Photoactivated Mixed In-Plane and Edge-Enriched p-Type MoS2 Flake-Based NO2 Sensor Working at Room Temperature.

Toxic gases are produced during the burning of fossil fuels. Room temperature (RT) fast detection of toxic gases is still challenging. Recently, MoS2 transition metal dichalcogenides have sparked great attention in the research community due to their performance in gas sensing applications. However, MoS2 based gas sensors still suffer from long response and recovery times, especially at RT. Considering this challenge, here, we report photoactivated highly reversible and fast detection of NO2 sensors at room temperature (RT) by using mixed in-plane and edge-enriched p-MoS2 flakes (mixed MoS2). The sensor showed fast response with good sensitivity of ∼10.36% for 10 ppm of NO2 at RT without complete recovery. However, complete recovery was obtained with better sensor performance under UV light illumination at RT. The UV assisted NO2 sensing showed improved performance in terms of fast response and recovery kinetics with enhanced sensitivity to 10 ppm NO2 concentration. The sensor performance is also investigated under thermal energy, and a better sensor performance with reduced sensitivity and high selectivity toward NO2 was observed. A detailed gas sensing mechanism based on the density functional theory (DFT) calculations for favorable NO2 adsorption sites on in-plane and edge-enriched MoS2 flakes is proposed. This study revealed the role of favorable adsorption sites in MoS2 flakes for the enhanced interaction of target gases and developed a highly sensitive, reversible, and fast gas sensor for next-generation toxic gases at room temperature.

Solvent Toolkit for Electrochemical Characterization of Hybrid Perovskite Films.

Organohalide lead (hybrid) perovskites have emerged as competitive semiconducting materials for photovoltaic devices due to their high performance and low cost. To further the understanding and optimization of these materials, solution-based methods for interrogating and modifying perovskite thin films are needed. In this work, we report a hydrofluoroether (HFE) solvent-based electrolyte for electrochemical processing and characterization of organic-inorganic trihalide lead perovskite thin films. Organic perovskite films are soluble in most of the polar organic solvents, and thus until now, they were not considered suitable for electrochemical processing. We have enabled electrochemical characterization and demonstrated a processing toolset for these materials utilizing highly fluorinated electrolytes based on a HFE solvent. Our results show that chemically orthogonal electrolytes based on HFE solvents do not dissolve organic perovskite films and thus allow electrochemical characterization of the electronic structure, investigation of charge transport properties, and potential electrochemical doping of the films with in situ diagnostic capabilities.

Tailoring Nanoscale Morphology of Polymer:Fullerene Blends Using Electrostatic Field.

To tailor the nanomorphology in polymer/fullerene blends, we study the effect of electrostatic field (E-field) on the solidification of poly(3-hexylthiophene-2, 5-diyl) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) bulk heterojunction (BHJ). In addition to control; wet P3HT:PC60BM thin films were exposed to E-field of Van de Graaff (VDG) generator at three different directions-horizontal (H), tilted (T), and vertical (V)-relative to the plane of the substrate. Surface and bulk characterizations of the field-treated BHJs affirmed that fullerene molecules can easily penetrate the spaghetti-like P3HT and move up and down following the E-field. Using E-field treatment, we achieved favorable morphologies with efficient charge separation, transport, and collection. We improve; (1) the hole mobility values up to 19.4 × 10-4 ± 1.6 × 10-4 cm2 V-1 s-1 and (2) the power conversion efficiency (PCE) of conventional and inverted OPVs up to 2.58 ± 0.02% and 4.1 ± 0.40%, respectively. This E-field approach can serve as a new morphology-tuning technique, which is generally applicable to other polymer-fullerene systems.

Shelf life stability comparison in air for solution processed pristine PDPP3T polymer and doped spiro-OMeTAD as hole transport layer for perovskite solar cell.

This data in brief includes forward and reverse scanned current density-voltage (J-V) characteristics of perovskite solar cells with PDPP3T and spiro-OMeTAD as HTL, stability testing conditions of perovskite solar cell shelf life in air for both PDPP3T and spiro-OMeTAD as HTL as per the description in Ref. [1], and individual J-V performance parameters acquired with increasing time exposed in ambient air are shown for both type of devices using PDPP3T and spiro-OMeTAD as HTL. The data collected in this study compares the device stability with time for both PDPP3T and spiro-OMeTAD based perovskite solar cells and is directly related to our research article "solution processed pristine PDPP3T polymer as hole transport layer for efficient perovskite solar cells with slower degradation" [2].

Critical kinetic control of non-stoichiometric intermediate phase transformation for efficient perovskite solar cells.

Organometal trihalide perovskites (OTP) have attracted significant attention as a low-cost and high-efficiency solar cell material. Due to the strong coordination between lead iodide (PbI2) and dimethyl sulfoxide (DMSO) solvent, a non-stoichiometric intermediate phase of MA2Pb3I8(DMSO)2 (MA = CH3NH3(+)) usually forms in the one-step deposition method that plays a critical role in attaining high power conversion efficiency. However, the kinetic understanding of how the non-stoichiometric intermediate phase transforms during thermal annealing is currently absent. In this work, we investigated such a phase transformation and provided a clear picture of three phase transition pathways as a function of annealing conditions. The interdiffusion of MAI and DMSO varies strongly with the annealing temperature and time, thus determining the final film composition and morphology. A surprising finding reveals that the best performing cells contain ∼18% of the non-stoichiometric intermediate phase, instead of pure phase OTP. The presence of such an intermediate phase enables smooth surface morphology and enhances the charge carrier lifetime. Our results highlight the importance of the intermediate phase growth kinetics that could lead to large-scale production of efficient solution processed perovskite solar cells.

Versatile Role of Solvent Additive for Tailoring Morphology in Polymer Solar Cells for Efficient Charge Transport.

In this work role of solvent additive namely 1,8 diiodoctane (DIO) on the nanoscale morphology and its relation with the charge transport of poly(diketopyrrolopyrrole-terthiophene) (PDPP3T):PCBM solar cells has been investigated. Addition of DIO led to enhanced structural ordering as observed from optical measurements. Photovoltaic devices processed with DIO additive showed improved efficiencies due to significant enhancement in short circuit current density. Atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM) images showed that DIO led to finer phase segregation that gave rise to better photovoltaic performance in additive processed active layers. Photoinduced current extraction by linearly increasing voltage (P-CELIV) measurements on PDPP3T:PCBM solar cells revealed higher mobility and extracted charge carrier density for DIO processed devices.

Interfacial Study To Suppress Charge Carrier Recombination for High Efficiency Perovskite Solar Cells.

We report effects of an interface between TiO2-perovskite and grain-grain boundaries of perovskite films prepared by single step and sequential deposited technique using different annealing times at optimum temperature. Nanoscale kelvin probe force microscopy (KPFM) measurement shows that charge transport in a perovskite solar cell critically depends upon the annealing conditions. The KPFM results of single step and sequential deposited films show that the increase in potential barrier suppresses the back-recombination between electrons in TiO2 and holes in perovskite. Spatial mapping of the surface potential within perovskite film exhibits higher positive potential at grain boundaries compared to the surface of the grains. The average grain boundary potential of 300-400 mV is obtained upon annealing for sequentially deposited films. X-ray diffraction (XRD) spectra indicate the formation of a PbI2 phase upon annealing which suppresses the recombination. Transient analysis exhibits that the optimum device has higher carrier lifetime and short carrier transport time among all devices. An optimum grain boundary potential and proper band alignment between the TiO2 electron transport layer (ETL) and the perovskite absorber layer help to increase the overall device performance.

Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a suitable passivation layer to suppress oxidation in metal oxide thin films for enhanced lifetime in inverted organic solar cells.

Solvent engineering towards controlled grain growth in perovskite planar heterojunction solar cells.

We report an effective solvent engineering process to enable controlled perovskite crystal growth and a wider window for processing uniform and dense methyl ammonium lead iodide (MAPbI3) perovskite films. Planar heterojunction solar cells fabricated with this method demonstrate hysteresis-free performance with a power conversion efficiency around 10%. The crystal structure of an organic-based Pb iodide intermediate phase is identified for the first time, which is critical in controlling the crystal growth and optimizing thin film morphology.

Benzothiadiazole-based polymer for single and double junction solar cells with high open circuit voltage.

Single and double junction solar cells with high open circuit voltage were fabricated using poly{thiophene-2,5-diyl-alt-[5,6-bis(dodecyloxy)benzo[c][1,2,5]thiadiazole]-4,7-diyl} (PBT-T1) blended with fullerene derivatives in different weight ratios. The role of fullerene loading on structural and morphological changes was investigated using atomic force microscopy (AFM) and X-ray diffraction (XRD). The XRD and AFM measurements showed that a higher fullerene mixing ratio led to breaking of inter-chain packing and hence resulted in smaller disordered polymer domains. When the PBT-T1:PC60BM weight ratio was 1 : 1, the polymer retained its structural order; however, large aggregated domains formed, leading to poor device performance due to low fill factor and short circuit current density. When the ratio was increased to 1 : 2 and then 1 : 3, smaller amorphous domains were observed, which improved photovoltaic performance. The 1 : 2 blending ratio was optimal due to adequate charge transport pathways giving rise to moderate short circuit current density and fill factor. Adding 1,8-diiodooctane (DIO) additive into the 1 : 2 blend films further improved both the short circuit current density and fill factor, leading to an increased efficiency to 4.5% with PC60BM and 5.65% with PC70BM. These single junction solar cells exhibited a high open circuit voltage at ∼ 0.9 V. Photo-charge extraction by linearly increasing voltage (Photo-CELIV) measurements showed the highest charge carrier mobility in the 1 : 2 film among the three ratios, which was further enhanced by introducing the DIO. The Photo-CELIV measurements with varying delay times showed significantly higher extracted charge carrier density for cells processed with DIO. Tandem devices using P3HT:IC60BA as bottom cell and PBT-T1:PC60BM as top cell exhibited a high open circuit voltage of 1.62 V with 5.2% power conversion efficiency.

Electron and force microscopy characterization of particle size effects and surface phenomena associated with individual natural organic matter fractions.

Natural organic matter (NOM) generically refers to organic substances found in soils, waters, and sediments. It is the brown-to-black, heterogeneous organic material produced through the diagenetic alteration of plant tissue and microbial biomass via a myriad of biotic and abiotic reactions. Since NOM is the primary source of organic carbon in the earth's surficial environment, understanding the processes by which NOM is produced is integral to understanding carbon sequestration, contaminant fate and transport, and other earth surface processes. NOM samples (HA0) consist of nonamphiphilic (HA1), lipid-like (L0 and L1), and strongly amphiphilic (HA2) components. Here we present the structure and morphology of self-assembled NOM components based on scanning electron microscopy (SEM), atomic force microscopy (AFM), and electrostatic force microscopy (EFM) characterizations. Effects of surface charge and hydrophobicity/hydrophilicity of the amphiphile on the interaction and resulting structures were investigated using SEM, AFM, and EFM. Data shows that the component's amphiphilic nature plays a key role in the formation of NOM. SEM data show that aggregates form while AFM/EFM analysis verifies the existence of hydrophobic/hydrophilic moieties in different fractions of HA0. Subsequently, the amphiphilic nature of HA2 will have a substantial effect on interfacial interactions and subsequent self-assembly of HA0's components.

Interplay of nanoscale domain purity and size on charge transport and recombination dynamics in polymer solar cells.

Charge transport and bimolecular recombination dynamics were correlated with nanomorphology in polymer solar cells. The morphology of poly(diketopyrrolopyrrole-terthiophene) (PDPP3T) and phenyl-C61-butyric acid methyl ester (PC60BM) blend films was modified using different solvent additives namely 1-chloronaphthalene (CN), 1,8-diiodooctane (DIO) and 1,8-octanedithiol (ODT) and their role on steady state and transient optoelectronic properties was investigated. The energy filtered transmission electron microscopy (EFTEM) images showed that additives (e.g. CN and DIO) improved the domain purity which leads to significantly higher short circuit current densities (Jsc). However when the cells were processed with the ODT additive, the fill factor (FF) and open circuit voltage (Voc) decreased dramatically. Films processed with the ODT additive showed a smaller domain size but were more connected compared to films processed using CN and DIO additives. Transient photocurrent analysis indicates faster charge collection in the case of CN and DIO processed solar cells and the slowest charge collection in ODT processed solar cells. Interestingly devices processed with the ODT additive also showed the longest charge carrier recombination lifetime and lowest bimolecular recombination coefficient. This is attributed to the smaller donor domains that are connected with each other to provide a more interconnected and efficient charge transport matrix but longer pathways in ODT films. Such a matrix helped the charge to escape from the donor-acceptor interfaces and thus reduces the bimolecular recombination, while the longer pathway increases the charge collection time. Further insight is provided into the selection of processing conditions to achieve an ideal active layer morphology consisting of domains with higher polymer purity and optimal size that lead to higher Jsc and FF.

Enhanced charge transport and photovoltaic performance of PBDTTT-C-T/PC70BM solar cells via UV-ozone treatment.

In this work, the electron transport layer of PBDTTT-C-T/PC70BM polymer solar cells were subjected to UV-ozone treatment, leading to improved cell performances from 6.46% to 8.34%. The solar cell efficiency reached a maximum of 8.34% after an optimal 5 minute UV-ozone treatment, and then decreased if treated for a longer time. To the best of our knowledge, the mechanism behind the effects of UV-ozone treatment on the improvement of charge transport and cell performance is not fully understood. We have developed a fundamental understanding of the UV-ozone treatment mechanism, which explains both the enhancements in charge transport and photovoltaic performance at an optimal treatment time, and also the phenomenon whereby further treatment time leads to a drop in cell efficiency. Transient photocurrent measurements indicated that the cell charge transport times were 1370 ns, 770 ns, 832 ns, 867 ns, and 1150 ns for the 0 min, 5 min, 10 min, 15 min, and 20 min UV-ozone treatment times, respectively. Therefore the 5 min UV-ozone treatment time led to the shortest transport time and the most efficient charge transport in the cells. The 5 min UV-ozone treated sample exhibited the highest peak intensity (E2) in the Raman spectra of the treated films, at about 437 cm(-1), indicating that it possessed the best wurtzite phase crystallinity of the ZnO films. Further increasing the UV-ozone treatment time from 5 to 20 min induced the formation of p-type defects (e.g. interstitial oxygen atoms), pushing the ZnO Fermi-level further away from the vacuum level, and decreasing the wurtzite crystallinity.

Photovoltaic devices and characterization of a dodecyloxybenzothiadiazole-based copolymer.

A conjugated copolymer based on alternating benzo[1,2-b;3,4-b']dithiophene (BDT) donor and dodecyloxy substituted benzo[c][1,2,5]thiadiazole (ABT) acceptor units was prepared for application in organic solar cells. A power conversion efficiency (PCE) of ~3% with a short-circuit current (Jsc) of 7.63 mA cm(-2), an open-circuit voltage (Voc) of 0.71 V and a fill-factor (FF) of 53.74% was obtained under the illumination of AM 1.5 solar irradiation (100 mW cm(-2)). Photovoltaic devices and their transient properties with a blend of the copolymer and the [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) at different ratios were studied using transient photovoltage (TPV), transient photocurrent (TPC) and atomic force microscopy (AFM) measurements. From the TPV and TPC measurements, the charge recombination times (τn) were found to be 21.1 µs, 12.6 µs and 10.5 µs, and the charge transport times (τd) were 1316 ns, 422 ns and 707 ns for the 1 : 0.5, 1 : 1 and 1 : 2 donor/acceptor (D/A) ratios, respectively. The 1 : 1 D/A ratio showed the shortest charge transport time (τd) and the longest charge diffusion length (Ln) according to L(n) [proportionality] √[τ(n)/τ(d)], leading to the highest device performance among the three ratios.

Kelvin probe force microscopic imaging of the energy barrier and energetically favorable offset of interfaces in double-junction organic solar cells.

A double-junction polymer solar cell (PSC) has attracted extensive attention as a promising approach to increasing efficiency. Tunneling/recombination interlayers between subcells play a critical role in double-junction PSCs. Interlayers include electron-transport layers (ETLs) such as Nb2O5, ZnO, and TiO(x) and hole-transport layers (HTLs) including PEDOT:PSS. These materials have all been used as interlayer materials, but it remains unclear which one is better than the other. Kelvin probe force microscopy (KFM) was used to identify the energy barrier and energetically favorable energy offset at the interfaces of acceptor-ETL (e.g., PCBM-Nb2O5, PCBM-ZnO, and PCBM-TiO(x)) and donor-HTL (e.g., MDMO-PPV/PEDOT:PSS). Here the interface refers to the junction of two materials, formed by drop-casting one on top of other. The interface is buried and is therefore not accessible to the KFM probe. The energy barrier for electron transport from PCBM to ETL was found at ∼0.20, ∼0.12, and ∼0.012 eV at the PCBM-Nb2O5, PCBM-ZnO, and PCBM-TiO(x) interfaces, respectively. Hole transport from the donor polymer to PEDOT:PSS was found to be energetically favorable with an energy offset of ∼0.14 eV to facilitate hole transport. The thickness independences of the energy barrier and energetically favorable energy offset at the interfaces of acceptor-ETL and donor-HTL were also observed. This work will provide guidance for researchers to identify and select appropriate materials as interlayers in double-junction PSCs.

Enhanced performance in dye-sensitized solar cells via carbon nanofibers-platinum composite counter electrodes.

A composite counter electrode (CE) made of electrospun carbon nanofibers (ECNs) and platinum (Pt) nanoparticles has been demonstrated for the first time to improve the performance of dye-sensitized solar cells (DSCs). The new ECN-Pt composite CE exhibited a more efficient electro-catalytic performance with lower charge transfer resistance (R(ct)), larger surface area, and faster reaction rate than those of conventional Pt. It reduced the overall series resistance (R(se)), decreased dark saturation current density (J(0)) and increased shunt resistance (R(sh)) of the DSCs, thereby leading to a higher fill factor (FF) and larger open circuit voltage (V(oc)). The reduced electron transport resistance (R(s)) and faster charge transfer rate in the CE led to a smaller overall cell series resistance (R(se)) in the ECN-Pt composite based DSCs. The DSCs based on an ECN-Pt CE achieved a η of ∼8%, which was improved over those of pure Pt or ECN based cells.

Nb2O5 as a new electron transport layer for double junction polymer solar cells.

Nb(2)O(5) as a new electron transport layer (ETL) was used for double junction polymer solar cells. The Nb(2)O(5) ETL was prepared by spin coating a Nb(2)O(5) sol-gel solution onto the active layer of the optical front subcell. The double junction devices using Nb(2)O(5) ETL exhibit an open circuit voltage (V(oc)) of 1.30 V, which is close to the sum of the s of the individual subcells. The current density-voltage (J-V) simulation showed that the double junction device performance using Nb(2)O(5) as ETL could be significantly increased by reducing the series resistance (R(se)) and matching the current densities of the individual subcells.