Revealing Variable Dependences in Hexagonal Boron Nitride Synthesis via Machine Learning.

Wafer-scale monolayer two-dimensional (2D) materials have been realized by epitaxial chemical vapor deposition (CVD) in recent years. To scale up the synthesis of 2D materials, a systematic analysis of how the growth dynamics depend on the growth parameters is essential to unravel its mechanisms. However, the studies of CVD-grown 2D materials mostly adopted the control variate method and considered each parameter as an independent variable, which is not comprehensive for 2D materials growth optimization. Herein, we synthesized a representative 2D material, monolayer hexagonal boron nitride (hBN), on single-crystalline Cu (111) by epitaxial chemical vapor deposition and varied the growth parameters to regulate the hBN domain sizes. Furthermore, we explored the correlation between two growth parameters and provided the growth windows for large flake sizes by the Gaussian process. This new analysis approach based on machine learning provides a more comprehensive understanding of the growth mechanism for 2D materials.

Rationalizing the Effect of Polymer-Controlled Growth of Perovskite Single Crystals on Optoelectronic Properties.

To improve and modulate the optoelectronic properties of single-crystal (SC) metal halide perovskites (MHPs), significant progress has been achieved. Polymer-assisted techniques are a great approach to control the growth rate of SCs effectively. However, the resultant optoelectrical properties induced by polymers are ambiguous and need to be taken into the consideration. In this study, we have synthesized methylammonium lead triiodide (MAPbI3) SCs using polyethylene glycol (PEG) and polystyrene (PS) polymers where PEG contains oxygen functionalities and PS does not. We studied the electrical properties of these SCs under dark and illumination conditions. It was observed that PEG-assisted SCs showed few defects with lower photocurrent as compared to the PS-assisted ones because of defect-mediated conductivity. The results are further verified by transient current response, responsivity, and capacitance-frequency measurements. The present study sheds light on the polymer selection for the growth of MHP SCs and their optoelectronic properties.

Facile NaF Treatment Achieves 20% Efficient ETL-Free Perovskite Solar Cells.

Electron transporting layer (ETL)-free perovskite solar cells (PSCs) exhibit promising progress in photovoltaic devices due to the elimination of the complex and energy-/time-consuming preparation route of ETLs. However, the performance of ETL-free devices still lags behind conventional devices because of mismatched energy levels and undesired interfacial charge recombination. In this study, we introduce sodium fluoride (NaF) as an interface layer in ETL-free PSCs to align the energy level between the perovskite and the FTO electrode. KPFM measurements clearly show that the NaF layer covers the surface of rough underlying FTO very well. This interface modification reduces the work function of FTO by forming an interfacial dipole layer, leading to band bending at the FTO/perovskite interface, which facilitates an effective electron carrier collection. Besides, the part of Na+ ions is found to be able to migrate into the absorber layer, facilitating enlarged grains and spontaneous passivation of the perovskite layer. As a result, the efficiency of the NaF-treated cell reaches 20%, comparable to those of state-of-the-art ETL-based cells. Moreover, this strategy effectively enhances the operational stability of devices by preserving 94% of the initial efficiency after storage for 500 h under continuous light soaking at 55 °C. Overall, these improvements in photovoltaic properties are clear indicators of enhanced interface passivation by NaF-based interface engineering.

Thiocyanate-Passivated Diaminonaphthalene-Incorporated Dion-Jacobson Perovskite for Highly Efficient and Stable Solar Cells.

Two-dimensional (2D) metal halide perovskites have recently emerged as promising photovoltaic materials due to their superior ambient stability and rich structural diversity. However, power conversion efficiencies (PCEs) of the 2D perovskites solar cells (PSCs) still lag behind their three-dimensional (3D) counterpart, particularly due to the anisotropy in the charge carrier mobility and inhomogeneous energy landscape. A promising alternative is Dion-Jacobson (D-J) phase quasi-2D perovskite, where the bulky organic diammonium cations are introduced into inorganic frameworks to remove the weak van der Waals interactions between interlayers and to improve the open-circuit voltage (Voc). Although the D-J phase 2D perovskite shows a homogeneous energy landscape and better charge transport, their poor crystallinity and existence of higher trap states remain a major challenge for the development of high-efficiency solar cells device. To address this issue, here, we report the eclipsed D-J phase 2D perovskite using 1,5-diaminonaphthalene cation and subsequently treated the film with ammonium thiocyanate (NH4SCN) additive to further improve the film crystallinity, out-of-plane orientation, and carrier mobility. We observe that 2 mol NH4SCN surface treatment in NDA-based D-J phase perovskite leads to better film morphology and improved crystallinity, as confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Time-resolved photoluminescence (TRPL) spectroscopy and steady-state space charge limited current (SCLC) mobility measurement reveal a significant reduction of trap-assisted nonradiative recombination and improvement of carrier mobility in the thiocyanate-passivated perovskite. Consequently, the PCE of the NH4SCN-treated (NDA)(MA)3(Pb)4(I)13 perovskite device enhanced nearly 46% from 10.3 to 15.08%. We have further studied intensity-dependent J-V characteristics, which demonstrate the reduction of ideality factor, confirming the effective suppression of trap-assisted nonradiative recombination, consistent with the transient PL results. Electrochemical impedance spectroscopy (EIS) confirms the improved charge carrier transport in NH4SCN additive-treated devices. Interestingly, our additive-engineered unsealed perovskite devices retained 75% of their initial efficiency after 1000 h of continuous storage under 60% relative humidity. This study opens up the strategy for developing high-efficiency and stable 2D perovskite solar cells.

Ultralow contact resistance between semimetal and monolayer semiconductors.

Advanced beyond-silicon electronic technology requires both channel materials and also ultralow-resistance contacts to be discovered1,2. Atomically thin two-dimensional semiconductors have great potential for realizing high-performance electronic devices1,3. However, owing to metal-induced gap states (MIGS)4-7, energy barriers at the metal-semiconductor interface-which fundamentally lead to high contact resistance and poor current-delivery capability-have constrained the improvement of two-dimensional semiconductor transistors so far2,8,9. Here we report ohmic contact between semimetallic bismuth and semiconducting monolayer transition metal dichalcogenides (TMDs) where the MIGS are sufficiently suppressed and degenerate states in the TMD are spontaneously formed in contact with bismuth. Through this approach, we achieve zero Schottky barrier height, a contact resistance of 123 ohm micrometres and an on-state current density of 1,135 microamps per micrometre on monolayer MoS2; these two values are, to the best of our knowledge, the lowest and highest yet recorded, respectively. We also demonstrate that excellent ohmic contacts can be formed on various monolayer semiconductors, including MoS2, WS2 and WSe2. Our reported contact resistances are a substantial improvement for two-dimensional semiconductors, and approach the quantum limit. This technology unveils the potential of high-performance monolayer transistors that are on par with state-of-the-art three-dimensional semiconductors, enabling further device downscaling and extending Moore's law.

Azahomofullerenes as New n-Type Acceptor Materials for Efficient and Stable Inverted Planar Perovskite Solar Cells.

Fullerene derivatives with a strong electron-accepting ability play a crucial role in enhancing both the performance and stability of perovskite solar cells (PSCs). However, most of the used fullerene molecules are based on [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), which limits the device performance due to difficulties in preparing high-quality and uniform thin films. Herein, solution-processable azahomofullerene (AHF) derivatives (abbreviated as AHF-1 and AHF-2) are reported as novel and effective electron-transport layers (ETLs) in p-i-n planar PSCs. Compared to the control PCBM ETL-based PSCs, the devices based on AHFs exhibit higher photovoltaic performances, which is attributed to the enhanced charge-transport properties and improved layer morphology leading to a maximum power conversion efficiency (PCE) of 20.21% in the case of the device based on AHF-2 ETL. Besides, due to the preferable energy band alignment with the perovskite layer, reduced trap states, and suppressed charge recombination, the device with AHF-2 ETL exhibits significantly suppressed hysteresis and improved stability under both ambient and thermal conditions.

Recent Progress in Growth of Single-Crystal Perovskites for Photovoltaic Applications.

The growth of high-quality single-crystal (SC) perovskite films is a great strategy for the fabrication of defect-free perovskite solar cells (PSCs) with photovoltaic parameters close to the theoretical limit, which resulted in high efficiency and superior stability of the device. Plenty of growth methods for perovskite SCs are available to achieve a maximum power conversion efficiency (PCE) surpassing 21% for SC-based PSCs. However, there is still a lot of room to further push the efficiency by considering new crystal growth techniques, interface engineering, passivation approaches, and additive engineering. In this review, we summarize the recent progress in the growth of SC-based perovskite films for the fabrication of high-efficiency and stable PSCs. We describe the impact of SC growth of perovskite films and their quality on the device performance and stability, compared with the commonly used polycrystalline perovskite films. In the last section, the challenges and potential of SCs in PSCs are also covered for future development.

Changes in the Electrical Characteristics of Perovskite Solar Cells with Aging Time.

The last decade has witnessed the impressive progress of perovskite solar cells (PSCs), with power conversion efficiency exceeding 25%. Nevertheless, the unsatisfactory device stability and current-voltage hysteresis normally observed with most PSCs under operational conditions are bottlenecks that hamper their further commercialization. Understanding the electrical characteristics of the device during the aging process is important for the design and development of effective strategies for the fabrication of stable PSCs. Herein, electrochemical impedance spectroscopical (IS) analyses are used to study the time-dependent electrical characteristics of PSC. We demonstrate that both the dark and light ideality factors are sensitive to aging time, indicating the dominant existence of trap-assisted recombination in the investigated device. By analyzing the capacitance versus frequency responses, we show that the low-frequency capacitance increases with increasing aging time due to the accumulation of charges or ions at the interfaces. These results are correlated with the observed hysteresis during the current-voltage measurement and provide an in-depth understanding of the degradation mechanism of PSCs with aging time.

Elucidation of the role of guanidinium incorporation in single-crystalline MAPbI3 perovskite on ion migration and activation energy.

Ion migration plays a significant role in the overall stability and power conversion efficiency of perovskite solar cells (PSCs). This process was found to be influenced by the compositional engineering of the A-site cation in the perovskite crystal structure. However, the effect of partial A-site cation substitution in a methylammonium lead iodide (MAPbI3) perovskite on the ion migration process and its activation energy is not fully understood. Here we study the effect of a guanidinium (GUA) cation on the ion transport dynamics in the single crystalline GUAxMA1-xPbI3 perovskite composition using temperature-dependent electrochemical impedance spectroscopy (EIS). We find that the small substitution of MA with GUA decreases the activation energy for iodide ion migration in comparison to pristine MAPbI3. The presence of a large GUA cation in the 3D perovskite structure induces lattice enlargement, which perturbs the atomic interactions within the perovskite lattice. Consequently, the GUAxMA1-xPbI3 crystal exhibits a higher degree of hysteresis during current-voltage (J-V) measurements than the single-crystalline MAPbI3 counterpart. Our results provide the fundamental understanding of hysteresis, which is commonly observed in GUA-based PSCs and a general protocol for in-depth electrical characterization of perovskite single crystals.

Heavy Water Additive in Formamidinium: A Novel Approach to Enhance Perovskite Solar Cell Efficiency.

Heavy water or deuterium oxide (D2 O) comprises deuterium, a hydrogen isotope twice the mass of hydrogen. Contrary to the disadvantages of deuterated perovskites, such as shorter recombination lifetimes and lower/invariant efficiencies, the serendipitous effect of D2 O as a beneficial solvent additive for enhancing the power conversion efficiency (PCE) of triple-A cation (cesium (Cs)/methylammonium (MA)/formaminidium (FA)) perovskite solar cells from ≈19.2% (reference) to 20.8% (using 1 vol% D2 O) with higher stability is reported. Ultrafast optical spectroscopy confirms passivation of trap states, increased carrier recombination lifetimes, and enhanced charge carrier diffusion lengths in the deuterated samples. Fourier transform infrared spectroscopy and solid-state NMR spectroscopy validate the N-H2 group as the preferential isotope exchange site. Furthermore, the NMR results reveal the induced alteration of the FA to MA ratio due to deuteration causes a widespread alteration to several dynamic processes that influence the photophysical properties. First-principles density functional theory calculations reveal a decrease in PbI6 phonon frequencies in the deuterated perovskite lattice. This stabilizes the PbI6 structures and weakens the electron-LO phonon (Fröhlich) coupling, yielding higher electron mobility. Importantly, these findings demonstrate that selective isotope exchange potentially opens new opportunities for tuning perovskite optoelectronic properties.

Atomic Layer Deposition of an Effective Interface Layer of TiN for Efficient and Hysteresis-Free Mesoscopic Perovskite Solar Cells.

Perovskite solar cells (PSCs) have experienced outstanding advances in power conversion efficiencies (PCEs) by employing new electron transport layers (ETLs), interface engineering, optimizing perovskite morphology, and improving charge collection efficiency. In this work, we study the role of a new ultrathin interface layer of titanium nitride (TiN) conformally deposited on a mesoporous TiO2 (mp-TiO2) scaffold using the atomic layer deposition method. Our characterization results revealed that the presence of TiN at the ETL/perovskite interface improves the charge collection as well as reduces the interface recombination. We find that the morphology (grain size) and optical properties of the perovskite film deposited on the optimized mp-TiO2/TiN ETL are improved drastically, leading to devices with a maximum PCE of 19.38% and a high open-circuit voltage (Voc) of 1.148 V with negligible hysteresis and improved environmental (∼40% RH) and thermal (80 °C) stabilities.

Cost-Effective and Semi-Transparent PbS Quantum Dot Solar Cells Using Copper Electrodes.

PbS quantum dots (QDs) have gained significant attention as promising solution-based materials for third generation of photovoltaic (PV) devices, thanks to their size-tunable band gap, air stability, and low-cost solution processing. Gold (Au), despite its high cost, is the standard electrode in the conventional PbS QD PV architecture because of its perfect alignment with valence levels of PbS QDs. However, to comply with manufacturing requirements for scalable device processing, alternative cost-effective electrodes are urgently required. Here, we employed an interface engineering approach and deposited poly(3-hexylthiophene-2,5-diyl) as a hole transport layer on 1,2-ethanedithiol-capped PbS QDs in order to adjust the valence band of QDs with the work function of inexpensive copper (Cu) electrodes. In fact, this is the first report of a Au-free PbS QD PV system employing the conventional device structure. Our Cu-based device shows a maximum power conversion efficiency (PCE) of 8.7% which is comparable with that of the Au-based device (10.2%). Interestingly, the P3HT-based device shows improved stability with relatively 10% PCE loss after 230 h under continuous illumination. Moreover, using an ultrathin Cu electrode, a semitransparent PbS QD PV is fabricated with a remarkably high average visible transparency of 26% and a PCE of 7.4%.

Tuning, optimization, and perovskite solar cell device integration of ultrathin poly(3,4-ethylene dioxythiophene) films via a single-step all-dry process.

For semicrystalline poly(3,4-ethylene dioxythiophene) (PEDOT), oxidative chemical vapor deposition (oCVD) enables systematic control over the b-axis lattice parameter (π-π stacking distance). Decreasing the b-axis lattice parameter increases the charge transfer integral, thus enhancing intracrystallite mobility. To reduce the barrier to intercrystallite transport, oCVD conditions were tailored to produce pure face-on crystallite orientation rather than the more common edge-on orientation. The face-on oriented oCVD PEDOT with the lowest b-axis lattice parameter displayed the highest in-plane electrical conductivity (σdc = 2800 S/cm), largest optical bandgap (2.9 eV), and lowest degree of disorder as characterized by the Urbach band edge energy. With the single step oCVD process at growth conditions compatible with direct deposition onto flexible plastic substrates, the ratio σdc/σop reached 50. As compared to spun-cast PEDOT:polystyrene sulfonate, integration of oCVD PEDOT as a hole transport layer (HTL) improved both the power conversion efficiency (PCE) and shelf-life stability of inverted perovskite solar cells (PSC).

Synergistic ligand exchange and UV curing of PbS quantum dots for effective surface passivation.

Lead sulfide (PbS) quantum dots (QDs) are promising materials in solution-processed photovoltaic (PV) devices due to their tunable bandgap and low-cost processing. Replacing the long oleic acid ligands of the as-synthesized QDs with shorter ligands is a key step for making functional QD PVs with correctly tuned band energies and reduced non-radiative recombination centers. In this work, we study the effect of ultraviolet (UV) treatment of PbS QD layers on the QD surface states during ligand exchange. We demonstrate that this straightforward approach effectively reduces the surface trap states and passivates the surface of QDs. We find that UV treatment reduces the density of hydroxyl groups attached to the QD surface and improves the bonding of short ligands to the QD surface. Multiple analyses show the reduction of nonradiative recombination centers for the UV-treated sample. The power conversion efficiency (PCE) of our optimized PbS QD device reached 10.7% (vs. 9% for the control device) and was maintained above 10% after 230 h of constant illumination.

Charge Accumulation, Recombination, and Their Associated Time Scale in Efficient (GUA) x (MA)1-x PbI3-Based Perovskite Solar Cells.

Here, we study the influence of guanidinium (GUA) ions on the open-circuit voltage (V oc) in the (GUA) x (MA)1-x PbI3 based perovskite solar cells. We demonstrate that incorporation of GUA forms electronic and ionic accumulation regions at the interface of the electron transporting layer and perovskite absorber layer. Our electrochemical impedance spectroscopy results prove that the formed accumulation region is associated with the enhanced surface charge capacitance and photovoltage. Furthermore, we also demonstrate the influence of the GUA ions on the enhanced interfacial and bulk electronic properties due to more efficient charge transfer between the bulk and interfaces and the reduced electronic defect energy levels.

A relatively wide-bandgap and air-stable donor polymer for fabrication of efficient semitransparent and tandem organic photovoltaics.

Organic photovoltaics (OPVs) have attracted tremendous attention in the field of thin-film solar cells due to their wide range of applications, especially for semitransparent devices. Here, we synthesize a dithiaindacenone-thiophene-benzothiadiazole-thiophene alternating donor copolymer named poly{[2,7-(5,5-didecyl-5H-1,8-dithia-as-indacenone)]-alt-[5,5-(5',6'-dioctyloxy-4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]} (PDTIDTBT), which shows a relatively wide bandgap of 1.82 eV, good mobility, and high transmittance and ambient stability. In this work, we fabricate an OPV device using monolayer graphene as top electrode. Due to the stability of PDTIDTBT in air and water, we use a wet transfer technique for graphene to fabricate semitransparent OPVs. We demonstrate OPVs based on the PDTIDTBT:Phenyl-C61/71-butyric acid methyl ester (PCBM) blend with maximum power conversion efficiencies (PCEs) of 6.1 and 4.75% using silver and graphene top electrodes, respectively. Our graphene-based device shows a high average visible transmittance (AVT) of 55%, indicating the potential of PDTIDTBT for window application and tandem devices. Therefore, we also demonstrate tandem devices using the PDTIDTBT:Phenyl-C61-butyric acid methyl ester (PC60BM) blend in both series and parallel connections with average PCEs of 7.3 and 7.95%, respectively. We also achieve a good average PCE of 8.26% with an average open circuit voltage (Voc) of 1.79 V for 2-terminal tandem OPVs using this blend. Based on tandem design, an OPV with PCE of 6.45% and AVT of 38% is demonstrated. Moreover, our devices show improved shelf life and ultraviolet (UV) stability (using CdSe/ZnS core shell quantum dots [QDs]) in ambient with 45% relative humidity.

Synergistic interface and compositional engineering of inverted perovskite solar cells enables highly efficient and stable photovoltaic devices.

Recently, interface and compositional engineering have been effective approaches in the field of perovskite solar cells (PSCs). In this work, the surface of the nickel oxide layer and perovskite composition are modified by poly[(9,9-bis(30-((N,N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] dibromide (PFN-P2) and deionized (DI) water, respectively, which result in a device with 20.5% efficiency and great stability.

Oxygen Plasma-Induced p-Type Doping Improves Performance and Stability of PbS Quantum Dot Solar Cells.

PbS quantum dots (QDs) have been extensively studied for photovoltaic applications, thanks to their facile and low-cost fabrication processing and interesting physical properties such as size dependent and tunable band gap. However, the performance of PbS QD-based solar cells is highly sensitive to the humidity level in the ambient air, which is a serious obstacle toward its practical applications. Although it has been previously revealed that oxygen doping of the hole transporting layer can mitigate the cause of this issue, the suggested methods to recover the device performance are time-consuming and relatively costly. Here, we report a low-power oxygen plasma treatment as a rapid and low-cost method to effectively recover the device performance and stability. Our optimization results show that a 10 min treatment is the best condition, resulting in an enhanced power conversion efficiency from 6.9% for the as-prepared device to 9% for the plasma treated one. Moreover, our modified device shows long-term shelf-life stability.

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array.

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as-deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air-stable active-layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water-repellent ability of the OPV device.

Efficient metal halide perovskite light-emitting diodes with significantly improved light extraction on nanophotonic substrates.

Metal halide perovskite has emerged as a promising material for light-emitting diodes. In the past, the performance of devices has been improved mainly by optimizing the active and charge injection layers. However, the large refractive index difference among different materials limits the overall light extraction. Herein, we fabricate efficient methylammonium lead bromide light-emitting diodes on nanophotonic substrates with an optimal device external quantum efficiency of 17.5% which is around twice of the record for the planar device based on this material system. Furthermore, optical modelling shows that a high light extraction efficiency of 73.6% can be achieved as a result of a two-step light extraction process involving nanodome light couplers and nanowire optical antennas on the nanophotonic substrate. These results suggest that utilization of nanophotonic structures can be an effective approach to achieve high performance perovskite light-emitting diodes.