Synergistic Surface Modification for High-Efficiency Perovskite Nanocrystal Light-Emitting Diodes: Divalent Metal Ion Doping and Halide-Based Ligand Passivation.

Surface defects of metal halide perovskite nanocrystals (PNCs) substantially compromise the optoelectronic performances of the materials and devices via undesired charge recombination. However, those defects, mainly the vacancies, are structurally entangled with each other in the PNC lattice, necessitating a delicately designed strategy for effective passivation. Here, a synergistic metal ion doping and surface ligand exchange strategy is proposed to passivate the surface defects of CsPbBr3 PNCs with various divalent metal (e.g., Cd2+ , Zn2+, and Hg2+ ) acetate salts and didodecyldimethylammonium (DDA+ ) via one-step post-treatment. The addition of metal acetate salts to PNCs is demonstrated to suppress the defect formation energy effectively via the ab initio calculations. The developed PNCs not only have near-unity photoluminescence quantum yield and excellent stability but also show luminance of 1175 cd m-2 , current efficiency of 65.48 cd A-1 , external quantum efficiency of 20.79%, wavelength of 514 nm in optimized PNC light-emitting diodes with Cd2+ passivator and DDA ligand. The "organic-inorganic" hybrid engineering approach is completely general and can be straightforwardly applied to any combination of quaternary ammonium ligands and source of metal, which will be useful in PNC-based optoelectronic devices such as solar cells, photodetectors, and transistors.

The Role of SnO2 Processing on Ionic Distribution in Double-Cation-Double Halide Perovskites.

Moving toward a future of efficient, accessible, and less carbon-reliant energy devices has been at the forefront of energy research innovations for the past 30 years. Metal-halide perovskite (MHP) thin films have gained significant attention due to their flexibility of device applications and tunable capabilities for improving power conversion efficiency. Serving as a gateway to optimize device performance, consideration must be given to chemical synthesis processing techniques. Therefore, how does common substrate processing techniques influence the behavior of MHP phenomena such as ion migration and strain? Here, we demonstrate how a hybrid approach of chemical bath deposition (CBD) and nanoparticle SnO2 substrate processing significantly improves the performance of (FAPbI3)0.97(MAPbBr3)0.03 by reducing micro-strain in the SnO2 lattice, allowing distribution of K+ from K-Cl treatment of substrates to passivate defects formed at the interface and produce higher current in light and dark environments. X-ray diffraction reveals differences in lattice strain behavior with respect to SnO2 substrate processing methods. Through use of conductive atomic force microscopy (c-AFM), conductivity is measured spatially with MHP morphology, showing higher generation of current in both light and dark conditions for films with hybrid processing. Additionally, time-of-flight secondary ionization mass spectrometry (ToF-SIMS) observed the distribution of K+ at the perovskite/SnO2 interface, indicating K+ passivation of defects to improve the power conversion efficiency (PCE) and device stability. We show how understanding the role of ion distribution at the SnO2 and perovskite interface can help reduce the creating of defects and promote a more efficient MHP device.

Disentangling Electronic Transport and Hysteresis at Individual Grain Boundaries in Hybrid Perovskites via Automated Scanning Probe Microscopy.

Underlying the rapidly increasing photovoltaic efficiency and stability of metal halide perovskites (MHPs) is the advancement in the understanding of the microstructure of polycrystalline MHP thin film. Over the past decade, intense efforts have been aimed at understanding the effect of microstructures on MHP properties, including chemical heterogeneity, strain disorder, phase impurity, etc. It has been found that grain and grain boundary (GB) are tightly related to lots of microscale and nanoscale behavior in MHP thin films. Atomic force microscopy (AFM) is widely used to observe grain and boundary structures in topography and subsequently to study the correlative surface potential and conductivity of these structures. For now, most AFM measurements have been performed in imaging mode to study the static behavior; in contrast, AFM spectroscopy mode allows us to investigate the dynamic behavior of materials, e.g., conductivity under sweeping voltage. However, a major limitation of AFM spectroscopy measurements is that they require manual operation by human operators, and as such only limited data can be obtained, hindering systematic investigations of these microstructures. In this work, we designed a workflow combining the conductive AFM measurement with a machine learning (ML) algorithm to systematically investigate grain boundaries in MHPs. The trained ML model can extract GBs locations from the topography image, and the workflow drives the AFM probe to each GB location to perform a current-voltage (IV) curve automatically. Then, we are able to have IV curves at all GB locations, allowing us to systematically understand the property of GBs. Using this method, we discovered that the GB junction points are less conductive, potentially more photoactive, and can play critical roles in MHP stability, while most previous works only focused on the difference between GB and grains.

Exploring the Relationship of Microstructure and Conductivity in Metal Halide Perovskites via Active Learning-Driven Automated Scanning Probe Microscopy.

Electronic transport and hysteresis in metal halide perovskites (MHPs) are key to the applications in photovoltaics, light emitting devices, and light and chemical sensors. These phenomena are strongly affected by the materials microstructure including grain boundaries, ferroic domain walls, and secondary phase inclusions. Here, we demonstrate an active machine learning framework for "driving" an automated scanning probe microscope (SPM) to discover the microstructures responsible for specific aspects of transport behavior in MHPs. In our setup, the microscope can discover the microstructural elements that maximize the onset of conduction, hysteresis, or any other characteristic that can be derived from a set of current-voltage spectra. This approach opens new opportunities for exploring the origins of materials functionality in complex materials by SPM and can be integrated with other characterization techniques either before (prior knowledge) or after (identification of locations of interest for detail studies) functional probing.

A Universal Perovskite Nanocrystal Ink for High-Performance Optoelectronic Devices.

Semiconducting lead halide perovskite nanocrystals (PNCs) are regarded as promising candidates for next-generation optoelectronic devices due to their solution processability and outstanding optoelectronic properties. While the field of light-emitting diodes (LEDs) and photovoltaics (PVs), two prime examples of optoelectronic devices, has recently seen a multitude of efforts toward high-performance PNC-based devices, realizing both devices with high efficiencies and stabilities through a single PNC processing strategy has remained a challenge.  In this work, diphenylpropylammonium (DPAI) surface ligands, found through a judicious ab-initio-based ligand search, are shown to provide a solution to this problem. The universal PNC ink with DPAI ligands presented here, prepared through a solution-phase ligand-exchange process, simultaneously allows single-step processed LED and PV devices with peak electroluminescence external quantum efficiency of 17.00% and power conversion efficiency of 14.92% (stabilized output 14.00%), respectively. It is revealed that a careful design of the aromatic rings such as in DPAI is the decisive factor in bestowing such high performances, ease of solution processing, and improved phase stability up to 120 days. This work illustrates the power of ligand design in producing PNC ink formulations for high-throughput production of optoelectronic devices; it also paves a path for "dual-mode" devices with both PV and LED functionalities.

Guanidinium-Pseudohalide Perovskite Interfaces Enable Surface Reconstruction of Colloidal Quantum Dots for Efficient and Stable Photovoltaics.

Complete surface passivation of colloidal quantum dots (CQDs) and their strong electronic coupling are key factors toward high-performance CQD-based photovoltaics (CQDPVs). Also, the CQD matrices must be protected from oxidative environments, such as ambient air and moisture, to guarantee air-stable operation of the CQDPVs. Herein, we devise a complementary and effective approach to reconstruct the oxidized CQD surface using guanidinium and pseudohalide. Unlike conventional halides, thiocyanate anions provide better surface passivation with effective replacement of surface oxygen species and additional filling of defective sites, whereas guanidinium cations promote the construction of epitaxial perovskite bridges within the CQD matrix and augment electronic coupling. Additionally, we replace a defective 1,2-ethanedithiol-treated CQD hole transport layer (HTL) with robust polymeric HTLs, based on a judicious consideration of the energy level alignment established at the CQD/HTL interface. These efforts collectively result in high-performance and stable CQDPVs with photocurrents over 30 mA cm-2, ∼80% quantum efficiency at excitonic peaks and stable operation under humid and ambient conditions. Elucidation of carrier dynamics further reveals that interfacial recombination associated with band alignment governs both the CQDPV performance and stability.

Solvent Engineering of Colloidal Quantum Dot Inks for Scalable Fabrication of Photovoltaics.

Development of colloidal quantum dot (CQD) inks enables single-step spin-coating of compact CQD films of appropriate thickness, enabling the promising performance of CQD photovoltaics (CQDPVs). Today's highest-performing CQD inks rely on volatile n-butylamine (BTA), but it is incompatible with scalable deposition methods since a rapid solvent evaporation results in irregular film thickness with an uneven surface. Here, we present a hybrid solvent system, consisting of BTA and N,N-dimethylformamide, which has a favorable acidity for colloidal stability as well as an appropriate vapor pressure, enabling a stable CQD ink that can be used to fabricate homogeneous, large-area CQD films via spray-coating. CQDPVs fabricated with the CQD ink exhibit suppressed charge recombination as well as fast charge extraction compared with conventional CQD ink-based PVs, achieving an improved power conversion efficiency (PCE) of 12.22% in spin-coated devices and the highest ever reported PCE of 8.84% among spray-coated CQDPVs.

Hybrid Surface Passivation for Retrieving Charge Collection Efficiency of Colloidal Quantum Dot Photovoltaics.

Efficient charge collection in photovoltaics is a key issue toward their high performance. Despite the promising performance of colloidal quantum dot (CQD)-based photovoltaics (CQDPVs), they suffer significant dissipation of photocurrent due to imperfect surface passivation of the CQD hole transport layer (HTL) by a single 1,2-ethaneditihol (EDT) ligand. To address the critical drawback of existing CQDPVs, we offer a hybrid passivation strategy, including both EDT and thiocyanate (SCN). The hybrid passivation leads to seamless surface passivation of CQDs, remarkably suppressing charge recombination. This strategy also augments the p-doping density of the CQD, resulting in a pronounced energy level bending at the active layer/HTL interface and facilitating efficient charge separation. Moreover, enhanced electronic coupling across the CQDs (originating from reduced inter-dot spacing) promotes rapid charge extraction. Consequently, the flawless charge collection by a hybrid-passivated HTL successfully retrieves the photocurrent, achieving an enhanced CQDPV power conversion efficiency of 12.70% compared with 11.49% for the control device.

Improving Charge Collection from Colloidal Quantum Dot Photovoltaics by Single-Walled Carbon Nanotube Incorporation.

Improving charge collection is one of the key issues for high-performance PbS colloidal quantum dot photovoltaics (CQDPVs) due to the considerable charge loss resulting from the low mobility and large defect densities of the 1,2-ethanedithiol-treated PbS quantum dot hole-transporting layer (HTL). To overcome these limitations, single-walled carbon nanotubes (SWNTs) and C60-encapsulated SWNTs (C60@SWNTs) are incorporated into the HTL in CQDPVs. SWNT-incorporated CQDPV demonstrates a significantly improved short-circuit current density (JSC), and C60@SWNT-incorporated CQDPV exhibits an even higher JSC than that of pristine SWNT. Both result in improved power-conversion efficiencies. Hole-selective, photoinduced charge extraction with linearly increasing voltage measurements demonstrates that SWNT or C60@SWNT incorporation improves hole-transporting behavior, rendering suppressed charge recombination and enhanced mobility of the HTL. The enhanced p-type characteristics and the improved hole diffusion lengths of SWNT- or C60@SWNT-incorporated HTL bring improvement of the entire hole-transporting length and enable lossless hole collection, which results in the JSC enhancement of the CQDPVs.

Vibrational Spectrocopic Studies of Organic Molecules After Encapsulation Inside Single-Walled Carbon Nanotubes.

7,7,8,8-tetracyano-p-quinodimethane (TCNQ), tetrathiafulvalene (TTF), and dodecanethiol (DoSH) were encapsulated inside single-walled carbon nanotubes (SWNTs), (TCNQ@SWNT, TTF@SWNT, and DoSH@SWNT). We measured the Fourier transform infra-red (FTIR) spectra and X-ray diffraction (XRD) patterns to confirm the encapsulation of organic molecules. Slight shifts of the FTIR peaks and the disappearance of an XRD peak at ~6°, corresponding to the SWNT (10) reflection, were observed. From the measurements of the current-voltage curves, it was revealed that the current of TTF@ SWNT and DoSH@SWNT decreased, and the current of TCNQ@SWNT increased compared with that of pristine SWNTs.

Electric Property Change of Single-Walled Carbon Nanotube by the Encapsulation of Aliphatic Thiols.

The encapsulation of single-walled carbon nanotubes (SWNTs) with aliphatic thiol compounds with a relatively small amount of ionization energy achieves n-type doping of SWNTs. Thiol compounds encapsulated inside nanotubes in vacuum drastically change the electric properties of SWNTs by a charge transfer between the two species. The simplicity of the synthetic process offers a viable route for large-scale production of SWNTs with controlled doping states by using mat-type SWNTs. Optical characterization (Raman and near-infrared spectrum) and electric property (conductivity) reveals that a charge transfer between the SWNTs and compounds occurs through the difference in the ionization energy and electron affinity. We confirm an electron density change in SWNTs through optical spectroscopy and conductivity measurement in vacuum. X-ray photoelectron spectroscopy also reveals that the compounds are predominantly encapsulated inside SWNTs.

Improved Field Emission of Three-Dimensional Single-Walled Carbon Nanotube Networks Suspended Between ZnO Nanorods.

We report field emission (FE) properties of three dimensional single-walled carbon nanotube (3-D SWNT) networks synthesized between ZnO nanorods on textured Si wafer. The FE properties are measured for turn-on field and field enhancement factor, and are compared with other types of SWNT films such as synthesized SWNT films and spray SWNT films. 3-D SWNT has lower turn-on field and higher field enhancement factor than other SWNT films.

A Study of the Wettability of Single-Walled Carbon Nanotube Films on Flat and Textured Si Substrates.

Contact angle measurements are investigated on the surface of single-walled carbon nanotube (SWNT) films directly formed on flat and textured Si substrates using a thermal chemical vapor deposition method. The SWNT films on the textured Si consist of a multiscale structure composed of nanoscale SWNTs and a microscale textured Si. They show superhydrophobic properties in which the water contact angle was around 161°. A direct surface treatment to them increase the contact angle to 174°. The reversible wettability of the SWNT films formed on the textured Si substrates is confirmed through the oxidation process using an acid mixture of nitric and sulfuric acids and a successive reduction procedure via heating treatment in an NH3 environment.

Conductivity Properties of Single-Walled Carbon Nanotubes Upon the Encapsulation of TTF and TCNQ.

N-type and p-type single-walled carbon nanotubes (SWNTs) were formed via the encapsulation of tetrathiafulvalene (TTF) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) inside SWNTs, respectively. Raman, near-infrared, and X-ray photoelectron spectrometer were used to confirm the encapsulation. From measurements of the current-voltage curves in a vacuum, it was revealed that current of TTF-encapsulated SWNTs decreased and TCNQ-encapsulated SWNTs increased comparing with that of pristine SWNTs. This was resulted from electron-donating (TTF) and withdrawing (TCNQ) character into SWNTs.

Suppressed Interfacial Charge Recombination of PbS Quantum Dot Photovoltaics by Graphene Incorporated into ZnO Nanoparticles.

Single-layer graphene (SLG) was incorporated into ZnO nanoparticles (NPs), and use of this material in photovoltaic devices generated significant changes. The Fermi level of ZnO NPs underwent a downshift, whereas the conduction and valence bands were maintained with increasing SLG concentrations. Furthermore, the effective defect densities were reduced and carrier mobility was enhanced. Colloidal quantum dot photovoltaics (CQDPVs) with the SLG-incorporated ZnO NP layer as an electron transporting layer achieved significant performance enhancement. Poor performing CQDPVs were also observed with incorporation of an excess amount of SLG. This trend paralleled the interfacial charge recombination trends of CQDPVs. Effective suppression of interfacial recombination was achieved for CQDPVs with an appropriate SLG concentration, whereas dramatically increased interfacial recombination was observed for CQDPVs with an excess of SLG. For CQDPVs with appropriate SLG incorporation, efficient defect passivation and enhanced electron mobility of ZnO NPs facilitated loss-less electron transfer and efficient electron extraction without compromising the favorable energy level alignment. Excess SLG incorporation led to an increase in recombination within the PbS QD layer due to the presence of an energy barrier. This simple and powerful strategy provides an effective method for modulating the interfacial properties of CQDPVs.

Field Emission and Electrical Properties of Perovskite.

We investigate characteristic field emission properties of methyl ammonium mixed-halide perovskite (CH3NH3PbI3-xClx) and their current change under one laser pulse. To analyze these properties, we fabricated inverted-type mixed-halide perovskite solar cells which exhibit a device efficiency of 9.31% under A.M 1.5 condition. Under one laser pulse varying from 420 nm to 580 nm, perovskite layer considerably reacted from 420 nm to 440 nm and then gradually decreased in current. A turnon field of 5.56 V and a field enhancement factor of 3183 were obtained from one spin-coating perovskite layer and in eight times of perovskite spin-coating cycles, a turn-on field of 6.70 V and a field enhancement factor of 5110 were observed.

Photocurrent Enhancement of CdSe Quantum-Dot Sensitized Solar Cells Incorporating Single-Walled Carbon Nanotubes.

We demonstrate quantum-dot sensitized solar cells (QDSSCs) which have colloidal CdSe quantum dots (TOPO-CdSe) as a sensitizer onto mesoporous TiO2 photoanodes. CdS quantum-dot (QD) layer plays a role of buffer layer for direct adsorption of TOPO-CdSe. We incorporate single-walled carbon nanotubes with TiO2 photoanode of our QDSSCs to facilitate efficient charge transfer. Shortcircuit current densities (Jsc) of our QDSSCs are enhanced while other parameters are maintained. Furthermore, we apply inert N2 pressure onto our sensitized photoanodes and observe 44% of Jsc enhancement with respect to pristine sample. Consequently, light-harvesting efficiency of our QDSSCs are increased. Significant series resistance reduction is observed from electrochemical impedance spectroscopy, indicating better interface contact between TiO2 photoanode and TOPOCdSe QD sensitizer are achieved.

Performance Enhancement of 3-Mercaptopropionic Acid-Capped CdSe Quantum-Dot Sensitized Solar Cells Incorporating Single-Walled Carbon Nanotubes.

We fabricated a series of linker-assisted quantum-dot-sensitized solar cells based on the ex situ self-assembly of CdSe quantum dots (QDs) onto TiO2 electrode using sulfide/polysulfide (S(2-)/Sn(2-)) as an electrolyte and Au cathode. Our cell were combined with single-walled carbon nanotubes (SWNTs) by two techniques; One was mixing SWNTs with TiO2 electrode and the other was spraying SWNTs onto Au electrode. Absorption spectra were used to confirm the adsorption of QDs onto TiO2 electrode. Cell performance was measured on samples containing and not-containing SWNTs. Samples mixing SWNTs with TiO2 showed higher cell efficiency, on the while sample spraying SWNTs onto Au electrode showed lower efficiency compared with pristine sample (not-containing SWNTs). Electrochemical impedance spectroscopy analysis suggested that SWNTs can act as either barriers or excellent carrier transfers according their position and mixing method.

Selective Growth of Metallic and Semiconducting Single Walled Carbon Nanotubes on Textured Silicon.

We fabricated the etched Si substrate having the pyramidal pattern size from 0.5 to 4.2 µm by changing the texturing process parameters, i.e., KOH concentration, etching time, and temperature. Single walled carbon nanotubes (SWNTs) were then synthesized on the etched Si substrates with different pyramidal pattern by chemical vapor deposition. We investigated the optical and electronic properties of SWNT film grown on the etched Si substrates of different morphology by using scanning electron microscopy, Raman spectroscopy and conducting probe atomic force microscopy. We confirmed that the morphology of substrate strongly affected the selective growth of the SWNT film. Semiconducting SWNTs were formed on larger pyramidal sized Si wafer with higher ratio compared with SWNTs on smaller pyramidal sized Si.