High‐Performance Inverted Polymer Solar Cells: Device Characterization,Optical Modeling,and Hole‐Transporting Modifications

Although high power conversion efficiencies (PCE) have already been demonstrated in conventional structure polymer solar cells (PSCs), the development of high performance inverted structure polymer solar cells is still lagging behind despite their demonstrated superior stability and feasibility for roll‐to‐roll processing. To address this challenge, a detailed study of solution‐processed, inverted‐structure PSCs based on the blends of a low bandgap polymer, poly(indacenodithiophene‐co‐phananthrene‐quinoxaline) (PIDT‐PhanQ) and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as the bulk heterojunction (BHJ) layer is carried out. Comprehensive characterization and optical modeling of the resulting devices is performed to understand the effect of device geometry on photovoltaic performance. Excellent device performance can be achieved by optimizing the optical field distribution and spatial profiles of excitons generation within the active layer in different device configurations. In the inverted structure, because the peak of the excitons generation is located farther away from the electron‐collecting electrode, a higher blending ratio of fullerene is required to provide higher electron mobility in the BHJ for achieving good device performance.     

Bulk heterojunction thin film formation by single and dual feed ultrasonic spray method for application in organic solar cells

We here present a way of preparing the polymer:fullerene BHJ using dual feed method which can lead to formation of pure phases. In this report, we present results of our initial experiments in this direction. The effect of process parameters on the thickness and surface roughness of the active layer has been discussed. The structural and optical properties have been studied using the optical microscope, UV-visible spectroscopy and photoluminescence spectroscopy. Significant PL quenching indicates efficient charge separation in the BHJ formed using this technique. We have also compared the BHJ thin films prepared with this dual feed ultrasonic technique with the single feed spray method. The BHJ formed using this technique has been used as an active layer in OSC.     

Comparison of contact designs for improved stability of broad areasemiconductor lasers

Patterned electrode designs are used to control optical mode shape in high-power semiconductor lasers by localizing current injection. In this letter, we present comparison of current density profiles in the active layer achieved by different contact designs. Single-voltage digitated contact, distributed regular and random Gaussian contact configurations are studied using numerical solutions of semiconductor device equations that govern electrostatic potential and carrier concentrations in three spatial dimensions. The results of our calculations indicate that lateral current profile is influenced by the contact shape in the transverse direction and the thickness of the junction on the contact side     

Solid Solvation Assisted Electrical Doping Conserves High-Performance in 500 nm Active Layer Organic Solar Cells

Organic solar cells (OSCs) process fascinating solution-printing capability to achieve low-cost and large-scale manufacture. However, the rapid power conversion efficiency (PCE) decay with active layer thickness enlargement inhibits the implement of OSCs’ potential advantages. To overcome the bottlenecks of PCE decay in thick active layer OSCs, the electrical doping with componential selectivity in bulk heterojunction (BHJ) film is achieved by introducing a solid solvation additive. Benefiting from the higher exciton splitting efficiency together with the longer drift (L_dr) and diffusion (L_diff) lengths, an OSC with 100 nm BHJ film demonstrates a PCE increment from 16.44% to 18.24% with prolonged dark and illuminated storage stabilities. Applying the solid solvation assisted (SSA) doping method in the OSCs with 500 nm active layer, the PCE significantly increases by 31.9%, from the original value of 11.79% to 15.55%. It further improves to 15.84% in a ternary blend thick-film device, which is the record value to the best of our knowledge. Besides, the SSA doping narrows the PCE gap between the 0.04 and 1 cm² devices. All improvements demonstrate the great potential of SSA doping for OSC commercial manufacture, since it optimizes the photovoltaic performance under all practical conditions of long-term, thick-film, and large-area.     

The effect of charge extraction layers on the photo-stability of vacuum-deposited versus solution-coated organic solar cells

Organic solar cells (OSCs) are studied for their photo-stability in inert atmosphere. Polymer solar cells with a bulk heterojunction (BHJ) of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) are contrasted with small molecule solar cells with a BHJ of chloroindium phthalocyanine (ClInPc) and C₆₀-fullerene. A series of charge extraction layers at the hole and electron collecting contacts are examined for their role in OSC performance and stability. The inter-compatibilities of these extraction layers in vacuum-deposited small molecule OSCs (SM-OSCs) versus solution-coated polymer OSCs (P-OSCs) are explored. Through photo-stability studies, we show that interfacial extraction layers are necessary to avoid contact photo-degradation, which otherwise leads to strong reductions in OSC efficiencies. We also highlight certain extraction layer combinations that result in strong inter-electrode degradation, and we discuss incompatibilities in extraction layers among SM-OSCs versus P-OSCs. Our results suggest that the presence of excitons at the organic-electrode interface likely plays a critical role in contact photo-degradation. By minimizing contact photo-degradation, which dominates the majority of short-term OSC degradation, a new avenue for studying OSC stability behavior and opportunities to focus on other losses in OSCs become possible.     

Thermal carrier generation in charge-coupled devices

The build-up of thermally generated carriers in a charge-coupled device shift register is characterized by constructing a model for the generation inside a single shift-register bit. Using the model, theoretical response curves are constructed for two practical modes of operation where the contribution from the generation of carriers can be substantial. Experiments are presented which confirm all aspects of the theoretical response curves, including the presence of an initial period of reduced generation in one of the two modes. Procedures for determining generation parameters directly from observed CCD characteristics are presented and implemented. One generation parameter, the minority carrier lifetime τ, is determined by employing the CCD connected in a gate-controlled diode configuration; two others, the depleted surface generation velocity s0, and the general shape of the depletion layer, are determined utilizing a curve fitting procedure. The spatial variation in generation rates is also investigated and found to possess a distribution which is skewed positively and not Gaussian.     

基于过渡金属氧化物薄膜为连接层的叠层有机电制发光器件的数值模型

By utilizing a two-step process to express the charge generation and separation mechanism of the transition metal oxides （TMOs） interconnector layer, a numerical model was proposed for tandem organic light emitting diodes （OLEDs） with a TMOs thin film as the interconnector layer. This model is valid not only for an n-type TMOs interconnector layer, but also for a p-type TMOs interconnector layer. Based on this model, the influences of different carrier injection barriers at the interface of the electrode/organic layer on the charge generation ability of interconnector layers were studied. In addition, the distribution characteristics of carrier concentration, electric field intensity and potential in the device under different carrier injection barriers were studied. The results show that when keeping one carrier injection barrier as a constant while increasing another carrier injection barrier, carri- ers injected into the device were gradually decreased, the carrier generation ability of the interconnector layer was gradually reduced, the electric field intensity at the interface of the organic/electrode was gradually enhanced, and the electric field distribution became nearly linear： the voltage drops in two light units gradually became the same. Meanwhile, the carrier injection ability decreased as another carrier injection barrier increased. The simulation re- sults agree with the experimental data. The obtained results can provide us with a deep understanding of the work mechanism of TMOs-based tandem OLEDs.     

A new technique for depth resolved carrier recombinationmeasurements applied to proton irradiated thyristors

A contactless technique for localized carrier recombination measurements is demonstrated and applied for depth resolved lifetime measurements of proton irradiated thyristors. The measurement principle is based on homogeneous generation of carriers by a laser pulse and the simultaneous detection of carriers using free carrier absorption of a focused infrared probe beam. The approach relies on the instantaneous detection of the build-up of carriers during a short excitation pulse for which diffusion effects become negligible. By comparing the measured number of carriers in a defect laced sample with the optical generation rate during the pulse, e.g., inferred from the number of generated carriers in a virgin Si sample, the lifetime is calculated. The resulting carrier recombination depth profiles show good agreement with Monte Carlo simulated ion damage profiles. In particular, the damage tail towards the surface is clearly resolved. This shows that defects created in the proton tracks are electrically active and need to be considered for proper device performance     

Molecular Intercalation and Cohesion of Organic Bulk Heterojunction Photovoltaic Devices

The phase separated bulk heterojunction (BHJ) layer in BHJ polymer:fullerene organic photovoltaic devices (OPV) are mechanically weak with low values of cohesion. Improved cohesion is important for OPV device thermomechanical reliability. BHJ devices are investigated and how fullerene intercalation within the active layer affects cohesive properties in the BHJ is shown. The intercalation of fullerenes between the side chains of the polymers poly(3,3″′‐didocecyl quaterthiophene) (PQT‐12) and poly(2,5‐bis(3‐hexadecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (pBTTT) is shown to enhance BHJ layer cohesion. Cohesion values range from ≈1 to 5 J m^?2, depending on the polymer:fullerene blend, processing conditions, and composition. Devices with non‐intercalated BHJ layers are found to have significantly reduced values of cohesion. The resulting device power conversion efficiencies (PCE) are also investigated and correlated with the device cohesion.     

Origin of high fill factor in polymer solar cells from semiconducting polymer with moderate charge carrier mobility

The fill factor of polymer bulk heterojunction solar cells (PSCs), which is mainly governed by the processes of charge carrier generation, recombination, transport and extraction, and the competition between them in the device, is one of the most important parameters that determine the power conversion efficiency of the device. We show that the fill factor of PSCs based on thieno[3,4-b]-thiophene/benzodithiophene (PTB7):[6,6]-phenyl C₇₁-butyric acid methylester (PC₇₁BM) blend that only have moderate carrier mobilities for hole and electron transport, can be enhanced to 76% by reducing the thickness of the photoactive layer. A drift–diffusion simulation study showed that reduced charge recombination loss is mainly responsible for the improvement of FF, as a result of manipulating spatial distribution of charge carrier in the photoactive layer. Furthermore, the reduction of the active layer thickness also leads to enhanced built-in electric field across the active layer, therefore can facilitate efficient charge carrier transport and extraction. Finally, the dependence of FF on charge carrier mobility and transport balance is also investigated theoretically, revealing that an ultrahigh FF of 80–82% is feasible if the charge mobility is high enough (∼10⁻³–10⁻¹ cm²/V s).     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

Using Bulk Heterojunctions and Selective Electron Trapping to Enhance the Responsivity of Perovskite–Graphene Photodetectors

Graphene field effect transistor sensitized by a layer of semiconductor (sensitizer/GFET) is a device structure that is investigated extensively for ultrasensitive photodetection. Among others, organometallic perovskite semiconductor sensitizer has the advantages of long carrier lifetime and solution processable. A further step to improve the responsivity is to design a structure that can promote electron–hole separation and selective carrier trapping in the sensitizer. Here, the use of a hybrid perovskite–organic bulk heterojunction (BHJ) as the light sensitizer to achieve this goal is demonstrated. Our spectroscopy and device measurements show that the CH₃NH₃PbI₃–PCBM BHJ/GFET device has improved charge separation yield and carrier lifetime as compared to a reference device with a CH₃NH₃PbI₃ sensitizer only. The key to these enhancement is the presence of [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), which acts as charge separation and electron trapping sites, resulting in a 30‐fold increase in the photoresponsivity. This work shows that the use of a small amount of electron or hole acceptors in the sensitizer layer can be an effective strategy for improving and tuning the photoresponsivity of sensitizer/GFET photodetectors.     

Hot-carrier-induced degradation of LDD polysilicon TFTs

In order to improve the stability of polysilicon thin-film transistors (TFTs) several drain junction architectures have been proposed. In this paper, the hot-carrier (HC) related stability of the lightly doped drain (LDD) TFT architecture is analyzed by using an iterative algorithm that relates the HC induced damage to the carrier injection across the device interfaces with gate and substrate oxide. The resulting creation of interface states and trapped charge is taken into account by using a system of rate equations that implements mathematically the Lais two step model, in which the generation of interface states is attributed to the trapping of hot-holes by centres into the oxide followed by the recombination with hot electrons. The rate equations are solved self-consistently with the aid of a device simulation program. By successive iterations, the time evolution of the interface state density and positive trapped charge distribution has been reconstructed, and the electrical characteristics calculated with this model are in good agreement with experimental data. This algorithm represent an improvement of an already proposed degradation model, in which the interface states formation dynamics is accounted by using a phenomenological approach. The present model has been applied to reproduce the degradation pattern of LDD TFTs and it is found that generation of interface states proceed almost symmetrically on the front and back device interfaces, starting from the points in which the transverse electric field peaks, and moving toward the drain side of the device. The final interface states distribution determines a sort of "bottleneck" in the active layer carrier density, that can explain the sensitivity to HC induced damage of both transfer and output characteristics.     

Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells

The performance of bulk‐heterojunction (BHJ) solar cells is strongly correlated with the nanoscale structure of the active layer. Various processing techniques have been explored to improve the nanoscale morphology of the BHJ layer, e.g., by varying the casting solvent, thermal annealing, solvent annealing, and solvent additives. This paper highlights the role of residual solvent in the “dried” BHJ layer, and the effect of residual solvents on PCBM diffusion and ultimately the stability of the morphology. We show that solvent is retained within the BHJ film despite prolonged heat treatment, leading to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM agglomerates. The addition of a small volume fraction of nitrobenzene to the casting solution inhibits the diffusion of PCBM in the dry film, resulting in smaller PCBM agglomerates, and improves the fill factor of the BHJ device to 0.61 without further tempering. The addition of nitrobenzene also increases the P3HT crystalline content, while increasing the onset temperature for melting of P3HT side chains and backbone. The melting temperature for PCBM is also higher with the nitrobenzene additive present.     

Successive Spray Deposition of P3HT/PCBM Organic Photoactive Layers: Material Composition and Device Characteristics

Controlling the active layer composition in organic electronic devices represents one of the major challenges in their fabrication. In particular, the composition of mixed donor/acceptor active layers for photosensitive device applications is known to strongly influence device performance. Here, an alternative approach for the preparation of organic heterojunction photoactive layers by successive spray deposition of the donor material, poly(3‐hexylthiophene) (P3HT), and acceptor material, [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM), is reported. Optical absorption spectra, X‐ray reflectivity, and cross‐sectional transmission electron microscopy investigations are used to indicate the penetration of PCBM into a previously deposited P3HT layer and the spontaneous formation of a bulk heterojunction (BHJ) within the active layer, which provides the large interfacial area needed for efficient exciton dissociation. It is shown that organic photodiodes composed of photoactive layers prepared using this fabrication method exhibit a performance comparable to conventional BHJ devices in which the active layer is rigorously blended in advance. Moreover, separate handling of the individual materials and their deposition from distinct solutions enables an enhanced control of the active layer composition and hence increases the ability of tuning device characteristics.     

An Electrode Design Rule for Organic Photovoltaics Elucidated Using a Low Surface Area Electrode

It is widely considered that charge carrier extraction in bulk‐heterojunction organic photovoltaics (BHJ OPVs) is most efficient when the area of contact between the semiconductor layers and the electrodes is maximized and the electrodes are electrically homogeneous. Herein, it is shown that ≈99% of the electrode surface can in fact be insulating without degrading the efficiency of charge carrier extraction, provided the spacing of the conducting areas is less than or equal to twice the optimal thickness of the BHJ layer. This striking result is demonstrated for BHJ OPVs with both conventional and inverted device architectures using two different types of BHJ OPVs, namely, PCDTBT:PC₇₀BM and the ternary blend PBDB‐T:ITIC‐m:PC₇₀BM. This finding opens the door to the use of a large pallet of materials for optical spacers and charge transport layers, based on a low density of conducting particles embedded in a wide bandgap insulating matrix.     

Novel brominated compounds using in binary additives based organic solar cells to achieve high efficiency over 10.3%

Solvent additives have been considered as a simple and efficient method to increase the performance of bulk-heterojunction (BHJ) organic solar cells, in which, the morphology of the active layer could obtain further improvements by using the binary solvent additives. In this paper, a series of brominated compounds, 1-Bromo-4-butylbenzene (Brbb), 1-Bromo-4-n-hexylbenzene (Brbh) and 1-Bromo-4-n-octylbenzene (Brbo), have been respectively incorporated with 1, 8-diiodooctane (DIO) and regarded as binary solvent additives to fabricate highly efficient bulk heterojunction (BHJ) organic solar cells (OSCs). Compared with the BHJ film based on single additive, the binary additives contained BHJ film shows increased optical absorption, efficient charge transport and better active layer morphology, leading to an enhancement of short-circuit current (J_SC) together with a higher achieved fill factor (FF). The conventional BHJ device using PTB7: PC₇₁BM or PTB7-th: PC₇₁BM with the binary solvent additives exhibit enhanced PCE of 8.13% and 10.31%, respectively, which is much higher than that of single additive based devices (7.04% for PTB7 and 8.73% for PTB7-th). The optimized performance of BHJ devices indicates that these brominated compounds are promising additives to improve device efficiency.     

Scanning capacitance microscopy and the role of localized charges in dielectric films: Infering or challenging?

Scanning capacitance microscopy (SCM) is considered a suitable technique to examine dopant profiles and to provide images of the charge carrier distribution in real device structures. A drawback of the application is the sensitivity of the method to different kinds of charges in the surface passivation layer. For a systematic study silicon structures with stripe patterns of different doping concentrations, covered either by a native oxide or by a thermally grown silicondioxide layer, were examined. The dependence of the dC/dV characteristic on the sweep rate of the tip bias and on the bias sweep direction was analyzed. Local charge trapping in the passivation layer was estimated from shifts of the peak position of the dC/dV versus V curves. It is demonstrated as to how features related to the charge trapping in the passivation layer and induced by a certain dc bias at the tip superimpose the dopant related features in the SCM image.     

Molecular engineering to improve carrier lifetimes for organic photovoltaic devices with thick active layers

The morphology of the bulk heterojunction absorber layer in an organic photovoltaic (OPV) device has a profound effect on the electrical properties and efficiency of the device. Previous work has consistently demonstrated that the solubilizing side-chains of the donor material affect these properties and device performance in a non-trivial way. Here, using Time-Resolved Microwave Conductivity (TRMC), we show by direct measurements of carrier lifetimes that the choice of side chains can also make a substantial difference in photocarrier dynamics. We have previously demonstrated a correlation between peak photoconductance measured by TRMC and device efficiencies; here, we demonstrate that TRMC photocarrier dynamics have an important bearing on device performance in a case study of devices made from donor materials with linear vs. branched side-chains and with variable active layer thicknesses. We use Grazing-Incidence Wide Angle X-ray Scattering to elucidate the cause of the different carrier lifetimes as a function of different aggregation behavior in the polymers. Ultimately, the results help establish TRMC as a technique for screening OPV donor materials whose devices maintain performance in thick active layers (>250 nm) designed to improve light harvesting, film reproducibility, and ease of processing.     

Gold nanorod enhanced organic photovoltaics: The importance of morphology effects

Organic photovoltaic devices with a 30% improvement in power conversion efficiency are achieved when gold nanorods (Au NR) are incorporated into the active bulk heterojunction (BHJ) layer. Detailed analysis of the system is provided through microscopy, device characterization, and spectroscopy, demonstrating that the enhancement effects are predominantly caused by induced morphology changes in the BHJ film rather than plasmonic effects. Wide angle X-ray diffraction provides evidence that the nanorods loaded into the BHJ film have an effect on polymer crystal orientation, leading to a systematic performance increase in the devices as a result of both internal and external efficiency improvements.