PbI2 Thin Films Research Articles

Lead-free methyl ammonium tin iodide perovskite thin film growth in single step via plasma enhanced chemical vapour deposition technique and its optoelectronic properties

In the present work, lead free methyl ammonium tin iodide (CH3NH3SnI3 or MASnI3) perovskite thin films have been deposited via single step plasma enhanced chemical vapour deposition (PECVD) technique. In our earlier work, we reported lead based methyl ammonium lead iodide (CH3NH3PbI3 or MAPbI3) perovskite thin film deposition in 2-step, using sputtering technique for the PbI2 thin films and PECVD technique for CH3NH3I (MAI) thin films. Similarly, CH3NH3SnI3 perovskite thin films are deposited in this work using PECVD technique in single step. Lead is substituted with tin due to its toxic behaviour, environmental and health related issues. CH3NH3SnI3 perovskite is doped n-type via changing the molar ratio of SnI2 and CH3NH3I. SnI2/CH3NH3I ratio is changed from 0.33 to 2 to study the n-type doping of CH3NH3SnI3 perovskite. Deposited CH3NH3SnI3 perovskite thin films are deposited over p-type silicon wafer to make n-type doped n-CH3NH3SnI3/p-Si heterojunction photodiode.

Hybrid Two‐Step Inkjet‐Printed Perovskite Solar Cells

Perovskite photovoltaics are on their way to commercialization, but crucial advancements are still required to realize scalable and reliable fabrication processes Concerning solution processing of perovskite top solar cells, the hybrid two‐step process offers an auspicious combination of good thin‐film formation control, even on textures, and high power conversion efficiencies (PCEs). Herein, a scalable fabrication process that consists of a hybrid two‐step process and combines evaporated PbI2 with inkjet‐printed organic precursor materials is addressed. It is shown that optimizing the printing parameters enables high PCEs, high reproducibility, and the potential for conformal growth on textured silicon. The perovskite films are free of macroscopic drying effects and omit the use of toxic solvents. To achieve optimal conversion, the morphology of the PbI2 thin film and the selected resolution in the printing process are decisive. To facilitate intermixing and enable stoichiometry, a dimethyl sulfoxide vapor treatment is introduced to increase the PbI2 porosity. Reproducible PCEs are demonstrated with champion devices showing 18.2% which are on par with spin‐coated counterparts. In the results, it is demonstrated that the hybrid two‐step process with an inkjet‐printed second step is a promising scalable process for reliable and high‐quality perovskite deposition even on texture, thereby paving the path toward industrialization.

Crystal Growth Nucleation Induced by CsPb2Br5 2D for Efficient and Stable Perovskite Solar Cells

Crystallization is a crucial step in obtaining high‐quality perovskite films. A 2D seed‐induced method is proposed for fabricating perovskite solar cells (PSCs). CsPb2Br5 significantly reduces the formation energy of perovskite according to the density functional theory calculations. The creation of perovskites is facilitated by CsPb2Br5, which also helps to improve the conditions for perovskite formation. The creation of large perovskite particles is accelerated by using a 2D seed‐precursor solution, which also improves the performance of PbI2 thin films. However, excessive doping can cause dopants to precipitate on the smooth surface of PbI2 thin films, resulting in the formation of perovskite thin films with numerous cracks, ultimately reducing device efficiency. Through meticulous optimization, the perovskite thin film obtained from a precursor solution with 30% concentration identifies the longest charge lifetime. With a remarkable power conversion efficiency of 24.06% under one solar illumination, the champion gadget demonstrates extraordinary photovoltaic performance. These results offer important insights for the logical design and manufacture of perovskite materials and have the potential to significantly advance PSC technology.

Static anti-solvent treatment on lead iodide in two-step deposition of methylammonium lead iodide perovskite thin films

Static anti-solvent treatment is rarely employed for perovskite thin film fabrication, even though this method is dependent only on fewer thin film growth parameters as compared to the dynamic anti-solvent application. Thus, studies on the influence of static anti-solvent treatment on the properties of perovskite thin films is important to gain insight to the growth processes, which is very scarce as well. In this study, we investigate the static anti-solvent treatment to tailor the morphology of Lead Iodide (PbI2) thin films for the fabrication of precursor-free Methylammonium Lead Iodide (MAPI) perovskite thin films through the two-step deposition method using Chlorobenzene as an anti-solvent. Remarkable influence of the anti-solvent loading time on the film morphology of PbI2 and MAPI thin films is observed. The crystallinity of PbI2 decreases upon increasing the anti-solvent loading time. A complete conversion of the precursors to MAPI along with the largest grain size are attained even at short loading times, ∼5s. Grain size does not increase considerably at higher loading times. Linear absorption studies on MAPI thin films show an increase in the Urbach energy with an increase in the loading time, which indicates an increase in the defect density. The increase in defect density with anti-solvent loading time is attributed to the concurrent decrease in the crystallinity of the PbI2 thin film. Steady-state and time-resolved photoluminescence (PL) studies performed on the MAPI thin films show highest PL intensity and life time at an optimum anti-solvent loading time (∼5s), which arises due to the trade off between largest grain size and lowest defect density. These observations not only highlights the need for an optimum crystallinity in the PbI2 thin films for the fabrication of superior quality MAPI thin films but also infers an optimum static anti-solvent loading time as the increase in grain size and life time enhances the device performance while an increase in defect density degrades the performance.

Structural, Optical, and Chemical Characteristics of High‐Quality PbI2 Thin Films via Chemical Solution Deposition with Thermal Annealing

Herein, a synthesis method for obtaining lead iodide through chemical bath deposition, a type of chemical solution deposition without the use of organic solvents, is presented; the process consists of three stages. In the first stage, tin hydroxide films are produced which act as a seed layer allowing for a better adherence of the film that is to be deposited. The second stage consists of the synthesis of the lead iodide films. Finally, annealing is done (100, 150, and 200 °C) with the purpose of promoting the polytypic transitions of the material and to study the effect of these structures on the properties of the material. Assessment of the structural and optical properties of the films is done by means of scanning electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, optical spectroscopy, Raman spectroscopy, and transmission electron microscopy, where a direct influence of the annealing in the induction of polytypes is observed. The resultant PbI2 films have a large‐area coverage across the substrate, wide‐bandgap (2.38 eV), and a structure that belongs to the 2H and 4H polytypes. Hence, it is suggested from these results that the chemically deposited PbI2 thin films are promising candidates for large‐area optoelectronic applications.

Valine-Modified PbI2 for the Growth of Pinhole-Free Lead Halide Perovskite Thin Films by Vapor–Solid Reaction

In recent years, the efficiency of perovskite solar cells (PSCs) has rapidly increased, making PSCs commercially viable and able to compete with silicon solar cells. However, the technology for large-scale production of perovskite thin films still poses a significant challenge to the commercialization of PSCs. This is mainly because the thickness of the perovskite light-absorbing film is less than 1 μm and easily produces pinholes during large-scale production, causing serious charge recombination and reducing the efficiency of the device. As a result, the efficiencies of most large-scale PSC modules are significantly lower than those of small-size devices. Vapor-reaction technology is considered a crucial method to enhance the uniformity of perovskite thin films. However, current techniques are not yet advanced enough to deposit pinhole-free perovskite thin films on a large scale. One major challenge is that lead iodide (PbI2) precursor thin films have a tendency to develop a sheet-like structure with a loose morphology, which contributes to the formation of pinholes in the perovskite film. Additionally, uncoordinated Pb2+ could be easily generated in the PbI2 film during thermal evaporation, causing an increase in trap-states in the perovskite crystal. To address this, we developed a valine treatment process in this study to change the preferred orientation of PbI2 from a sheet-like to a particle-like aggregate and obtained compact PbI2 thin films. Meanwhile, this valine vapor treatment can significantly reduce the uncoordinated Pb2+ in PbI2 films. Based on this, we successfully prepared pinhole-free perovskite thin films using a vapor–solid reaction. Perovskite films based on these valine-treated PbI2 exhibited a reduced trap density and significantly improved PSCs’ performance, with a maximum efficiency exceeding 21%. Large-area PSC mini-modules (5 cm × 5 cm) produced from the perovskite film (30 cm × 30 cm) showed uniformly distributed power conversion efficiency values exceeding 17%, with the highest value reaching 18.78%. We believe that this facile valine vapor treatment holds great potential for the large-scale production of stable and high-efficiency PSC modules.

Crossover from strong to weak exciton confinement in thickness-controlled epitaxial PbI2 thin films

Spatially confined excitons undergo two distinct quantization effects depending on the confinement length, the enhanced binding energy under strong confinement, and the center-of-mass quantization under weak one. However, the transition between them has not been experimentally identified in two-dimensional (2D) materials due to the lack of thin films satisfying large-scale uniformity and atomic-level flatness in a wide thickness range. Here, we reveal the crossover in high-quality epitaxial thin films of a 2D semiconductor PbI2 grown by molecular beam epitaxy. The absorption spectra exhibit oscillatory structures manifesting the exciton center-of-mass quantization, and the quantization energies show an additional blue shift associated with the strong confinement effect below five-layer thickness (35 Å). The precise control of exciton quantum states will lead to the further development of optoelectronic functionalities of 2D materials.

Effect of changing substrate temperature of PbI2 thin films deposited by spray technique on the structural ,optical and electrical properties

تم تحضير طبقات متعددة الكريستالات من يوديد الرصاص باستخدام تقنية الرش على ركائز زجاجية للتطبيق المحتمل في الكشف النووي. درس هذا البحث تأثير تغير درجة حرارة الركيزة لأغشية PbI2 على الخصائص التركيبية والبصرية والكهربائية عند درجات حرارة مختلفة للركيزة ( 150.200.250) درجة مئوية.

Impact of Sb-insertion on structural, optical, and dielectric characteristics of the PbI2 thin film

Antimony (Sb) has been widely used as an additive in solar cells for enhanced performance. We described a simple, affordable, solution-processed approach for producing pure and antimony (Sb3+)-doped lead iodide (PbI2) thin films with varying doping ratios (0.5, 1.0, 2.0, and 3.0%). Structural, optical, and dielectric properties were investigated using XRD and UV–Vis spectroscopy. The XRD spectra illustrated that the synthesized PbI2 thin films have a preferred orientation along the c-axis (001) with a hexagonal structure. The crystalline sizes of PbI2 increased by increasing the Sb-doping concentration up to 1%, then decreased with 2% and 3% Sb-doping. In the visible and NIR regions, the optical transparency of the grown films were in between 70 and 80%. The optical band gap changes inversely with the crystalline sizes; it decreases with 0.5% and 1% Sb-doping and increases with further doping. As the energy gap is spanned between 2.39 and 2.27 eV, therefore, Sb: PbI2 films are ideal for use in solar cells. The resulting refractive index values were found to rise as the Sb doping concentration increased. Sb-doping decreases optical conductivity and dielectric constant.

In Situ Growth of PbS/PbI2 Heterojunction and Its Photoelectric Properties.

In this paper, PbI2 thin films with a uniform surface morphology and compact structure were prepared by adjusting the spin coating process parameters. On such a basis, the PbS/PbI2 heterojunction was fabricated on the PbI2 surface by the method of in situ chemical replacement growth. The results show that the PbS/PbI2 heterojunction grown by this method has a clear interface and is closely combined. The introduction of a PbS layer enables its spectral response range to cover the visible and near-infrared regions. Compared with the PbI2 thin film device, its responsivity is increased by three orders of magnitude, its response time reduced by 42%, and its recovery time decreased by nearly 1/2 under 450 nm illumination. In the case that there is no response for the PbI2 thin film device under 980 nm illumination, the specific detectivity of the PbS/PbI2 heterojunction device still amounts to 1.8 × 108 Jones. This indicates that the in situ chemical replacement is a technique that can construct a high-quality heterojunction in a simple process. PbS/PbI2 heterojunction fabricated by this method has a visible–near-infrared light detection response range, which provides a new idea for creating visible–near-infrared common-path detection systems.

Structure and optical properties of pbI2 thin film by thermal evaporation technique

In this search structural, optical and electrical properties were studied by preparing a sample of lead iodide applied to glass bases by thermal evaporation process. The film showed a hexagonal crystalline shape. The value of the energy gap for a sample of 200 nm thickness is 2.9051 eV the intensity is at the plane (003) it’s equal 12.5 nm in this research the value of the energy gap was (2.15eV-2.33) eV and the electrical properties were studied for a sample of. The measurements were made for the electrical conductivity, mobility, carrier’s concentration and finally the Hall coefficient. The results are (1.038*10-5, 0.6727*10+2, 1.009*1012 and 2.631*106) respectively

Gamma ray effects on the properties of PbI2 thin films

This study reports the impact of γ-ray exposure on the nanostructural, morphological, and optical characteristics of lead iodide (PbI2) thin films (TFs). These PbI2 were deposited on glass substrates using a spin coating technique. The γ-ray irradiation was carried out using Co-60 gamma source with dose range from 0 to 100 kGy. The X-ray diffraction (XRD) results revealed a decrease in crystallinity and an increase in crystallite size of PbI2 as a function of γ-ray dose. Field emission scanning electron microscopy (FESEM) exhibited the variations in surface morphology with increasing γ-ray dose. The elemental composition of as prepared TFs was confirmed by energy dispersive X-rays (EDX) analysis. The optical transmission of PbI2 TFs was evaluated with varying the γ-ray doses. The estimated energy band gap (Eg) reduced from 2.54 to 2.45 eV with γ-ray dose. Photoluminescence (PL) spectra represent a broad peak centered at 507.64 nm with a hump present at 519.73 nm in the as prepared sample, which grow gradually with increasing the γ-ray dose. The maximum value of mobility was found to be 10.48 cm2 V−1 s−1 at 50 kGy. The change in the mobility is associated with the density of structural defects influenced by γ-ray doses. These effects conclude that γ-irradiation played a key role in structural, electrical and optical properties of the PbI2 TFs and proposes that the γ-irradiation response makes it a good candidate for radiation detecting material application.

Interfacial Engineering of Perovskite Solar Cells with Evaporated PbI2 Ultrathin Layers.

Perovskite solar cells are one of the most promising thin-film photovoltaic techniques, which have an unprecedented progress in the last decade. It is well-recognized in the perovskite community that nonradiative recombination losses and the open-circuit voltage deficit are the dominant limiting factors to further improve the device efficiency. Recently, multiple groups have reported that lead iodide can effectively passivate both perovskite grain boundaries and the interfaces between perovskite and charge transport layers. However, most of the excess PbI2 was processed with solution methods and formed PbI2 grains, which cannot cover perovskite layers completely. It is also very challenging to spin-coat PbI2 layers directly on perovskites, which requires orthogonal solvents. In this work, we deposit additional PbI2 thin layers directly on perovskite thin films via thermal evaporation. The impact of PbI2 layers on the perovskite thin films and devices is systematically investigated. It was found that the evaporated PbI2 thin films can effectively reduce the nonradiative recombination and enhance the device performance. The optimized thickness of the PbI2 layer was determined to be around 10 nm, which results in a relatively high Voc of 1.18 V and power conversion efficiency of 21.52%.

Optimization of optoelectrical properties during synthesizing methylammonium lead iodide perovskites via a two-step dry process

We investigated the defect states and optoelectrical properties of methylammonium lead iodide (MAPbI3) perovskite films synthesized via a two-step dry process. To synthesize MAPbI3 thin films, PbI2 thin films were deposited via rf magnetron sputtering and were subsequently exposed to methylammonium iodide (MAI) vapor to synthesize MAPbI3 thin films. By using deep level transient spectroscopy and space-charge-limited current methods, the defect density of the perovskite films was proven to be reduced by about 6 times as the reaction temperature increased from 90 to 110 °C. At a high reaction temperature of 130 °C, the deformation process could occur, resulting in a rising trap density within the perovskite film. Along with a significant decline in defect density, the photoresponsivity of films fabricated at 110 °C were higher by about 2.05 and 18.76 times more than those of samples prepared at 100 and 130 °C, respectively. An excellent detectivity of 1.17 × 1013 Jones was observed from the sample synthesized at 110 °C, demonstrating the superiority of a two-step dry process.

Orientation-Controlled Large-Area Epitaxial PbI2 Thin Films with Tunable Optical Properties.

Lead iodide (PbI2) as a layered material has emerged as an excellent candidate for optoelectronics in the visible and ultraviolet regime. Micrometer-sized flakes synthesized by mechanical exfoliation from bulk crystals or by physical vapor deposition have shown a plethora of applications from low-threshold lasing at room temperature to high-performance photodetectors with large responsivity and faster response. However, large-area centimeter-sized growth of epitaxial thin films of PbI2 with well-controlled orientation has been challenging. Additionally, the nature of grain boundaries in epitaxial thin films of PbI2 remains elusive. Here, we use mica as a model substrate to unravel the growth mechanism of large-area epitaxial PbI2 thin films. The partial growth leading to uncoalesced domains reveals the existence of inversion domain boundaries in epitaxial PbI2 thin films on mica. Combining the experimental results with first-principles calculations, we also develop an understanding of the thermodynamic and kinetic factors that govern the growth mechanism, which paves the way for the synthesis of high-quality large-area PbI2 on other substrates and heterostructures of PbI2 on single-crystalline graphene. The ability to reproducibly synthesize high-quality large-area thin films with precise control over orientation and tunable optical properties could open up unique and hitherto unavailable opportunities for the use of PbI2 and its heterostructures in optoelectronics, twistronics, substrate engineering, and strain engineering.

Temperature Dynamics of MAPbI3 and PbI2 Photolysis: Revealing the Interplay between Light and Heat, Two Enemies of Perovskite Photovoltaics

Regardless of the impressive photovoltaic performances demonstrated for lead halide perovskite solar cells, their practical implementation is severely impeded by the low device stability. Complex lead halides are sensitive to both light and heat, which are unavoidable under realistic solar cell operational conditions. Suppressing these intrinsic degradation pathways requires a thorough understanding of their mechanistic aspects. Herein, we explored the temperature effects in the light-induced decomposition of MAPbI3 and PbI2 thin films under anoxic conditions. The analysis of the aging kinetics revealed that MAPbI3 photolysis and PbI2 photolysis have quite high effective activation energies of ∼85 and ∼106 kJ mol-1, respectively, so decreasing the temperature from 55 to 30 °C can extend the perovskite lifetime by factors of >10-100. These findings suggest that controlling the temperature of the perovskite solar panels might allow the long operational lifetimes (>20 years) required for the practical implementation of this promising technology.

Study of the Optical and Structural Properties of PbI2 Thin Films Prepared by Spin Coating Technique at Room Temperature

Lead iodide thin films were deposited on a glass substrate using a spin coating technique. Powder of with a concentration (0.2M) was dissolved in a solution of Dimethylformamide (DMF). the thickness of the prepared films was controlled through the time of deposition and the spinning speed. the X-ray patterns show that the PbI2 thin films have hexagonal structures The bandgap of the thin films was measured optically and found to be about 2.45 eV. The FTIR measurements depicted the vibration modes from 1650 to 700 cm−1; the energy bandgap from the diffused reflectivity measurements was 2.4 eV; which is in a good agreement with energy gap from Tauc plot. (FESEM) images shows the nano rod shape of particles with large pores and non uniform distribution of particles

In Situ Vapor-Phase Halide Exchange of Patterned Perovskite Thin Films.

Metal halide perovskites (MHPs) exhibit optoelectronic properties that are dependent on their ionic composition, and the feasible exploitation of these properties for device applications requires the ability to control the ionic composition integrated with the patterning process. Herein, the halide exchange process of MHP thin films directly combined with the patterning process via a vapor transport method is demonstrated. Specifically, the patterned arrays of CH3 NH3 PbBr3 (MAPbBr3 ) are obtained by stepwise conversion from polymer-templated PbI2 thin films to CH3 NH3 PbI3 (MAPbI3 ), followed by halide exchange via precursor switching from CH3 NH3 I to CH3 NH3 Br. It is confirmed that the phase transformation from MAPbI3 patterns to MAPbBr3 shows time- and position-dependences on the substrate during halide exchange following the solid-solution model with Avrami kinetics. The photodetectors fabricated from the completely exchanged MAPbBr3 patterns display exceptional air stability and reversible detectivity from "apparent death" upon removing the adsorbed impurities, thereby suggesting the superior structural stability of perovskite patterns prepared through vapor-phase halide exchange. The results demonstrate the potential of chemical vapor deposition patterning of MHP materials in multicomponent optoelectronic device systems.

Lead iodide thin-film morphological-dependent metastability investigation by electrical conductivity

This study describes the metastability properties of lead iodide (PbI2) thin films which were deposited by thermal chemical vapor deposition (CVD) and spin coating on ultrasonically and chemically cleaned microscope glass substrates. Morphological differences due to deposition techniques were defined by scanning electron microscopy (SEM). Deposited PbI2 thin films have been exposed to laboratory atmosphere ambient, vacuum, and enhanced deionize water vapor (EDIWV) in order to define metastability changes. Samples metastability changes have been investigated by current–voltage (I–V), time-dependent conductivity, and annealing cycle method depending on atmospheric conditions. Activation energy of PbI2 thin films was calculated from temperature-dependent dark conductivity. Based on results gathered from this work, degradation of PbI2 dependent on atmospheric condition and surface morphology with the aspect of meta/instability view has been tried to analyzed.

Structural, morphological and optical properties of lead iodide thin film for the two step coated perovskite

The PbI2 thin films were prepared by 461 mg PbI2/ 1 ml DMF solution with inclusion of 1, 2, 3 and 5 vol% hydriodic acid. The lead iodide thin films were coated on indium tin oxide/PEDOT:PSS substrates at different spin speeds; 3000 rpm, 4000 rpm and 5000 rpm for 60 s. The influence of hydriodic acid on the crystallization was investigated using X-ray diffractometer and the analysis revealed that the 2 vol% hydriodic acid is crucial value for the crystallinity and damage threshold of the under layer PEDOT:PSS. Scanning electron microscopy showed that by altering the volume of the acid the morphology of the films can be well controlled. Especially band gap, changed optical properties as a reflection of acid effect were also observed by absorbance and transmittance behavior obtained by UV–vis spectrophotometer. Consequently, it is conclude that the lead iodide film prepared with using the precursor solution including 2 vol% HI at 4000 rpm has best crystallinity and nearly void-free smooth morphology.