Sn-Based Perovskite Halides for Electronic Devices.

Because of its less toxicity and electronic structure analogous to that of lead, tin halide perovskite (THP) is currently one of the most favorable candidates as an active layer for optoelectronic and electric devices such as solar cells, photodiodes, and field-effect transistors (FETs). Promising photovoltaics and FETs performances have been recently demonstrated because of their desirable electrical and optical properties. Nevertheless, THP's easy oxidation from Sn2+ to Sn4+ , easy formation of tin vacancy, uncontrollable film morphology and crystallinity, and interface instability severely impede its widespread application. This review paper aims to provide a basic understanding of THP as a semiconductor by highlighting the physical structure, energy band structure, electrical properties, and doping mechanisms. Additionally, the key chemical instability issues of THPs are discussed, which are identified as the potential bottleneck for further device development. Based on the understanding of the THPs properties, the key recent progress of THP-based solar cells and FETs is briefly discussed. To conclude, current challenges and perspective opportunities are highlighted.

Carbon Nanodots as Electron Transport Materials in Organic Light Emitting Diodes and Solar Cells.

Charge injection and transport interlayers play a crucial role in many classes of optoelectronics, including organic and perovskite ones. Here, we demonstrate the beneficial role of carbon nanodots, both pristine and nitrogen-functionalized, as electron transport materials in organic light emitting diodes (OLEDs) and organic solar cells (OSCs). Pristine (referred to as C-dots) and nitrogen-functionalized (referred to as NC-dots) carbon dots are systematically studied regarding their properties by using cyclic voltammetry, Fourier-transform infrared (FTIR) and UV-Vis absorption spectroscopy in order to reveal their energetic alignment and possible interaction with the organic semiconductor's emissive layer. Atomic force microscopy unravels the ultra-thin nature of the interlayers. They are next applied as interlayers between an Al metal cathode and a conventional green-yellow copolymer-in particular, (poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,1',3}-thiadiazole)], F8BT)-used as an emissive layer in fluorescent OLEDs. Electrical measurements indicate that both the C-dot- and NC-dot-based OLED devices present significant improvements in their current and luminescent characteristics, mainly due to a decrease in electron injection barrier. Both C-dots and NC-dots are also used as cathode interfacial layers in OSCs with an inverted architecture. An increase of nearly 10% in power conversion efficiency (PCE) for the devices using the C-dots and NC-dots compared to the reference one is achieved. The application of low-cost solution-processed materials in OLEDs and OSCs may contribute to their wide implementation in large-area applications.

Preparation of hydrogen, fluorine and chlorine doped and co-doped titanium dioxide photocatalysts: a theoretical and experimental approach.

Titanium dioxide (TiO2) has a strong photocatalytic activity in the ultra-violet part of the spectrum combined with excellent chemical stability and abundance. However, its photocatalytic efficiency is prohibited by limited absorption within the visible range derived from its wide band gap value and the presence of charge trapping states located at the band edges, which act as electron-hole recombination centers. Herein, we modify the band gap and improve the optical properties of TiO2 via co-doping with hydrogen and halogen. The present density functional theory (DFT) calculations indicate that hydrogen is incorporated in interstitial sites while fluorine and chlorine can be inserted both as interstitial and oxygen substitutional defects. To investigate the synergy of dopants in TiO2 experimental characterization techniques such as Fourier transform infrared (FTIR), X-ray diffraction (XRD), X-ray and ultra-violet photoelectron spectroscopy (XPS/UPS), UV-Vis absorption and scanning electron microscopy (SEM) measurements, have been conducted. The observations suggest that the oxide's band gap is reduced upon halogen doping, particularly for chlorine, making this material promising for energy harvesting devices. The studies on hydrogen production ability of these materials support the enhanced hydrogen production rates for chlorine doped (Cl:TiO2) and hydrogenated (H:TiO2) oxides compared to the pristine TiO2 reference.

Molecular materials as interfacial layers and additives in perovskite solar cells.

Solar cells based on organo-metal halide perovskites have gained unprecedented research interest over the last few years due to their low-cost solution processability, high power conversion efficiency, which has recently reached a certified value of 25.2%, and abundance of raw materials. Nevertheless, the best efficiencies remain below the Shockley-Queisser theoretical limit of 32.5% due to several losses arising from either defect traps present in the bulk of the perovskite absorber or at the device heterointerfaces. While bulk defects are detrimental for the device performance by mainly limiting the open circuit voltage, interfacial layers are also crucial. They dictate the charge transfer/transport from the perovskite layer to the collecting electrodes, hence influencing the device photocurrent, but also act as protective barriers against oxygen and moisture penetration. Molecular materials and additives are widely used to improve the bulk properties of perovskite absorbers through the formation of high-quality perovskite films with superior optoelectronic properties, and improved crystallinity, and also of electronically clean interfaces with minimum losses during charge transfer/transport. In this review, we analyze the predominant pathways that contribute to voltage and current losses due to poor interfaces and also due to non-radiative recombination losses arising from inferior perovskite morphology and its inherent polycrystalline and highly defective nature. We then discuss strategies for achieving interfacial organic and inorganic molecular materials for application as electron and hole transport layers in perovskite solar cells with ideal energy levels, high charge mobilities and improved thermal, photo, and structural stability. Moreover, the prerequisites for molecular additives to achieve dimensionality engineering, defect passivation, molecular cross-linking, interfacial energy alignment and electronic doping are thoroughly discussed. Finally, we examine prospects for future research directions and commercialization.

Suppressing the Photocatalytic Activity of Zinc Oxide Electron-Transport Layer in Nonfullerene Organic Solar Cells with a Pyrene-Bodipy Interlayer.

Organic solar cells based on nonfullerene acceptors have recently witnessed a significant rise in their power conversion efficiency values. However, they still suffer from severe instability issues, especially in an inverted device architecture based on the zinc oxide bottom electron transport layers. In this work, we insert a pyrene-bodipy donor-acceptor dye as a thin interlayer at the photoactive layer/zinc oxide interface to suppress the degradation reaction of the nonfullerene acceptor caused by the photocatalytic activity of zinc oxide. In particular, the pyrene-bodipy-based interlayer inhibits the direct contact between the nonfullerene acceptor and zinc oxide hence preventing the decomposition of the former by zinc oxide under illumination with UV light. As a result, the device photostability was significantly improved. The π-π interaction between the nonfullerene acceptor and the bodipy part of the interlayer facilitates charge transfer from the nonfullerene acceptor toward pyrene, which is followed by intramolecular charge transfer to bodipy part and then to zinc oxide. The bodipy-pyrene modified zinc oxide also increased the degree of crystallization of the photoactive blend and the face-on stacking of the polymer donor molecules within the blend hence contributing to both enhanced charge transport and increased absorption of the incident light. Furthermore, it decreased the surface work function as well as surface energy of the zinc oxide film all impacting in improved power conversion efficiency values of the fabricated cells with champion devices reaching values up to 9.86 and 11.80% for the fullerene and nonfullerene-based devices, respectively.

A hysteresis-free perovskite transistor with exceptional stability through molecular cross-linking and amine-based surface passivation.

Organo-metal halide perovskite field-effect transistors present serious challenges in terms of device stability and hysteresis in the current-voltage characteristics. Migration of ions located at grain boundaries and surface defects in the perovskite film are the main reasons for instability and hysteresis issues. Here, we introduce a perovskite grain molecular cross-linking approach combined with amine-based surface passivation to address these issues. Molecular cross-linking was achieved through hydrogen bond interactions between perovskite halogens and dangling bonds present at grain boundaries and a hydrophobic cross-linker, namely diethyl-(12-phosphonododecyl)phosphonate, added to the precursor solution. With our approach, we obtained smooth and compact perovskite layers composed of tightly bound grains hence significantly suppressing the generation and migration of ions. Moreover, we achieved efficient surface passivation of the perovskite films upon surface treatment with an amine-bearing polymer, namely polyethylenimine ethoxylated. With our synergistic grain and surface passivation approach, we were able to demonstrate the first perovskite transistor with a complete lack of hysteresis and unprecedented stability upon continuous operation under ambient conditions. Added to the merits are its ambipolar transport of opposite carriers with balanced hole and electron mobilities of 4.02 and 3.35 cm2 V-1 s-1, respectively, its high Ion/Ioff ratio >104 and the lowest sub-threshold swing of 267 mV dec-1 reported to date for any perovskite transistor. These remarkable achievements obtained through a cost-effective molecular cross-linking of grains combined with amine-based surface passivation of the perovskite films open a new era and pave the way for the practical application of perovskite transistors in low-cost electronic circuits.

Ambipolar Triple Cation Perovskite Field Effect Transistors and Inverters.

Ambipolar perovskite field-effect transistors and inverters with balanced mobilities are demonstrated. Thin-film field-effect-transistor-like inverters are developed, and a maximum gain of 23 in the first quadrant for VDD = 80 V is obtained.

Bandgap tuning of mixed organic cation utilizing chemical vapor deposition process.

Bandgap tuning of a mixed organic cation perovskite is demonstrated via chemical vapor deposition process. The optical and electrical properties of the mixed organic cation perovskite can be manipulated by varying the growth time. A slight shift of the absorption band to shorter wavelengths is demonstrated with increasing growth time, which results in the increment of the current density. Hence, based on the optimized growth time, our device exhibits an efficiency of 15.86% with negligible current hysteresis.

New Horizons for Perovskite Solar Cells Employing DNA-CTMA as the Hole-Transporting Material.

We investigate solution-processed low-temperature lead-halide perovskite solar cells employing deoxyribose nucleic acid (DNA)-hexadecyl trimethyl ammonium chloride (CTMA) as the hole-transport layer and (6,6)-phenyl C61 -butyric acid methyl ester (PCBM) as electron-acceptor layer in an inverted p-i-n device configuration. The perovskite solar cells utilizing a bio-based charge-transport layer demonstrate power conversion efficiency values of 15.86 %, with short-circuit current density of 20.85 mA cm(-2) , open circuit voltage of 1.04 V, and fill factor of 73.15 %, and improved lifetime. DNA-based devices maintained above 85 % of the initial efficiency after 50 days in air.

Organohalide Lead Perovskites for Photovoltaic Applications.

Perovskite solar cells have recently exhibited a significant leap in efficiency due to their broad absorption, high optical absorption coefficient, very low exciton binding energy, long carrier diffusion lengths, efficient charge collection, and very high open-circuit potential, similar to that of III-IV semiconductors. Unlike silicon solar cells, perovskite solar cells can be developed from a variety of low-temperature solutions processed from inexpensive raw materials. When the perovskite absorber film formation is optimized using solvent engineering, a power conversion efficiency of over 21% has been demonstrated, highlighting the unique photovoltaic properties of perovskite materials. Here, we review the current progress in perovskite solar cells and charge transport materials. We highlight crucial challenges and provide a summary and prospects.

Organic devices based on nickel nanowires transparent electrode.

Herein, we demonstrate a facile approach to synthesize long nickel nanowires and discuss its suitability to replace our commonly used transparent electrode, indium-tin-oxide (ITO), by a hydrazine hydrate reduction method where nickel ions are reduced to nickel atoms in an alkaline solution. The highly purified nickel nanowires show high transparency within the visible region, although the sheet resistance is slightly larger compared to that of our frequently used transparent electrode, ITO. A comparison study on organic light emitting diodes and organic solar cells, using commercially available ITO, silver nanowires, and nickel nanowires, are also discussed.

High performance polymer tandem solar cell.

A power conversion efficiency of 9.02% is obtained for a fully solution-processed polymer tandem solar cell, based on the diketopyrrolopyrrole unit polymer as a low bandgap photoactive material in the rear subcell, in conjunction with a new robust interconnecting layer. This interconnecting layer is optically transparent, electrically conductive, and physically strong, thus, the charges can be collected and recombined in the interconnecting layer under illumination, while the charge is generated and extracted under dark conditions. This indicates that careful interface engineering of the charge-carrier transport layer is a useful approach to further improve the performance of polymer tandem solar cells.

Fine-tuning optical and electronic properties of graphene oxide for highly efficient perovskite solar cells.

Simplifying the process of fine-tuning the electronic and optical properties of graphene oxide (GO) is of importance in order to fully utilize it as the hole interfacial layer (HIL). We introduced silver trifluoromethanesulfonate (AgOTf), an inorganic chemical dopant, that tunes and controls the properties of single-layered GO films synthesized by chemical vapor deposition. The morphology, work function, mobility, sheet resistance, and transmittance of the GO film were systematically tuned by various doping concentrations. We further developed a solution-processable low-temperature hole interfacial layer (HIL) poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS):AgOTf-doped GO HIL in highly efficient perovskite solar cells. The PEDOT: PSS:AgOTf-doped GO HIL grants the desirable charge-collection in the HIL allowing the entire device to be prepared at temperatures less than 120 °C. The fabricated perovskite solar cells utilize a rigid substrate and demonstrate compelling photovoltaic performance with a power conversion efficiency (PCE) of 11.90%. Moreover, flexible devices prepared using a polyethylene terephthalate (PET)/ITO demonstrate a PCE of 9.67%, while ITO-free flexible devices adopting PET/aluminum doped zinc oxide (AZO)/silver (Ag)/AZO demonstrate a PCE of 7.97%. This study shows that the PEDOT: PSS:AgOTf-doped GO HIL has significant potential to contribute to the development of low-cost solar cells.

Plasmon enhanced organic devices utilizing highly ordered nanoimprinted gold nanodisks and nitrogen doped graphene.

High performance organic devices including polymer solar cells (PSCs) and light emitting diodes (PLEDs) were successfully demonstrated with the presence of highly ordered nanoimprinted Au nanodisks (Au NDs) in their solution-processed active/emissive layers, respectively. PSCs and PLEDs were fabricated using a low bandgap polymer and acceptor, nitrogen doped multiwalled carbon nanotubes poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]-thiophenediyl] (n-MWCNTs:PTB7), and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) and (4,4-N,N-dicarbazole) biphenyl (CBP) doped with tris(2-phenylpyridine) iridium(iii) (Ir(ppy)3) as active/emissive layers, respectively. We synthesized nitrogen doped graphene and used it as anodic buffer layer in both devices. The localized surface plasmon resonance (LSPR) effect from Au NDs clearly contributed to the increase in light absorption/emission in the active layers from electromagnetic field enhancement, which originated from the excited LSPR in PSCs and PLEDs. In addition to the high density of LSPR and strong exciton-SP coupling, the electroluminescent (EL) enhancement is ascribed to enhanced spontaneous emission rates. This is due to the plasmonic near-field effect induced by Au NDs. The PSCs and PLEDs exhibited 14.98% (8.08% to 9.29%) under one sun of simulated air mass 1.5 global (AM1.5G) illumination (100 mW cm(-2)) and 19.18% (8.24 to 9.82 lm W(-1)) enhancement in the power conversion efficiencies (PCEs) compared to the control devices without Au NDs.

Effect of ZnO:Cs2CO3 on the performance of organic photovoltaics.

We demonstrate a new solution-processed electron transport layer (ETL), zinc oxide doped with cesium carbonate (ZnO:Cs2CO3), for achieving organic photovoltaics (OPVs) with good operational stability at ambient air. An OPV employing the ZnO:Cs2CO3 ETL exhibits a fill factor of 62%, an open circuit voltage of 0.90 V, and a short circuit current density of -6.14 mA/cm(2) along with 3.43% power conversion efficiency. The device demonstrated air stability for a period over 4 weeks. In addition, we also studied the device structure dependence on the performance of organic photovoltaics. Thus, we conclude that ZnO:Cs2CO3 ETL could be employed in a suitable architecture to achieve high-performance OPV.

High-performance inverted tandem polymer solar cells utilizing thieno[3,4-c]pyrrole-4,6-dione copolymer.

We demonstrated the inverted solution processed tandem polymer solar cells, in which transparent pH-neutral poly(3,4-ethylenedioxylenethiophene)-polystylene sulfonic acid (PEDOT:PSS) and lithium zinc oxide layers were used as a recombination layer. We have used poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione):[6,6]-phenyl-C61 butyric acid methyl ester (PBDTTPD:PC61BM) and poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d] silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]:[6,6]-phenyl-C70 butyric acid methyl ester (PSBTBT:PC70BM) as the active layers for front and rear subcells, respectively. The pH-neutral PEDOT:PSS/LZO serves as an electron- and hole-collecting and recombination layer. Our tandem solar cells showed a high open circuit voltage (Voc) of 1.54 V, a short circuit current density (Jsc) of 7.55 mA/cm(2), and a fill factor (FF) of 64.79% along with the power conversion efficiency of 7.53%. The Voc value of our tandem solar cells is an ideal summation of Voc values from front and rear subcells.

Inverted organic photovoltaic device with a new electron transport layer.

We demonstrate that there is a new solution-processed electron transport layer, lithium-doped zinc oxide (LZO), with high-performance inverted organic photovoltaic device. The device exhibits a fill factor of 68.58%, an open circuit voltage of 0.86 V, a short-circuit current density of -9.35 cm/mA2 along with 5.49% power conversion efficiency. In addition, we studied the performance of blend ratio dependence on inverted organic photovoltaics. Our device also demonstrates a long stability shelf life over 4 weeks in air.

High performance organic photovoltaics with zinc oxide and graphene oxide buffer layers.

We report air stable inverted organic photovoltaics (OPVs) incorporating graphene oxide (GO) and solution processed zinc oxide (ZnO) as hole transport and electron transport layers, respectively. Both the hole transport layer and the electron transport layer (HTL and ETL) are of advantage in high transparency and environmental stability. The use of GO and ZnO in poly(2,7-carbazole) derivative (PCDTBT):fullerene derivative (PC70BM)-based inverted OPVs leads to an improved device stability and enhanced high open circuit voltage (V(oc)) of 0.81 V, a short-circuit current density (J(sc)) of 14.10 mA cm(-2), and a fill factor (FF) of 54.44 along with a power conversion efficiency of 6.20%.

Extremely stable all solution processed organic tandem solar cells with TiO2/GO recombination layer under continuous light illumination.

One approach to harvest a wide solar spectral solar energy is to stack two solar cells with different absorption characteristics in a tandem cell architecture. Herein, solution processed tandem solar cells, with highly transparent titanium oxide (TiO2) and graphene oxide (GO) as an efficient recombination layer, were designed, fabricated and characterized. We have adopted poly[(4,4'-bis(3-ethylhexyl)dithieno[3,2-b:''3'-d]silole)-2,6-diyl-alt-(2,5-(3-(2-ethylhexyl)thiophen-2-yl)thiazolo[5,4-d]thiazole]:indene-C60 bisadduct (PSEHTT:ICBA) and poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]:[6,6]-phenyl-C70 butyric acid methyl ester (PSBTBT:PC70BM) as the active layers for the front and rear cells, respectively. The TiO2/GO serves as an electron and hole collecting and recombination layer. The tandem solar cells showed a high open circuit voltage (VOC) 1.62 V, a moderate short circuit current density (JSC) 8.23 mA cm(-2), fill factor (FF) 62.98%, leading to the power conversion efficiency of 8.40%. The obtained VOC value of tandem solar cells is ideal for the summation of VOCs attained from front and rear cells and it is evident that our tandem solar cells are well connected in series. Moreover, this tandem cell exhibits a 20% drop in conversion efficiency under continuous AM illumination for 2880 h.