental properties of solution‐processed Sb2S3 materials is presented, and then interface engineering, defect passivation and control strategies, crystal orientation and modulation methods, device structure, and the performance of Sb2S3 solar cells are focused, highlighting the primary advancements and major challenges based on this technology. Finally, several creative perspectives and constructive innovation strategies for future research on Sb2S3 photovoltaic devices are provided, indicating a roadmap for the practical application of other inorganic semiconductor heterojunction thin film solar cells.

Inorganic Thin-Film Solar Cells: Challenges at the Terawatt-Scale

Thin-film solar cells have been referred to as second-generation solar photovoltaics (PV) or next-generation solutions for the renewable energy industry. The layer of absorber materials used to produce thin-film cells can vary in thickness, from nanometers to a few micrometers. This is much thinner than conventional solar cells. This review focuses on inorganic thin films and, therefore, hybrid inorganic–organic perovskite, organic solar cells, etc., are excluded from the discussion. Two main families of thin-film solar cells, i.e., silicon-based thin films (amorphous (a-Si) and micromorph silicon (a-Si/c-Si), and non-silicon-based thin films (cadmium telluride (CdTe) and copper–indium–gallium diselenide (CIGS)), are being deployed on a commercial scale. These commercial technologies, until a few years ago, had lower efficiency values compared to first-generation solar PV. In this regard, the concept of driving enhanced performance is to employ low/high-work-function metal compounds to form asymmetric electron and hole heterocontacts. Moreover, there are many emerging thin-film solar cells conceived to overcome the issue of using non-abundant metals such as indium (In), gallium (Ga), and tellurium (Te), which are components of the two commercial thin-film technologies, and therefore to reduce the cost-effectiveness of mass production. Among these emerging technologies are kesterite CZTSSE, intensively investigated as an alternative to CIGS, and Sb2(S,Se)3. In this review, after a general overview of the current scenario of PV, the three main challenges of inorganic thin-film solar cells, i.e., the availability of (safe) metals, power conversion efficiency (PCE), and long-term stability, are discussed.

Flexible Substrate‐Structured Sb2S3 Solar Cells with Back Interface Selenization

AbstractAntimony sulfide (Sb2S3) with a 1D molecular structure has strong bending characteristics, showing great application potential in flexible devices. Herein, the flexible substrate‐structured Sb2S3 solar cells is developed and improve device performances by the back interface selenization. The high‐quality Sb2S3 film with an optimal thickness of 1.8 µm, ensuring efficient spectra utilization, is deposited on flexible Mo foils by the rapid thermal evaporation technique. To solve the issues of back interfacial recombination and charge transport, the 20 nm MoSe2 layer between Sb2S3 film and Mo foil is fabricated by substrate selenization in the tube furnace. Further investigations indicate that the MoSe2 layer improves the interfacial energy band alignments and induces the [hk1] orientation of Sb2S3 film, thereby passivating defects and enhancing the carrier transport capacity. The flexible solar cell in the structure of Mo foil/MoSe2/Sb2S3/CdS/ITO/Ag, exhibiting good flexibility to stand thousands of bending, achieves an efficiency of 3.75%, which is the highest for Sb2S3 devices in substrate configuration. The presented flexible structure and back interfacial selenization study will provide new prospects for inorganic Sb2S3 thin film solar cells.

Two‐Step Cooling Strategy for Synergistic Control of CuZn and SnZn Defects Enabling 12.87% Efficiency (Ag,Cu)2ZnSn(S,Se)4 Solar Cells

AbstractAbundant intrinsic defects and defect clusters in Cu2ZnSn(S,Se)4 (CZTSSe) solar cells lead to severe nonradiative recombination and limited photoelectric performance. Therefore, developing effective method to suppress the detrimental defects is the key to achieve high‐efficiency solar cell. Herein, a convenient two‐step cooling strategy in selenization process is reported to suppress the CuZn and SnZn defects and defect clusters synergistically. The results show that rapid cooling during section from selenization temperature to turning temperature can inhibit the volatilization of Sn and restrain the corresponding Sn‐related defects, while slow cooling during the subsequent temperature section can reduce the degree of Cu‐Zn disorder. Benefitting from the synergistic effect of two‐step cooling, a significantly lowered concentration of SnZn and CuZn defect and their defect clusters [2CuZn+SnZn] in absorber is observed, meanwhile, a reduced band tailing effect and promoted carrier collection efficiency of the photovoltaic device is obtained. Finally, a device with improved open‐circuit voltage (Voc) of 505.5 mV and efficiency of 12.87% is achieved. This study demonstrates the impact of cooling process on defects controlling for the first time and provides a simple and effective new strategy for intrinsic defect control, which may be universal in other inorganic thin film solar cells.

Bismuth Complex Controlled Morphology Evolution and CuSCN-Induced Transport Improvement Enable Efficient BiI3 Solar Cells.

Bismuth triiodide (BiI3) is a particularly promising absorber material for inorganic thin-film solar cells due to its merits of nontoxicity and low cost. However, one key factor that limits the efficiency of BiI3 solar cells is the film morphology, which is strongly correlated with the trap states of the BiI3 film. Herein, we report a coordination engineering strategy by using Lewis base dimethyl sulfoxide (DMSO) to induce the formation of a stable BiI3(DMSO)2 complex for controlling the morphology of BiI3 films. Density functional theory calculations further provide a theoretical framework for understanding the interaction of the BiI3(DMSO)2 complex with BiI3. The obtained BiI3(DMSO)2 complex could assist the fabrication of highly uniform and pinhole-free films with preferred crystallographic orientation. This high-quality film enables reduced trap densities, a suppressed charge recombination, and improved carrier mobility. In addition, the use of copper(I) thiocyanate (CuSCN) as a hole transport layer improves the charge transport, enabling the realization of solar cells with a record power conversion efficiency of 1.80% and a champion fill factor of 51.5%. Our work deepens the insights into controlling the morphology of BiI3 thin films through the coordination engineering strategy and paves the way toward further improving the photovoltaic performances of BiI3 solar cells.

Unveiling microscopic carrier loss mechanisms in 12% efficient Cu2ZnSnSe4 solar cells

Understanding carrier loss mechanisms at microscopic regions is imperative for the development of high-performance polycrystalline inorganic thin-film solar cells. Despite the progress achieved for kesterite, a promising environmentally benign and earth-abundant thin-film photovoltaic material, the microscopic carrier loss mechanisms and their impact on device performance remain largely unknown. Herein, we unveil these mechanisms in state-of-the-art Cu2ZnSnSe4 (CZTSe) solar cells using a framework that integrates multiple microscopic and macroscopic characterizations with three-dimensional device simulations. The results indicate the CZTSe films have a relatively long intragrain electron lifetime of 10–30 ns and small recombination losses through bandgap and/or electrostatic potential fluctuations. We identify that the effective minority carrier lifetime of CZTSe is dominated by a large grain boundary recombination velocity (~104 cm s−1), which is the major limiting factor of present device performance. These findings and the framework can greatly advance the research of kesterite and other emerging photovoltaic materials.

Mo Contact via High-Power Impulse Magnetron Sputtering on Polyimide Substrate

It has always been a huge challenge to prepare the Mo back contact of inorganic compound thin film solar cells (e.g., CIGS, CZTS, Sb2Se3) with good conductivity and adhesion at the same time. High-power impulse magnetron sputtering (HiPIMS) has been proposed as one solution to improve the properties of the thin film. In this study, the HiPIMS technology replaced the traditional DC power sputtering technology to deposit Mo back contact on polyimide (PI) substrates by adjusting the experimental parameters of HiPIMS, including working pressure and pulse DC bias. When the Mo back contact is prepared under a working pressure of 5 mTorr and bias voltage of −20 V, the conductivity of the Mo back contact is 9.9 × 10−6 Ω·cm, the residual stress of 720 MPa, and the film still has good adhesion. Under the minimum radius of curvature of 10 mm, the resistivity change rate of Mo back contact does not increase by more than 15% regardless of the 1680 h or 1500 bending cycle tests, and the Mo film still has good adhesion in appearance. Experimental results show that, compared with traditional DC sputtering, HiPIMS coating technology has better conductivity and adhesion at the same time, and is especially suitable for PI substrates.

Perovskite Solar Cells Go Bifacial-Mutual Benefits for Efficiency and Durability.

Bifacial solar cells hold the potential to achieve a higher power output per unit area than conventional monofacial devices without significantly increasing manufacturing costs. However, efficient bifacial designs are challenging to implement in inorganic thin-film solar cells because of their short carrier lifetimes and high rear surface recombination. The emergence of perovskite photovoltaic (PV) technology creates a golden opportunity to realize efficient bifacial thin-film solar cells, owing to their outstanding optoelectronic properties and unique features of device physics. More importantly, transparent conducting oxide electrodes can prevent electrode corrosion by halide ions, mitigating one major instability issue of the perovskite devices. Here, the theory of bifacial PV devices is summarized and the advantages of bifacial perovskite solar cells, such as high power output, enhanced device durability, and low economic and environmental costs, are reviewed. The limitations and challenges for bifacial perovskite solar cells are also discussed. Finally, the awareness of bifacial solar cells as a feasible commercialization pathway of perovskite PV for mainstream solar power generation and building-integrated PV is advocated and future research directions are suggested.

Quasi-Vertically-Orientated Antimony Sulfide Inorganic Thin-Film Solar Cells Achieved by Vapor Transport Deposition.

The one-dimensional photovoltaic absorber material Sb2S3 requires crystal orientation engineering to enable efficient carrier transport. In this work, we adopted the vapor transport deposition (VTD) method to fabricate vertically aligned Sb2S3 on a CdS buffer layer. Our work shows that such a preferential vertical orientation arises from the sulfur deficit of the CdS surface, which creates a beneficial bonding environment between exposed Cd2+ dangling bonds and S atoms in the Sb2S3 molecules. The CdS/VTD-Sb2S3 interface recombination is suppressed by such properly aligned ribbons at the interface. Compared to typical [120]-oriented Sb2S3 films deposited on CdS by the rapid thermal evaporation (RTE) method, the VTD-Sb2S3 thin film is highly [211]- and [121]-oriented and the performance of the solar cell is increased considerably. Without using any hole transportation layer, a conversion efficiency of 4.73% is achieved with device structure of indium tin oxide (ITO)/CdS/Sb2S3/Au. This work provides a potential way to obtain vertically aligned thin films on different buffer layers.

Efficient and stable TiO2/Sb2S3 planar solar cells from absorber crystallization and Se-atmosphere annealing

Inorganic Sb2S3 thin film solar cells show wide application prospects in low cost, non-toxicity and high stability solar cells comparing with well-developed CIGS, CdTe and organohalide perovskite materials. The present work successfully fabricated Sb2S3 film utilizing rapid thermal evaporation (RTE) method. By optimizing the crystal growth technique, smooth and non-pinhole Sb2S3 film was deposited on compact TiO2 substrate. The corresponding planar TiO2/Sb2S3 solar cells without hole transport material (HTM) assistance achieved an efficiency of 2.5%. To eliminate S-shape J-V curves and improve the fill factor, the as-deposited Sb2S3 film was further annealed in selenium atmosphere. The efficiency and fill factor of Se-atmosphere annealed Sb2S3 devices were improved to 3.2% and 55%, respectively. The device improvement mechanism of Se-annealing process were systematically illustrated by cryogenic measurements, impedance analysis and capacitance-voltage characterizations. The post-annealing could help to improve junction quality, passivate absorber defects and decrease back contact barrier. The Se-atmosphere annealed Sb2S3 devices could stand continuous one sun illumination for 400 h and the efficiency was almost the same. After storing in air for six months, the average efficiencies still hold more than 90% of initial value. The present developed environment-friendly stable devices and efficient treatment technique were expected to enrich the research of thin film solar cell.

Efficient hybrid solution strategy to fabricate Cu(In,Ga)(S,Se)2 solar cells

Hybrid solution process is a powerful liquid deposited strategy merging the advantage of molecular precursor solution and nanocrystals ink. A novel hybrid solution approach is presented to fabricate Cu(In,Ga)(S,Se)2 (CIGSSe) absorber layer using fully dissolved CIGS precursor solution and the CIGS nanocrystals. Such attractive strategy could significantly improve the single deposited thickness and enhance the quality of as-prepared CIGS film compared with the pure CIGS molecular precursor solution and the CIGS nanocrystals ink. Photovoltaic absorber layers based on CIGSSe chalcopyrite structure show the high-quality microstructural performance and are incorporated into solar cells with power conversion efficiency of 10.19%. The high performance of resulted optoelectronic devices represents a chance to extend the hybrid solution process to other inorganic semiconductor thin film solar cells.

Solution processed n-In2S3/p-P3HT planar hybrid solar cell

In2S3 is one of the widely used semiconductors in optoelectronic applications. It has already been used as an n-type buffer layer instead of highly toxic CdS semiconductor in copper indium sulfide based inorganic thin film solar cells. In this work, thin films of In2S3 were prepared on ITO coated glass and glass substrates by a solution based spin casting process. The optical, morphological, and structural characterizations of the In2S3 thin film were studied by Uv-vis spectroscopy, X-ray diffraction, and scanning electron microscopy. According to the X-ray diffraction result the thin film exhibited tetragonal β-phase. The Uv-vis study showed that the In2S3 film exhibited optical band gap of ~2.42 eV. Furthermore, a thin film of In2S3 has also been applied as an inorganic electron accepting semiconductor layer for preparing the planar inorganic/organic hybrid solar cell. The hybrid device with the In2S3 layer exhibited performance with an open-circuit voltage (Voc) of ~0.343 V, short-circuit current density (Jsc) of ~0.528 mA/cm2, fill factor of ~0.53, and power conversion efficiency (η) of ~0.12 %.

Transfer Printed Flexible and Stretchable Thin Film Solar Cells Using a Water‐Soluble Sacrificial Layer

Recently, the rapid and significant progress in the development of various stretchable electronics has triggered intense research interest. Although the remarkable features of transfer printing processes have enabled the use of inorganic crystalline semiconductors in various types of stretchable devices, including solar cells, light‐emitting diodes, circuits, and photodetectors, there are few examples of stretchable electronics using thin film semiconductors. Transfer printing of inorganic amorphous thin film semiconductors remains a challenge because no suitable sacrificial layer is available. To meet this challenge, a water‐soluble germanium oxide sacrificial layer is developed. Stretchable inorganic amorphous thin film solar cells are produced using a transfer printing process with a water‐soluble sacrificial layer. This first attempt to fabricate stretchable solar cells with inorganic amorphous thin film semiconductors significantly broadens the scope of solar cell applications. Moreover, the germanium oxide sacrificial layer can be used in other thin film electronics applications.

Contrasting the Material Chemistry of Cu2ZnSnSe4 and Cu2ZnSnS(4-x)Se x.

Earth-abundant sustainable inorganic thin-film solar cells, independent of precious elements, pivot on a marginal material phase space targeting specific compounds. Advanced materials characterization efforts are necessary to expose the roles of microstructure, chemistry, and interfaces. Herein, the earth-abundant solar cell device, Cu2ZnSnS(4-x)Se x , is reported, which shows a high abundance of secondary phases compared to similarly grown Cu2ZnSnSe4.

Lead Halide Perovskite Photovoltaic as a Model p-i-n Diode.

The lead halide perovskite photovoltaic cells, especially the iodide compound CH3NH3PbI3 family, exhibited enormous progress in the energy conversion efficiency in the past few years. Although the first attempt to use the perovskite was as a sensitizer in a dye-sensitized solar cell, it has been recognized at the early stage of the development that the working of the perovskite photovoltaics is akin to that of the inorganic thin film solar cells. In fact, theoretically perovskite is always treated as an ordinary direct band gap semiconductor and hence the perovskite photovoltaics as a p-i-n diode. Despite this recognition, research effort along this line of thought is still in pieces and incomplete. Different measurements have been applied to different types of devices (different not only in the materials but also in the cell structures), making it difficult to have a coherent picture. To make the situation worse, the perovskite photovoltaics have been plagued by the irreproducible optoelectronic properties, most notably the sweep direction dependent current-voltage relationship, the hysteresis problem. Under such circumstances, it is naturally very difficult to analyze the data. Therefore, we set out to make hysteresis-free samples and apply time-tested models and numerical tools developed in the field of inorganic semiconductors. A series of electrical measurements have been performed on one type of CH3NH3PbI3 photovoltaic cells, in which a special attention was paid to ensure that their electronic reproducibility was better than the fitting error in the numerical analysis. The data can be quantitatively explained in terms of the established models of inorganic semiconductors: current/voltage relationship can be very well described by a two-diode model, while impedance spectroscopy revealed the presence of a thick intrinsic layer with the help of a numerical solver, SCAPS, developed for thin film solar cell analysis. These results point to that CH3NH3PbI3 is an ideal intrinsic semiconductor, which happens to be very robust against accidental doping, and that the perovskite photovoltaic cell is in fact a model p-i-n diode. The analytical methods and diagnostic tools available in the inorganic semiconductor PV cells are useful and should be fully exploited in the effort of improving the efficiency. One outstanding question is why the perovskite stays intrinsic. Considering the defects and impurities that must abound in the perovskite layers formed by the spin-coating process, for example, there must be physicochemical mechanism keeping it from being doped. This may be related to the special band structure making up the band gap in this ionic solid. Understanding the mechanism may open a door for the wider utility of this class of solid.

Efficient inorganic solar cells from aqueous nanocrystals: the impact of composition on carrier dynamics

Efficient inorganic thin-film solar cells are fabricated from aqueous CdTe nanocrystals and a power conversion efficiency of 5.73% is achieved. Annealing-induced variation of material composition and charge dynamics are investigated in detail.

All Solution‐Processed Chalcogenide Solar Cells – from Single Functional Layers Towards a 13.8% Efficient CIGS Device

Solution processing of inorganic thin films has become an important thrust in material research community because it offers low‐cost and high‐throughput deposition of various functional coatings and devices. Especially inorganic thin film solar cells – macroelectronic devices that rely on consecutive deposition of layers on large‐area rigid and flexible substrates – could benefit from solution approaches in order to realize their low‐cost nature. This article critically reviews existing deposition approaches of functional layers for chalcogenide solar cells with an extension to other thin film technologies. Only true solutions of readily available metal salts in appropriate solvents are considered without the need of pre‐fabricated nanoparticles. By combining three promising approaches, an air‐stable Cu(In,Ga)Se2 thin film solar cell with efficiency of 13.8% is demonstrated where all constituent layers (except the metal back contact) are processed from solutions. Notably, water is employed as the solvent in all steps, highlighting the potential for safe manufacturing with high utilization rates.

Plasmonic effects of au/ag bimetallic multispiked nanoparticles for photovoltaic applications.

In recent years, there has been considerable interest in the use of plasmons, that is, free electron oscillations in conductors, to boost the performance of both organic and inorganic thin film solar cells. This has been driven by the possibility of employing thin active layers in solar cells in order to reduce materials costs, and is enabled by significant advances in fabrication technology. The ability of surface plasmons in metallic nanostructures to guide and confine light in the nanometer scale has opened up new design possibilities for solar cell devices. Here, we report the synthesis and characterization of highly monodisperse, reasonably stable, multipode Au/Ag bimetallic nanostructures using an inorganic additive as a ligand for photovoltaic applications. A promising surface enhanced Raman scattering (SERS) effect has been observed for the synthesized bimetallic Au/Ag multispiked nanoparticles, which compare favorably well with their Au and Ag spherical nanoparticle counterparts. The synthesized plasmonic nanostructures were incorporated on the rear surface of an ultrathin planar c-silicon/organic polymer hybrid solar cell, and the overall effect on photovoltaic performance was investigated. A promising enhancement in solar cell performance parameters, including both the open circuit voltage (VOC) and short circuit current density (JSC), has been observed by employing the aforementioned bimetallic multispiked nanoparticles on the rear surface of solar cell devices. A power conversion efficiency (PCE) value as high as 7.70% has been measured in a hybrid device with Au/Ag multispiked nanoparticles on the rear surface of an ultrathin, crystalline silicon (c-Si) membrane (∼ 12 μm). This value compares well to the measured PCE value of 6.72% for a similar device without nanoparticles. The experimental observations support the hope for a sizable PCE increase, due to plasmon effects, in thin-film, c-Si solar cells in the near future.

Contacts on polyester textile as a flexible substrate for solar cells

In the present work, the authors have studied conductive surfaces on polyester fabrics by using two types of commercially available conductive polymers; polyaniline and poly (3,4-ethylenedioxythiophene)-poly (styrenesulphonate) (PEDOT: PSS) with 100 nm aluminium thin film evaporated on top of the polymer so the fabric becomes a conductive substrate for inorganic thin film solar cells. Conductive polymer surfaces on woven polyester fabrics were obtained by knife-over-table coating technique. Surface resistivities for polyaniline and PEDOT: PSS coated fabrics were measured and found in the range of 400 × 103 and 1 × 103 Ω/□, respectively. Thermal stability tests were carried out to evaluate the effect of specific periods of heal treatment at different elevated temperatures on resistance of polymer coated conducting textiles. PEDOT: PSS exhibited better stability than panipol. According to long term tests, PEDOT: PSS coated samples showed improvement in conductivity over 3 days whereas panipol showed the opposite. Transmission Line Model tests were performed to measure aluminium/polymer contact resistances which were found to be 120 × 103 Ω for polyaniline and about 46.3 Ω for PEDOT: PSS. Mechanical bending tests for aluminium/PEDOT: PSS/fabric samples showed that the polymer can maintain the conductivity of samples by bridging micro-cracks in the metal film.

Absorption efficiency enhancement in inorganic and organic thin film solar cells via plasmonic honeycomb nanoantenna arrays

We demonstrate theoretically that by embedding plasmonic honeycomb nanoantenna arrays into the active layers of inorganic (c-Si) and organic (P3HT:PCBM/PEDOT:PSS) thin film solar cells, absorption efficiency can be improved. To obtain the solar cell absorption spectrum that conforms to the solar radiation, spectral broadening is achieved by breaking the symmetry within the Wigner-Seitz unit cell on a uniform hexagonal grid. For optimized honeycomb designs, absorption efficiency enhancements of 106.2% and 20.8% are achieved for c-Si and P3HT:PCBM/PEDOT:PSS thin film solar cells, respectively. We have demonstrated that the transverse modes are responsible for the enhancement in c-Si solar cells, whereas both the longitudinal and transverse modes, albeit weaker, are the main enhancement mechanisms for P3HT:PCBM/PEDOT:PSS solar cells. For both inorganic and organic solar cells, the absorption enhancement is independent of polarization.