Low-Dimensional 2-thiopheneethylammonium Lead Halide Capping Layer Enables Efficient Single-Junction Methylamine-Free Wide-Bandgap and Tandem Perovskite Solar Cells

Wide-bandgap (WBG) perovskite solar cells (PSCs) have garnered significant attention for their potential applications in tandem solar cells. However, their large open-circuit voltage (V_OC) deficit and serious photo-induced halide segregation remain the main challenges that impede their applications. Herein, a post-treatment strategy without thermal annealing is presented to form a 2D top layer of 2-thiopheneethylammonium lead halide (n = 1) on WBG perovskites. This thermal annealing-free post-treatment method can more effectively passivate the defects of WBG methylamine (MA)-free formamidinium/cesium lead iodide/bromide perovskite films and suppress photo-induced perovskite phase segregation, as compared with the thermal annealing method that yields multi-2D phases. The resulting opaque and semi-transparent 1.66 eV-bandgap perovskite solar cells deliver maximum power conversion efficiencies of 21.47% (a small V_OC deficit of 0.43 V) and 19.11%, respectively, both of which are among the highest reports for inverted MA-free WBG PSCs. Consequently, four-terminal all-perovskite tandem cells realize a remarkable efficiency of 26.64%, showing great promise for their applications in efficient multi-junction tandem solar cells.     

Suppressing the Photoinduced Halide Segregation in Wide-Bandgap Perovskite Solar Cells by Strain Relaxation

Efficient and stable wide bandgap (WBG) perovskite solar cells (PSCs) are imperative for fabricating superior tandem devices. However, small crystal grains and light-induced phase segregation of WBG perovskite result in large open-circuit voltage (V_OC) deficits, critically impeding the development of the related devices. Herein, the effective functional groups of Lewis-base trans-Ferulic acid (t-FA) are employed to release the residual microstrain in the perovskite lattice. Larger perovskite crystals are formed by strengthening the interaction between the perovskite solute and solution. The lattice structure is stabilized to suppress light-induced halide segregation. Finally, the power conversion efficiency (PCE) of the optimized device with a bandgap of ≈1.77 eV is increased from 17.33% to 19.31% with the enhancement of V_OC. Moreover, replacing a mixture of MeO-2PACZ and Me-4PACZ as the hole transporting layer (HTL), the PCE further lifts to 19.9% and V_OC is 1.32 V, one of the highest performances reported for WBG PSCs, especially for devices prepared entirely by solution spin-coating. Therefore, this study provides a practicable alternative for realizing efficient WBG PSCs, which can contribute to the growth of perovskite-based tandem devices.     

Efficient Inverted Perovskite Solar Cells with a Fill Factor Over 86% via Surface Modification of the Nickel Oxide Hole Contact

The poor interface quality between nickel oxide (NiO_x) and halide perovskites limits the performance and stability of NiO_x-based perovskite solar cells (PSCs). Here a reactive surface modification approach based on the in situ decomposition of urea on the NiO_x surface is reported. The pyrolysis of urea can reduce the high-valence state of nickel and replace the adsorbed hydroxyl group with isocyanate. Combining theoretical and experimental analyses, the treated NiO_x films present suppressed surface states and improved transport energy level alignment with the halide perovskite absorber. With this strategy, NiO_x-based PSCs achieve a champion power conversion efficiency (PCE) of 23.61% and a fill factor of over 86%. The device's efficiency remains above 90% after 2000 h of thermal aging at 85 °C. Furthermore, perovskite solar modules achieve PCE values of 18.97% and 17.18% for areas of 16 and 196 cm², respectively.     

In Situ Synthesis of Molybdenum Carbide Nanoparticles Incorporated into Laser-Patterned Nitrogen-Doped Carbon for Room Temperature VOC Sensing

Carbon laser-patterning (CLaP) is emerging as a new tool for the precise and selective synthesis of functional carbon-based materials for on-chip applications. The aim of this work is to demonstrate the applicability of laser-patterned nitrogen-doped carbon (LP-NC) for resistive gas-sensing applications. Films of pre-carbonized organic nanoparticles on polyethylenetherephthalate are carbonized with a CO₂-laser. Upon laser-irradiation a compositional and morphological gradient in the films is generated with a carbon content of 92% near the top surface. The specific surface areas of the LP-NC are increased by introducing sodium iodide (NaI) as a porogen. Electronic conductivity and surface area measurements corroborate the deeper penetration of the laser-energy into the film in the presence of NaI. Furthermore, impregnation of LP-NC with MoC_1−x (<10 nm) nanoparticles is achieved by addition of ammonium heptamolybdate into the precursor film. The resulting doping-sensitive nano-grain boundaries between p-type carbon and metallic MoC_1−x lead to an improvement of the volatile organic compounds sensing response of ΔR/R₀ = −3.7% or −0.8% for 1250 ppm acetone or 900 ppm toluene at room temperature, respectively, which is competitive with carbon-based sensor materials. Further advances in sensitivity and in situ functionalization are expected to make CLaP a useful method for printing selective sensor arrays.     

Centimeter-Sized Single Crystals of Two-Dimensional Hybrid Iodide Double Perovskite (4,4-Difluoropiperidinium)4AgBiI8 for High-Temperature Ferroelectricity and Efficient X-Ray Detection

Ferroelectricity and X-ray detection property have been recently implemented for the first time in hybrid bromide double perovskites. It sheds a light on achieving photosensitive and ferroelectric multifunctional materials based on 2D lead-free hybrid halide double perovskites. However, the low T_c, small P_s, and relatively low X-ray sensitivity in the reported bromide double perovskites hinder practical applications. Herein, the authors demonstrate a novel 2D lead-free iodide double perovskite (4,4-difluoropiperidinium)₄AgBiI₈ (1) for high-performance X-ray sensitive ferroelectric devices. Centimeter-sized single crystal of 1 is obtained and exhibits an excellent ferroelectricity including a high T_c up to 422 K and a large P_s of 10.5 μC cm⁻². Moreover, due to a large X-ray attenuation and efficient charge carrier mobility (μ)–charge carrier lifetime (τ) product, the crystal 1 also exhibits promising X-ray response with a high sensitivity up to 188 μC·Gy_air⁻¹ cm⁻² and a detection limit below 3.13 μGy_air·s⁻¹. Therefore, this finding is a step further toward practical applications of lead-free halide perovskite in high-performance photoelectronic devices. It will afford a promising platform for exploring novel photosensitive ferroelectric multifunctional materials based on lead-free double perovskites.     

Pure Blue Electroluminescence by Differentiated Ion Motion in a Single Layer Perovskite Device

Blue electroluminescence is highly desired for emerging light-emitting devices for display applications and optoelectronics in general. However, saturated, efficient, and stable blue emission has been challenging to achieve, particularly in mixed-halide perovskites, where intrinsic ion motion and halide segregation compromises spectral purity. Here, CsPbBr_3−xCl_x perovskites, polyelectrolytes, and a salt additive are leveraged to demonstrate pure blue emission from single-layer light-emitting electrochemical cells (LECs). The electrolytes transport the ions from salt additives, enhancing charge injection and stabilizing the inherent perovskite emissive lattice for highly pure and sustained blue emission. Substituting Cl into CsPbBr₃ tunes the perovskite luminescence from green through blue. Sky blue and saturated blue devices produce International Commission on Illumination coordinates of (0.105, 0.129) and (0.136, 0.068), respectively, with the latter meeting the US National Television Committee standard for the blue primary. Likewise, maximum luminances of 2900 and 1000 cd m⁻², external quantum efficiencies (EQEs) of 4.3% and 3.9%, and luminance half-lives of 5.7 and 4.9 h are obtained for sky blue and saturated blue devices, respectively. Polymer and LiPF₆ inclusion increases photoluminescence efficiency, suppresses halide segregation, induces thin-film smoothness and uniformity, and reduces crystallite size. Overall, these devices show superior performance among blue perovskite light-emitting diodes (PeLEDs) and general LECs.     

Novel In0.52Al0.48As/In0.53Ga0.47As metamorphic high electron mobility transistors on GaAs substrate with InxGa1−xP graded buffer layers

Compositionally graded In_xGa_1−xP (x=0.48→x=1) metamorphic layers have been grown on GaAs substrate by solid source molecular beam epitaxy using a valved phosphorus cracker cell. Three series of samples were grown to optimize the growth temperature, V/III ratio and grading rate of the buffer layer. X-ray diffraction (XRD) and photoluminescence (PL) were used to characterize the samples. The following results have been obtained: (1) XRD measurement shows that all the samples are nearly fully strain relaxed and the strain relaxation ratio is about 96%; (2) the full-width at half-maximum (FWHM) of the XRD peak shows that the sample grown at 480°C offers better material quality; (3) the grading rate does not influence the FWHM of XRD and PL results; (4) adjustment of the V/III ratio from 10 to 20 improves the FWHM of XRD peak, and the linewidth of PL peak is close to the data obtained for the lattice-matched sample on InP substrate. The optimization of growth conditions will benefit the metamorphic HEMTs grown on GaAs using graded InGaP as buffer layers.     

Systematic optical and x-ray study of In x Ga1−x As on InP

We present a systematic study of In _x Ga_1−x As on InP grown by molecular beam epitaxy using the characterization techniques of Fourier transform photoluminescence, x-ray diffraction, micro-Raman spectroscopy, and photoreflectance spectroscopy. The four techniques were used to determine and correlate the fundamental parameters of band-gap energy, phonon frequency and composition. Comparing room temperature (293 K) PL and low temperature PL indicate the presence of a partially ionized acceptor with binding energy of about 13 meV in the unintentionally doped material. Double crystal x-ray diffraction (XRD) using a symmetric <400> and asymmetric <224> reflections was also employed. The use of two reflections gives precise lattice constants, composition, and extent of film relaxation. Micro-Raman spectroscopy was used to measure phonon frequencies in the In _x Ga_1−x As films and correlated to XRD composition. Room temperature photoreflectance (PR) was used to determine band-gap energy for both the low and intermediate field cases. Band gap energies determined at room temperature by PL and PR were in agreement within experimental error.     

Anisotropic In Situ Strain-Engineered Halide Perovskites for High Mechanical Flexibility

Even though halide perovskite materials have been increasingly investigated as flexible devices, mechanical properties under flexible environments have rarely been reported on. Herein, a nonconventional deposition technique that can generate extra compressive or tensile stress in representative inorganic CsPbBr₃ and hybrid MAPbI₃ (methylammonium lead iodide) halide perovskites is proposed for higher mechanical flexibility. As an impressive result of bending fracture evaluation, fracture energy is substantially improved by ≈260% for CsPbBr₃ and ≈161% for MAPbI₃ with the maximum compressive strain of −1.33%. Origin of the flexibility enhancements by the in situ strain is verified with structural simulation where the anisotropic lattice distortion, that is, contraction in the ab plane and elongation along the c-axis, is evident with changes in atomic bond lengths and angles in the halide perovskites. Other mechanical properties such as hardness, film strength, and fracture toughness are also discussed with direct comparisons between the inorganic and hybrid halides. Beyond the successful adjustment of this in situ deposition technique, the strain-dependent mechanical properties are expected to be extensively useful for designing halides-based flexible devices.     

Mixed Halide Formation in Lead-Free Antimony-Based Halide Perovskite for Boosted CO2 Photoreduction: Beyond Band Gap Tuning

Photocatalytic conversion of carbon dioxide (CO₂) into value-added fuels is a vastly promising anthropogenic chemical carbon cycle to combat the greenhouse effect while meeting the ever-increasing energy demand. Recently, lead-based halide perovskites have demonstrated great potential in various applications including photochemical reduction of CO₂. However, in view of lead toxicity, the exploration of a lead-free alternative is crucial for long term application. Herein, a series of lead-free mixed halide perovskites Cs₃Sb₂Cl_xBr_9−x (0 ≤ x ≤ 9) is prepared via a facile antisolvent recrystallization technique, where the incorporation of a secondary halide enhances the charge transfer and separation while allowing precise tuning of bandgap between 2.59 and 2.90 eV. Theoretical calculations further reveal that the formation of mixed Cl/Br halides engenders favorable charge redistribution due to lower octahedral distortion, which in turn strengthens CO₂ adsorption and activation. Under visible light illumination, the optimal dual halide perovskite, Cs₃Sb₂Cl₄Br₅ manifests substantial twofold and fourfold enhancements of CH₄ yield over the single halide perovskite, Cs₃Sb₂Br₉ and Cs₃Sb₂Cl₉, respectively. In brief, this study provides a compelling demonstration of lead-free mixed halide perovskites for photocatalytic CO₂ reduction, and it is anticipated to drive further application of perovskite-based photocatalysts toward a diverse range of artificial photoredox reactions.     

Vapor Phase Growth of Centimeter-Sized Band Gap Engineered Cesium Lead Halide Perovskite Single-Crystal Thin Films with Color-tunable Stimulated Emission

Single crystal metal halide perovskites thin films are considered to be a promising optical, optoelectronic materials with extraordinary performance due to their low defect densities. However, it is still difficult to achieve large-scale perovskite single-crystal thin films (SCTFs) with tunable bandgap by vapor-phase deposition method. Herein, the synthesis of CsPbCl_3(1–x)Br_3x SCTFs with centimeter size (1 cm × 1 cm) via vapor-phase deposition is reported. The Br composition of CsPbCl_3(1–x)Br_3x SCTFs can be gradually tuned from x = 0 to x = 1, leading the corresponding bandgap to change from 2.29 to 2.91 eV. Additionally, an low-threshold (≈23.9 µJ cm⁻²) amplified spontaneous emission is achieved based on CsPbCl_3(1–x)Br_3x SCTFs at room temperature, and the wavelength is tuned from 432 to 547 nm by varying the Cl/Br ratio. Importantly, the high-quality CsPbCl_3(1–x)Br_3x SCTFs are ideal optical gain medium with high gain up to 1369.8 ± 101.2 cm⁻¹. This study not only provides a versatile method to fabricate high quality CsPbCl_3(1–x)Br_3x SCTFs with different Cl/Br ratio, but also paves the way for further research of color-tunable perovskite lasing.     

Organic–Inorganic Perovskite Light‐Emitting Electrochemical Cells with a Large Capacitance

While perovskite light‐emitting diodes typically made with high work function anodes and low work function cathodes have recently gained intense interests. Perovskite light‐emitting devices with two high work function electrodes with interesting features are demonstrated here. Firstly, electroluminescence can be easily obtained from both forward and reverse biases. Secondly, the results of impedance spectroscopy indicate that the ionic conductivity in the iodide perovskite (CH₃NH₃PbI₃) is large with a value of ≈10^?8 S cm^?1. Thirdly, the shift of the emission spectrum in the mixed halide perovskite (CH₃NH₃PbI_3?xBr_x) light‐emitting devices indicates that I^? ions are mobile in the perovskites. Fourthly, this work shows that the accumulated ions at the interfaces result in a large capacitance (≈100 μF cm^?2). The above results conclusively prove that the organic–inorganic halide perovskites are solid electrolytes with mixed ionic and electronic conductivity and the light‐emitting device is a light‐emitting electrochemical cell. The work also suggests that the organic–inorganic halide perovskites are potential energy‐storage materials, which may be applicable in the field of solid‐state supercapacitors and batteries.     

Monitoring the Formation of a CH3NH3PbI3–xClx Perovskite during Thermal Annealing Using X‐Ray Scattering

Grazing incidence wide and small angle X‐ray scattering (GIWAXS and GISAXS) measurements have been used to study the crystallization kinetics of the organolead halide perovskite CH₃NH₃PbI_3–xCl_x during thermal annealing. In situ GIWAXS measurements recorded during annealing are used to characterize and quantify the transition from a crystalline precursor to the perovskite structure. In situ GISAXS measurements indicate an evolution of crystallite sizes during annealing, with the number of crystallites having sizes between 30 and 400 nm increasing through the annealing process. Using ex situ scanning electron microscopy, this evolution in length scales is confirmed and a concurrent increase in film surface coverage is observed, a parameter crucial for efficient solar cell performance. A series of photovoltaic devices are then fabricated in which perovskite films have been annealed for different times, and variations in device performance are explained on the basis of X‐ray scattering measurements.     

Thermoelectric Properties of SnO<Subscript>2</Subscript> Ceramics Doped with Sb and Zn

Polycrystalline SnO₂-based samples (Sn_0.97−x Sb_0.03Zn _x O₂, x = 0, 0.01, 0.03) were prepared by solid-state reactions. The thermoelectric properties of SnO₂ doped with Sb and Zn were investigated from 300 K to 1100 K. X-ray diffraction (XRD) analysis revealed all XRD peaks of all the samples as identical to the rutile structure, except for the x = 0.03 sample, which had a small amount of Zn₂SbO₄ as a secondary phase. We found that the power factor of the x = 0.03 sample was significantly improved due to the simultaneous increase in the electrical conductivity and the Seebeck coefficient. A power factor value of ∼2 × 10⁻⁴ W m⁻¹ K⁻² was obtained for the x = 0.03 sample at 1060 K, 126% higher than that for the undoped sample.     

Suppressed Lattice Disorder for Large Emission Enhancement and Structural Robustness in Hybrid Lead Iodide Perovskite Discovered by High-Pressure Isotope Effect

The soft nature of organic–inorganic halide perovskites renders their lattice particularly tunable to external stimuli such as pressure, undoubtedly offering an effective way to modify their structure for extraordinary optoelectronic properties. Here, using the methylammonium lead iodide as a representative exploratory platform, it is observed that the pressure-driven lattice disorder can be significantly suppressed via hydrogen isotope effect, which is crucial for better optical and mechanical properties previously unattainable. By a comprehensive in situ neutron/synchrotron-based analysis and optical characterizations, a remarkable photoluminescence (PL) enhancement by threefold is convinced in deuterated CD₃ND₃PbI₃, which also shows much greater structural robustness with retainable PL after high peak-pressure compression–decompression cycle. With the first-principles calculations, an atomic level understanding of the strong correlation among the organic sublattice and lead iodide octahedral framework and structural photonics is proposed, where the less dynamic CD₃ND₃⁺ cations are vital to maintain the long-range crystalline order through steric and Coulombic interactions. These results also show that CD₃ND₃PbI₃-based solar cell has comparable photovoltaic performance as CH₃NH₃PbI₃-based device but exhibits considerably slower degradation behavior, thus representing a paradigm by suggesting isotope-functionalized perovskite materials for better materials-by-design and more stable photovoltaic application.     

Use of tertiarybutylphosphine for OMVPE growth of (AlxGa1-x)o.51 In0.49P

This paper reports the results of atmospheric pressure organometallic vapor phase epitaxial growth of (Al _x Ga_1-x )_{0.51 0.49}P thin films using tertiarybutylphosphine (TBP) as the phosphorus source. The trimethylalkyls were used as group III sources. The growth temperature was 680° C. It was observed that V/III ratio dramatically affected the surface morphology and photoluminescence (PL). The epilayers grown at a V/III ratio lower than 60 had rough surfaces and weak PL emission. An input V/III ratio larger than 70 was required to obtain good surfaces and strong PL emission. Good quality (Al_xGa_1-x )_{0.51 0.49}P epilayers forx ≤ 0.62 were obtained at a V/III ratio of 85. The surface morphologies were smooth except for the occurrence of dense oval-shaped hillocks forx > 0.42. The Al distribution coefficient using TBP is the same as for phosphine (PH₃), which was used as the phosphorus source in previous AlGalnP growth. No parasitic reactions between TBP and trimethylalkyls were observed. 10 and 300 K PL emission was observed for all epilayers withx ≤ 0.62. However, the PL peak energy did not follow the band gap, as obtained for (Al_xGa_1-x )_{0.51 0.49}P epilayers grown using PH₃. The PL peak energy at both 10 and 300 K increased with increasingx forx ≤ 0.35, and then became nearly constant with further increases inx. In this region the PL is believed to be from a process involving a deep energy level, induced by an impurity from the TBP, bound to theX conduction band minimum. It was concluded that TBP has the potential to replace PH₃ for OMVPE growth of Al-containing compounds, although the purity needs to be improved.     

Structural and Thermoelectric Properties of Chimney–Ladder Compounds in the Ru-Mn-Si System

We have investigated phase relationships of the sesquisilicide alloys in the Ru-Mn-Si system. A series of chimney–ladder phases Ru_1−x Mn _x Si _y (0.14 ≤ x ≤ 0.97, 1.584 ≤ y ≤ 1.741) are formed over a wide compositional range between Ru₂Si₃ and Mn₄Si₇. We also investigated thermoelectric properties of the directionally solidified Ru_1−x Mn _x Si _y alloys as a function of Mn content and temperature. The dimensionless figure of merit ZT for alloys with high Mn content (x ≥ 0.75) increases as the Mn content increases. The alloy with x = 0.90 exhibits ZT as high as 0.76 at 874 K.     

Tunable properties of cadmium substituted ZnS nanocrystals

Tailored Zn_1−xCd_xS (x = 0, 0.25, 0.5, 0.75 and 1) nanoparticles, synthesized by co-precipitation method under ultrasonic irradiation, were studied by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), UV–Vis and photoluminescence (PL) spectroscopy measurements. According to the XRD results, substitution of Zn²⁺ by Cd²⁺ ion leads to an increase in the lattice parameters and the average size of zinc blended nanoparticles are in the range of 3–4 nm. Transmission electron microscopy image revealed the formation of nano-sized particles with dimension of 5 nm confirming that the samples are quantum dots. The shift observed in the absorption edges by increasing Cd²⁺ ion substitution is ascribed by the alloying effect but the enhancement of band gap energy compared to that of the corresponding bulk value is attributed to the nanometric grain size and quantum confinement effects. The position and intensity of PL emission peaks are tuned with Cd²⁺/Zn²⁺ ion content.     

Photoluminescence studies on InGaAlP layers grown by low-pressure metalorganic chemical vapor deposition

The optical properties for In_0.5(Ga_1-x Al _x )_0.5P (0 <x < 0.4) layers, grown by low-pressure Metalorganic Chemical Vapor Deposition, have been studied with photolominescence (PL) measurement. The PL intensity decreases with the increase of the Al composition (0 <x < 0.4). This dependence could not be accounted for only by the electron overflow from theΓ band to the X band. And the PL intensity is directly proportional to the excitation power at low temperature, below 50 K. On the other hand, the PL intensity is proportional to the second power of the excitation power at a high temperature range (>200 K). These results indicate that non-radiative recombination centers bound to theΓ band in In_0.5(Ga_1-x Al _x )_0.5P play a very important role in the radiation mechanism. PL dependence also shows these non-radiative recombination centers are thought to have strong relation to the aluminum substitution for In_0.5(Ga_1-x Al _x )_0.5P.     

Ultrastable and Reversible Fluorescent Perovskite Films Used for Flexible Instantaneous Display

All‐inorganic halide perovskite materials are regarded as promising materials in information display applications owing to their tunable color, narrow emission peak, and easy processability. However, the photoluminescence (PL) stability of halide perovskite films is still inferior due to their poor thermal stability and hygroscopic properties. Herein, all‐inorganic perovskite films are prepared through vacuum thermal deposition method to enhance thermal and hygroscopic stability. By intentionally adding extra bromide source, a structure of CsPbBr₃ nanocrystals embedded in a CsPb₂Br₅ matrix (CsPbBr₃/CsPb₂Br₅) is formed via an air exposure process, leading to impressive PL stability in ambient atmosphere. In addition, the as‐fabricated CsPbBr₃/CsPb₂Br₅ structure shows enhanced PL intensity due to the dielectric confinement. The CsPbBr₃/CsPb₂Br₅ structure film can almost reserve its initial PL intensity after four months, even stored in ambient atmosphere. The PL intensity for CsPbBr₃/CsPb₂Br₅ films vanishes at elevated temperature and recovers by cooling down in a short time. The reversible PL conversion process can be repeated over hundreds of times. Based on the reversible PL property, prototype thermal‐driven information display devices are demonstrated by employing heating circuits on flexible transparent substrates. These robust perovskite films with reversible PL characteristics promise an alternative solid‐state emitting display.