Energy-Level Interpretation of Carbazole Derivatives in Self-Assembling Monolayer.

Energy-level alignment is a crucial factor in the performance of thin-film devices, such as organic light-emitting diodes and photovoltaics. One way to adjust these energy levels is through chemical modification of the molecules involved. However, this approach may lead to unintended changes in the optical and/or electrical properties of the compound. An alternative method for energy-level adjustment at the interface is the use of self-assembling monolayers (SAMs). Initially, SAMs with passive spacers were employed, creating a surface dipole moment that altered the work function (WF) of the electrode. However, recent advancements have led to the synthesis of SAM molecules with active spacers. This development necessitates considering not only the modification of the electrode's WF but also the ionization energy (IE) of the molecule itself. To measure both the IE of SAM molecules and their impact on the electrode's WF, a relatively simple method is photo-electric emission spectroscopy. Solar cell performance parameters have a higher correlation coefficient with the ionization energy of SAM molecules with carbazole derivatives as spacers (up to 0.97) than the work function of the modified electrode (up to 0.88). Consequently, SAMs consisting of molecules with active spacers can be viewed as hole transport layers rather than interface layers.

Fluorene- and fluorenone-based molecules as electron-transporting SAMs for photovoltaic devices.

New semiconductors containing fluorene or fluorenone central fragments along with phosphonic acid anchoring groups were synthesized and investigated as electron transporting materials for possible application in photovoltaic devices. These derivatives demonstrate good thermal stability and suitable electrochemical properties for effective electron transport from perovskite, Sb2S3 and Sb2Se3 absorber layers. Self-assembled fluorene and fluorenone electron-transporting materials have shown improved substrate wettability, indicating bond formation between monolayer-forming compounds and the ITO, TiO2, Sb2S3, or Sb2Se3 surface. Additionally, investigated materials have compatible energetic band alignment and can passivate perovskite interface defects, which makes them interesting candidates for application in the n-i-p structure perovskite solar cell.

Asymmetric Triphenylethylene-Based Hole Transporting Materials for Highly Efficient Perovskite Solar Cells.

Molecular hole-transporting materials (HTMs) having triphenylethylene central core were designed, synthesized, and employed in perovskite solar cell (PSC) devices. The synthesized HTM derivatives were obtained in a two- or three-step synthetic procedure, and their characteristics were analyzed by various thermoanalytical, optical, photophysical, and photovoltaic techniques. The most efficient PSC device recorded a 23.43% power conversion efficiency. Furthermore, the longevity of the device employing V1509 HTM surpassed that of PSC with state-of-art spiro-OMeTAD as the reference HTM.

Branched Fluorenylidene Derivatives with Low Ionization Potentials as Hole-Transporting Materials for Perovskite Solar Cells.

A group of small-molecule hole-transporting materials (HTMs) that are based on fluorenylidene fragments were synthesized and tested in perovskite solar cells (PSCs). The investigated compounds were synthesized by a facile two-step synthesis, and their properties were measured using thermoanalytical, optoelectronic, and photovoltaic methods. The champion PSC device that was doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) reached a power conversion efficiency of 22.83%. The longevity of the PSC device with the best performing HTM, V1387, was evaluated in different conditions and compared to that of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD), showing improved stability. This work provides an alternative HTM strategy for fabricating efficient and stable PSCs.

Investigation of biphenyl enamines for applications as p-type semiconductors.

Due to the ease of synthesis and the ability to easily tune properties, organic semiconductors are widely researched and used in many optoelectronic applications. Requirements such as thermal stability, appropriate energy levels and charge-carrier mobility have to be met in order to consider the suitability of an organic semiconductor for a specific application. Balancing of said properties is not a trivial task; often one characteristic is sacrificed to improve the other and therefore a search for well-balanced materials is necessary. Herein, seven new charge-transporting biphenyl-based enamine molecules are reported. The new materials were synthesized using a simple one-step reaction without the use of expensive transition metal catalysts. It was observed that subtle variations in the structure lead to notable changes in the properties. Materials exhibited high thermal stability and relatively high carrier drift mobility, reaching 2 × 10-2 cm2V-1 s-1 (for BE3) at strong electric fields. Based on the results, three materials show the potential to be applied in organic light emitting diodes and solar cells.

Chloride-Based Additive Engineering for Efficient and Stable Wide-Bandgap Perovskite Solar Cells.

Metal halide perovskite based tandem solar cells are promising to achieve power conversion efficiency beyond the theoretical limit of their single-junction counterparts. However, overcoming the significant open-circuit voltage deficit present in wide-bandgap perovskite solar cells remains a major hurdle for realizing efficient and stable perovskite tandem cells. Here, a holistic approach to overcoming challenges in 1.8 eV perovskite solar cells is reported by engineering the perovskite crystallization pathway by means of chloride additives. In conjunction with employing a self-assembled monolayer as the hole-transport layer, an open-circuit voltage of 1.25 V and a power conversion efficiency of 17.0% are achieved. The key role of methylammonium chloride addition is elucidated in facilitating the growth of a chloride-rich intermediate phase that directs crystallization of the desired cubic perovskite phase and induces more effective halide homogenization. The as-formed 1.8 eV perovskite demonstrates suppressed halide segregation and improved optoelectronic properties.

Epitaxial Lateral Overgrowth of GaN on a Laser-Patterned Graphene Mask.

Epitaxial lateral overgrowth (ELO) of GaN epilayers on a sapphire substrate was studied by using a laser-patterned graphene interlayer. Monolayer graphene was transferred onto the sapphire substrate using a wet transfer technique, and its quality was confirmed by Raman spectroscopy. The graphene layer was ablated using a femtosecond laser, which produced well-defined patterns without damaging the underlying sapphire substrate. Different types of patterns were produced for ELO of GaN epilayers: stripe patterns were ablated along the [1¯100]sapphire and [112¯0]sapphire directions, a square island pattern was ablated additionally. The impact of the graphene pattern on GaN nucleation was analyzed by scanning electron microscopy. The structural quality of GaN epilayers was studied by cathodoluminescence. The investigation shows that the laser-ablated graphene can be integrated into the III-nitride growth process to improve crystal quality.

The Crystalline Structure of Thin Bismuth Layers Grown on Silicon (111) Substrates.

Bismuth films with thicknesses between 6 and ∼30 nm were grown on Si (111) substrate by molecular beam epitaxy (MBE). Two main phases of bismuth - α-Bi and ß-Bi - were identified from high-resolution X-ray diffraction (XRD) measurements. The crystal structure dependencies on the layer thicknesses of these films were analyzed. ß-Bi layers were epitaxial and homogenous in lateral regions that are greater than 200 nm despite the layer thickness. Further, an increase in in-plane 2θ values showed the biaxial compressive strain. For comparison, α-Bi layers are misoriented in six in-plane directions and have ß-Bi inserts in thicker layers. That leads to smaller (about 60 nm) lateral crystallites which are compressively strained in all three directions. Raman measurement confirmed the XRD results. The blue-sift of Raman signals compared with bulk Bi crystals occurs due to the phonon confinement effect, which is larger in the thinnest α-Bi layers due to higher compression.

MOVPE Growth of GaN via Graphene Layers on GaN/Sapphire Templates.

The remote epitaxy of GaN epilayers on GaN/sapphire templates was studied by using different graphene interlayer types. Monolayer, bilayer, double-stack of monolayer, and triple-stack of monolayer graphenes were transferred onto GaN/sapphire templates using a wet transfer technique. The quality of the graphene interlayers was examined by Raman spectroscopy. The impact of the interlayer type on GaN nucleation was analyzed by scanning electron microscopy. The graphene interface and structural quality of GaN epilayers were studied by transmission electron microscopy and X-ray diffraction, respectively. The influence of the graphene interlayer type is discussed in terms of the differences between remote epitaxy and van der Waals epitaxy. The successful exfoliation of GaN membrane is demonstrated.

Cut from the Same Cloth: Enamine-Derived Spirobifluorenes as Hole Transporters for Perovskite Solar Cells.

To attain commercial viability, perovskite solar cells (PSCs) have to be reasonably priced, highly efficient, and stable for a long period of time. Although a new record of a certified power conversion efficiency (PCE) value over 25% was achieved, PSC performance is limited by the lack of hole-transporting materials (HTMs), which extract positive charges from the light-absorbing perovskite layer and carry them to the electrode. Here, we report spirobifluorene-based HTMs with finely tuned energy levels, high glass-transition temperature, and excellent charge mobility and conductivity enabled by molecularly engineered enamine arms. HTMs are synthesized using simple condensation chemistry, which does not require costly catalysts, inert reaction conditions, and time-consuming product purification procedures. Enamine-derived HTMs allow the fabrication of PSCs reaching a maximum PCE of 19.2% and stability comparable to spiro-OMeTAD. This work demonstrates that simple enamine condensation reactions could be used as a universal path to obtain HTMs for highly efficient and stable PSCs.

Adduct-based p-doping of organic semiconductors.

Electronic doping of organic semiconductors is essential for their usage in highly efficient optoelectronic devices. Although molecular and metal complex-based dopants have already enabled significant progress of devices based on organic semiconductors, there remains a need for clean, efficient and low-cost dopants if a widespread transition towards larger-area organic electronic devices is to occur. Here we report dimethyl sulfoxide adducts as p-dopants that fulfil these conditions for a range of organic semiconductors. These adduct-based dopants are compatible with both solution and vapour-phase processing. We explore the doping mechanism and use the knowledge we gain to 'decouple' the dopants from the choice of counterion. We demonstrate that asymmetric p-doping is possible using solution processing routes, and demonstrate its use in metal halide perovskite solar cells, organic thin-film transistors and organic light-emitting diodes, which showcases the versatility of this doping approach.

Oxidized Spiro-OMeTAD: Investigation of Stability in Contact with Various Perovskite Compositions.

The power conversion efficiency of perovskite solar cells (PSCs) has risen steadily in recent years; however, one important aspect of the puzzle remains to be solved-the long-term stability of the devices. We believe that understanding the underlying reasons for the observed instability and finding means to circumvent it is crucial for the future of this technology. Not only the perovskite itself but also other device components are susceptible to thermal degradation, including the materials comprising the hole-transporting layer. In particular, the performance-enhancing oxidized hole-transporting materials have attracted our attention as a potential weak component in the system. Therefore, we performed a series of experiments with oxidized spiro-OMeTAD to determine the stability of the material interfaced with five most popular perovskite compositions under thermal stress. It was found that oxidized spiro-OMeTAD is readily reduced to the neutral molecule upon interaction with all five perovskite compositions. Diffusion of iodide ions from the perovskite layer is the main cause for the reduction reaction which is greatly enhanced at elevated temperatures. The observed sensitivity of the oxidized spiro-OMeTAD to ion diffusion, especially at elevated temperatures, causes a decrease in the conductivity observed in the doped films of spiro-OMeTAD, and it also contributes significantly to a drop in the performance of PSCs operated under prolonged thermal stress.

Monolithic perovskite/silicon tandem solar cell with >29% efficiency by enhanced hole extraction.

Tandem solar cells that pair silicon with a metal halide perovskite are a promising option for surpassing the single-cell efficiency limit. We report a monolithic perovskite/silicon tandem with a certified power conversion efficiency of 29.15%. The perovskite absorber, with a bandgap of 1.68 electron volts, remained phase-stable under illumination through a combination of fast hole extraction and minimized nonradiative recombination at the hole-selective interface. These features were made possible by a self-assembled, methyl-substituted carbazole monolayer as the hole-selective layer in the perovskite cell. The accelerated hole extraction was linked to a low ideality factor of 1.26 and single-junction fill factors of up to 84%, while enabling a tandem open-circuit voltage of as high as 1.92 volts. In air, without encapsulation, a tandem retained 95% of its initial efficiency after 300 hours of operation.

The detrimental effect of AlGaN barrier quality on carrier dynamics in AlGaN/GaN interface.

Carrier recombination and scattering at the semiconductor boundaries can substantially limit the device efficiency. However, surface and interface recombination is generally neglected in the nitride-based devices. Here, we study carrier recombination and diffusivity in AlGaN/GaN/sapphire heterointerfaces with AlGaN barriers of different quality. We employ the light induced transient grating and time-resolved photoluminescence spectroscopy techniques to extract carrier lifetime in different depths of the GaN buffer as well as in the AlGaN barrier, and to evaluate the carrier diffusion coefficient in the buffer. Moreover, we assess interface recombination velocity, Shockley-Read-Hall and radiative recombination rates. We reveal the adverse barrier influence on carrier dynamics in the underlying buffer: AlGaN barrier accelerates the nonradiative carrier recombination in the GaN buffer. The interface recombination velocity in the GaN buffer increases with decreasing AlGaN barrier quality, and the dominating recombination mechanism switches from Shockley-Read-Hall to interface recombination. These phenomena are governed by a cumulative effect of various interface-deteriorating barrier defects. Meanwhile, the carrier diffusivity in the GaN buffer is not affected by the AlGaN barrier. We conclude that barrier-accelerated interface recombination can become a major carrier loss mechanism in AlGaN/GaN interface, and may substantially limit the efficiency in nitride-based UV LEDs.

Inexpensive Hole-Transporting Materials Derived from Tröger's Base Afford Efficient and Stable Perovskite Solar Cells.

The synthesis of three enamine hole-transporting materials (HTMs) based on Tröger's base scaffold are reported. These compounds are obtained in a three-step facile synthesis from commercially available materials without the need of expensive catalysts, inert conditions or time-consuming purification steps. The best performing material, HTM3, demonstrated 18.62 % PCE in PSCs, rivaling spiro-OMeTAD in efficiency, and showing markedly superior long-term stability in non-encapsulated devices. In dopant-free PSCs, HTM3 outperformed spiro-OMeTAD by a factror of 1.6. The high glass-transition temperature (Tg =176 °C) of HTM3 also suggests promising perspectives in device applications.

Highly efficient nanocrystalline CsxMA1-xPbBrx perovskite layers for white light generation.

Perovskite light converting layers optimization for cost-efficient white light emitting diodes (LED) was demonstrated. High excitation independent internal quantum efficiency (IQE) of 80% and weakly excitation dependent PL spectra suitable for white light generation were obtained in the mixed cation CsxMA1-xPbBr3 perovskite nanocrystal layers with optimal x = 0.3 being determined by effective surface passivation and phase mixing as revealed by x-ray diffraction. Enhancement of the PL homogeneity and the external quantum efficiency (EQE) were secured when using 2,2',2″-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole (TPBi) additive in the layer preparation process. Excitation dependent PL intensity, decay time, and IQE revealed that the high emission efficiency of the layers originates from a dominant radiative localized exciton recombination (130 ns) weakly influenced by the nonradiative free carrier recombination (750 ns). Warm and cool white LEDs with correlated color temperature 3000 K and 5600 K, and color rendering index 82 and 74, respectively, were realized by using the optimized perovskite layers, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) red emitter and a blue LED.

Significant Carrier Extraction Enhancement at the Interface of an InN/p-GaN Heterojunction under Reverse Bias Voltage.

In this paper, a superior-quality InN/p-GaN interface grown using pulsed metalorganic vapor-phase epitaxy (MOVPE) is demonstrated. The InN/p-GaN heterojunction interface based on high-quality InN (electron concentration 5.19 × 1018 cm-3 and mobility 980 cm²/(V s)) showed good rectifying behavior. The heterojunction depletion region width was estimated to be 22.8 nm and showed the ability for charge carrier extraction without external electrical field (unbiased). Under reverse bias, the external quantum efficiency (EQE) in the blue spectral region (300⁻550 nm) can be enhanced significantly and exceeds unity. Avalanche and carrier multiplication phenomena were used to interpret the exclusive photoelectric features of the InN/p-GaN heterojunction behavior.

Efficient and Stable Perovskite Solar Cells Using Low-Cost Aniline-Based Enamine Hole-Transporting Materials.

Metal-halide perovskites offer great potential to realize low-cost and flexible next-generation solar cells. Low-temperature-processed organic hole-transporting layers play an important role in advancing device efficiencies and stabilities. Inexpensive and stable hole-transporting materials (HTMs) are highly desirable toward the scaling up of perovskite solar cells (PSCs). Here, a new group of aniline-based enamine HTMs obtained via a one-step synthesis procedure is reported, without using a transition metal catalyst, from very common and inexpensive aniline precursors. This results in a material cost reduction to less than 1/5 of that for the archetypal spiro-OMeTAD. PSCs using an enamine V1091 HTM exhibit a champion power conversion efficiency of over 20%. Importantly, the unsealed devices with V1091 retain 96% of their original efficiency after storage in ambient air, with a relative humidity of 45% for over 800 h, while the devices fabricated using spiro-OMeTAD dropped down to 42% of their original efficiency after aging. Additionally, these materials can be processed via both solution and vacuum processes, which is believed to open up new possibilities for interlayers used in large-area all perovskite tandem cells, as well as many other optoelectronic device applications.

Long-Term Stability of the Oxidized Hole-Transporting Materials used in Perovskite Solar Cells.

The vast majority of the hole transporting materials require the use of chemical doping as an essential step for preparation of efficient perovskite solar cells. An oxidized organic hole-transporting material, obtained during a doping procedure, could potentially be one of the weak links in the device composition. It is not uncommon for the solar cell to heat up under summer sun; therefore, all device components must possess some degree of resistance to repetitive thermal stress. In the current publication, a series of oxidized hole-transporting materials have been synthesized and their long-term stability investigated. During thermal stability testing of the films, kept at 100 °C under an inert atmosphere, it was observed that oxidized HTMs start to degrade and partly revert to original unoxidized material. It is known that oxidized HTM, formed during doping, is responsible for the increased conductivity and ultimately for better efficiency of hole extraction process in the PSC device; therefore, observed instability of the oxidized HTMs in the thin films at elevated temperatures could be one of the causes of drop in conductivity reported for the doped spiro-OMeTAD. It could also potentially be one of the reasons why perovskite solar cells lose their efficiency under prolonged thermal stress.

Methoxydiphenylamine-substituted fluorene derivatives as hole transporting materials: role of molecular interaction on device photovoltaic performance.

The molecular structure of the hole transporting material (HTM) play an important role in hole extraction in a perovskite solar cells. It has a significant influence on the molecular planarity, energy level, and charge transport properties. Understanding the relationship between the chemical structure of the HTM's and perovskite solar cells (PSCs) performance is crucial for the continued development of the efficient organic charge transporting materials. Using molecular engineering approach we have constructed a series of the hole transporting materials with strategically placed aliphatic substituents to investigate the relationship between the chemical structure of the HTMs and the photovoltaic performance. PSCs employing the investigated HTMs demonstrate power conversion efficiency values in the range of 9% to 16.8% highlighting the importance of the optimal molecular structure. An inappropriately placed side group could compromise the device performance. Due to the ease of synthesis and moieties employed in its construction, it offers a wide range of possible structural modifications. This class of molecules has a great potential for structural optimization in order to realize simple and efficient small molecule based HTMs for perovskite solar cells application.