The Origin of the High Voltage in DPM12/P3HT Organic Solar Cells

Organic solar cells made using a blend of DPM12 and P3HT are studied. The results show that higher V_oc can be obtained when using DPM12 in comparison to the usual mono‐substituted PCBM electron acceptor. Moreover, better device performances are also registered when the cells are irradiated with sun‐simulated light of 10–50 mW cm^?2 intensity. Electrochemical and time‐resolved spectroscopic measurements are compared for both devices and a 100‐mV shift in the density of states (DOS) is observed for DPM12/P3HT devices with respect to PCBM/P3HT solar cells and slow polaron‐recombination dynamics are found for the DPM12/P3HT devices. These observations can be directly correlated with the observed increase in V_oc, which is in contrast with previous results that correlated the higher V_oc with different ideality factors obtained using dark‐diode measurements. The origin for the shift in the DOS can be correlated to the crystallinity of the blend that is influenced by the properties of the included fullerene.     

Organic Photodetectors and their Application in Large Area and Flexible Image Sensors: The Role of Dark Current

Organic photodetectors (OPDs) have gained increasing interest as they offer cost‐effective fabrication methods using low temperature processes, making them particularly attractive for large area image detectors on lightweight flexible plastic substrates. Moreover, their photophysical and optoelectronic properties can be tuned both at a material and device level. Visible‐light OPDs are proposed for use in indirect‐conversion X‐ray detectors, fingerprint scanners, and intelligent surfaces for gesture recognition. Near‐infrared OPDs find applications in biomedical imaging and optical communications. For most applications, minimizing the OPD dark current density (J_d) is crucial to improve important figures of merits such as the signal‐to‐noise ratio, the linear dynamic range, and the specific detectivity (D*). Here, a quantitative analysis of the intrinsic dark current processes shows that charge injection from the electrodes is the dominant contribution to J_d in OPDs. J_d reduction is typically addressed by fine‐tuning the active layer energetics and stratification or by using charge blocking layers. Yet, most experimental J_d values are higher than the calculated intrinsic limit. Possible reasons for this deviation are discussed, including extrinsic defects in the photoactive layer and the presence of trap states. This provides the reader with guidelines to improve the OPD performances in view of imaging applications.     

p‐CuO/n‐Si heterojunction solar cells with high open circuit voltage and photocurrent through interfacial engineering

Heterojunction solar cells of p‐type cupric oxide (CuO) and n‐type silicon (Si), p‐CuO/n‐Si, have been fabricated using conventional sputter and rapid thermal annealing techniques. Photovoltaic properties with an open‐circuit voltage (V_oc) of 380 mV, short circuit current (J_sc) of 1.2 mA/cm², and a photocurrent of 2.9 mA/cm² were observed for the solar cell annealed at 300 °C for 1 min. When the annealing duration was increased, the photocurrent increased, but the V_oc was found to reduce because of the degradation of interface quality. An improvement in the V_oc resulting to a record value of 509 mV and J_sc of 4 mA/cm² with a high photocurrent of ~12 mA/cm² was achieved through interface engineering and controlling the phase transformation of CuO film. X‐ray diffraction, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy analysis have been used to investigate the interface properties and crystal quality of sputter‐deposited CuO thin film. The improvement in V_oc is mainly due to the enhancement of crystal quality of CuO thin film and interface properties between p‐CuO and n‐Si substrate. The enhancement of photocurrent is found to be due to the reduction of carrier recombination rate as revealed by transient photovoltage spectroscopy analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

The Role of Sulfur in Solution‐Processed Cu2ZnSn(S,Se)4 and its Effect on Defect Properties

Understanding the electrically active defects in kesterite Cu₂ZnSn(S,Se)₄(CZTSSe) is critical for the continued development of solar cells based on this material, but challenging due to the complex nature of this polycrystalline multinary material. A comparative study of CZTSSe alloys with three different bandgaps, made by introducing different fractions of sulfur during the annealing process, is presented. Using admittance spectroscopy, drive level capacitance profiling, and capacitance‐voltage profiling, the dominant defect energy level present in the low sulfur content device is determined to be 0.134 eV above the valence band maximum, with a bulk defect density of 8 × 10¹⁴ cm^?3, while the high sulfur content device shows a deeper defect energy level of 0.183 eV and a higher bulk defect density, 8.2 × 10¹⁵ cm^?3. These findings are consistent with the current density–voltage characteristics of the resulting solar cells and their external quantum efficiency. It suggests that as the sulfur content increases, the bandgap of the absorber is enlarged, leading to an increasing open‐circuit voltage (V_oc), that is accompanied by stronger recombination due to the higher defect density of the sulfur‐rich absorber. This is reflected in large V_oc deficit and poor carrier collection of the high sulfur content device.     

An Organic Electrochemical Transistor Integrated Photodetector for High Quality Photoplethysmogram Signal Acquisition

The organic photodiode (OPD) is a promising building block for solution-processable, flexible, lightweight, and miniaturized photodetectors, ideal for wearable applications. Despite the advances in materials used in OPDs, their photocurrent and light responsivity are limited, and alternative methods are required to boost the signal response. Herein, a miniaturized organic electrochemical transistor (OECT) is integrated with an OPD module to unlock the potential of OPDs to acquire physiological signals. In this integrated photodetector (IPD) system, the light intensity regulates the OPD voltage output that modulates the OECT channel current. The high transconductance of the OECT provides efficient voltage-to-current conversion, enhancing the signal-to-noise ratio on the sensing site. A microscale, p-type enhancement-mode OECT with high g_m and fast switching speed performs better in this application than depletion-mode OECT of the same geometry. The IPD achieves a photocurrent and responsivity 318 and 140 times higher than the standalone OPD, respectively. It is shown that with the IPD, the amplitude of the photoplethysmogram signals detected by the OPD is enhanced by a factor of 2.9 × 10³, highlighting its potential as a wearable biosensor and to detect weak, often uncaptured, light-based signals from living systems.     

Self-Powered Organic Photodetectors with High Detectivity for Near Infrared Light Detection Enabled by Dark Current Reduction

Organic photodetectors (OPDs) for near infrared (NIR) light detection represents cutting-edge technology for optical communication, environmental monitoring, biomedical imaging, and sensing. Herein, a series of self-powered OPDs with high detectivity are constructed by the sequential deposition (SD) method. The dark currents (J_d) of SD devices are effectively reduced in comparison to blend casting (BC) ones due to the vertical phase segregation structure. Impressively, the J_d values of SD devices based on D18 and Y6 system is reduced to be 2.1 × 10⁻¹¹ A cm⁻² at 0 V, which is two orders of magnitude lower than those of the BC devices. The D* value of the SD device is superior to that of BC device under different bias voltages (0, −0.5, −1.0, and −2.0 V) due to the reduction of dark current, which originates from the fine vertical phase separation structure of the SD device. The mechanism studies shows that the vertical phase segregation structure can effectively suppress the unfavorable charge injection, thus reducing the dark current. Also, the surface energy is proven to play a key role in the photocurrent stability. In addition, the flexible OPDs demonstrate excellent performance in photoplethysmography test.     

High‐Performance Ferroelectric Polymer Side‐Gated CdS Nanowire Ultraviolet Photodetectors

An efficient ferroelectric‐enhanced side‐gated single CdS nanowire (NW) ultraviolet (UV) photodetector at room temperature is demonstrated. With the ultrahigh electrostatic field from polarization of ferroelectric polymer, the depletion of the intrinsic carriers in the CdS NW channel is achieved, which significantly reduces the dark current and increases the sensitivity of the UV photodetector even after the gate voltage is removed. Meanwhile, the low frequency noise current power of the device reaches as low as 4.6 × 10^?28 A² at a source‐drain voltage V_ds = 1 V. The single CdS NW UV photodetector exhibits high photoconductive gain of 8.6 × 10⁵, responsivity of 2.6 × 10⁵ A W^?1, and specific detectivity (D*) of 2.3 × 10¹⁶ Jones at a low power density of 0.01 mW cm^?2 for λ = 375 nm. In addition, the spatially resolved scanning photocurrent mapping across the device shows strong photocurrent signals near the metal contacts. This is promising for the design of a controllable, high‐performance, and low power consumption ultraviolet photodetector.     

Water-soluble poly(3,4-ethylenedioxythiophene)/nano-crystalline TiO2 heterojunction solar cells

Nanocrystalline titanium dioxide (TiO₂) thin films were prepared by the sol-gel method and were then used to fabricate an indium-tin oxide (ITO)/nano-crystalline TiO₂/poly(3,4-ethylenedioxythiophene) (PEDOT)/Au device. The junction thus obtained shows a rectifying behavior. Their current-voltage (I-V) characteristics in dark indicate that a heterojunction at the nano-crystalline TiO₂/PEDOT interface has been created. The measured open-circuit voltage (V_oc) and short-circuit current (I_sc) for the device under illumination with 50 mW/cm² light intensity under AM 1.5 conditions (device dimension was 1 cm²) are V_oc=0.39 V, I_sc=54.9 μA/cm², the filling factor (FF)=0.429 and the energy conversion efficiency (η)=0.03%.     

Integrating Efficient Optical Gain in High‐Mobility Organic Semiconductors for Multifunctional Optoelectronic Applications

Simultaneously integrating efficient optical gain and high charge carrier mobility in organic semiconductors for multifunctional optoelectronic applications is challenging. Here, a new thiophene/phenylene derivative, 5,5′‐bis(2,2‐diphenylvinyl)‐bithiophene (BDPV2T), containing an appropriate butterfly molecular configuration in a π‐conjugated structure, is designed to achieve both solid‐state emission and charge transport properties. The prepared BDPV2T crystals exhibit excellent light‐emitting characteristics with a photoluminescence quantum yield of 30%, low light‐amplification threshold of 8 kW cm^?2, high optical net gain up to 70 cm^?1, and high charge carrier mobility up to 1 cm² V^?1 s^?1 in their J‐aggregate single crystals. These BDPV2T single crystal characteristics ensure their application potential for photodetectors, field‐effect transistors, and light‐emitting transistors. High optoelectronic performances are achieved with photoresponsivity of 2.0 × 10³ A W^?1 and light on/off ratio of 5.4 × 10⁵ in photodetectors, and efficient ambipolar charge transport (µ_h: 0.14 cm² V^?1 s^?1, µ_e: 0.02 cm² V^?1 s^?1) and electroluminescence characteristics in light‐emitting transistors. The remarkably integrated optoelectronic properties of BDPV2T suggest it is a promising candidate for organic multifunctional and electrically pumped laser applications.     

Synthesis of Ultrathin,Homogeneous Copolymer Dielectrics to Control the Threshold Voltage of Organic Thin‐Film Transistors

This work demonstrates that threshold voltage (V_T) of organic thin‐film transistors (OTFTs) can be controlled systematically by introducing new copolymer dielectrics with electropositive functionality. A series of homogeneous copolymer dielectrics are polymerized from two monomers, 1,3,5‐trimethyl‐1,3,5‐trivinyl cyclotrisiloxane (V3D3) and 1‐vinylimidazole (VI), via initiated chemical vapor deposition. The chemical composition of the copolymer dielectrics is exquisitely controlled to tune the V_T of C₆₀ OTFTs. In particular, all the copolymer dielectrics demonstrated in this work exhibit extremely low leakage current densities (lower than 2.5 × 10^?8 A cm^?2 at ±3 MV cm^?1) even with a thickness less than 23 nm. Furthermore, by introducing an ultrathin pV3D3 interfacial layer (about 3 nm) between the copolymer dielectrics and C₆₀ semiconductor, the high mobility of the C₆₀ OTFTs (about 1 cm² V^?1 s^?1) remains unperturbed, showing that V_T can be controlled independently by tuning the composition of the copolymer dielectrics. Coupled with the ultralow dielectric thickness, the independent V_T controllability allows the V_T to be aligned near 0 V with sub‐3 V operating voltage, which enables a substantial decrease of device power consumption. The suggested method can be employed widely to enhance device performance and reduce power consumption in various organic integrated circuit applications.     

Lending Triarylphosphine Oxide to Phenanthroline: a Facile Approach to High‐Performance Organic Small‐Molecule Cathode Interfacial Material for Organic Photovoltaics utilizing Air‐Stable Cathodes

Cathode interfacial material (CIM) is critical to improving the power conversion efficiency (PCE) and long‐term stability of an organic photovoltaic cell that utilizes a high work function cathode. In this contribution, a novel CIM is reported through an effective and yet simple combination of triarylphosphine oxide with a 1,10‐phenanthrolinyl unit. The resulting CIM possesses easy synthesis and purification, a high T _g of 116 °C and attractive electron‐transport properties. The characterization of photovoltaic devices involving Ag or Al cathodes shows that this thermally deposited interlayer can considerably improve the PCE, due largely to a simultaneous increase in V _oc and FF relative to the reference devices without a CIM. Notably, a PCE of 7.51% is obtained for the CIM/Ag device utilizing the active layer PTB7:PC₇₁BM, which far exceeds that of the reference Ag device and compares well to that of the Ca/Al device. The PCE is further increased to 8.56% for the CIM/Al device (with J _sc = 16.81 mA cm^?2, V _oc = 0.75 V, FF = 0.68). Ultraviolet photoemission spectroscopy studies reveal that this promising CIM can significantly lower the work function of the Ag metal as well as ITO and HOPG, and facilitate electron extraction in OPV devices.     

Elucidating the Origins of Subgap Tail States and Open‐Circuit Voltage in Methylammonium Lead Triiodide Perovskite Solar Cells

Recombination via subgap trap states is considered a limiting factor in the development of organometal halide perovskite solar cells. Here, the impact of active layer crystallinity on the accumulated charge and open‐circuit voltage (V_oc) in solar cells based on methylammonium lead triiodide (CH₃NH₃PbI₃, MAPI) is demonstrated. It is shown that MAPI crystallinity can be systematically tailored by modulating the stoichiometry of the precursor mix, where small quantities of excess methylammonium iodide (MAI) improve crystallinity, increasing device V_oc by ≈200 mV. Using in situ differential charging and transient photovoltage measurements, charge density and charge carrier recombination lifetime are determined under operational conditions. Increased V_oc is correlated to improved active layer crystallinity and a reduction in the density of trap states in MAPI. Photoluminescence spectroscopy shows that an increase in trap state density correlates with faster carrier trapping and more nonradiative recombination pathways. Fundamental insights into the origin of V_oc in perovskite photovoltaics are provided and it is demonstrated why highly crystalline perovskite films are paramount for high‐performance devices.     

Low dark current inverted organic photodetectors employing MoOx:Al cathode interlayer

We report low dark current small molecule organic photodetectors (OPDs) with an inverted geometry for image sensor applications. Adopting a very thin MoO_x:Al cathode interlayer (CIL) in the inverted OPD with a reflective top electrode results in a remarkably low dark current density (J_d) of 5.6 nA/cm² at reverse bias of 3 V, while maintaining high external quantum efficiency (EQE) of 56.1% at visible wavelengths. The effectiveness of the CIL on the diode performance has been further identified by application to inverted OPDs with a semi-transparent top electrode, leading to a significantly low J_d of 0.25 nA/cm², moderately high EQE_{540 nm} of 25.8%, and subsequently high detectivity of 8.95 × 10¹² Jones at reverse bias of 3 V. Possible origins of reduced dark currents in the OPD by using the MoO_x:Al CIL are further described in terms of the change of interfacial energy barrier and surface morphology.     

Cyano‐Substituted Oligo(p‐phenylene vinylene) Single Crystals: A Promising Laser Material

Organic crystals that combine high charge‐carrier mobility and excellent light‐emission characteristics are expected to be of interest for light‐emitting transistors and diodes, and may offer renewed hope for electrically pumped laser action. High‐luminescence‐efficiency cyano‐substituted oligo(p‐ phenylene vinylene) (CN‐DPDSB) crystals (η ≈ 95%) grown by the physical vapor transport method is reported here, with high mobilities (at ≈10^?2 cm² V^?1 s^?1 order of magnitude) as measured by time‐of‐flight. The CN‐DPDSB crystals have well‐balanced bipolar carrier‐transport characteristics (μ_hole≈ 2.5–5.5 × 10^?2 cm² V^?1 s^?1; μ_electron ≈ 0.9–1.3 × 10^?2 cm² V^?1 s^?1) and excellent optically pumped laser properties. The threshold for amplified spontaneous emission (ASE) is about 4.6 μJ per pulse (23 KW cm^?2), while the gain coefficient at the peak wavelength of ASE and the loss coefficient caused by scattering are ≈35 and ≈1.7 cm^?1, respectively. This indicates that CN‐DPDSB crystals are promising candidates for organic laser diodes.     

Development of a‐SiOx:H solar cells with very high Voc × FF product

In this study, deposition conditions for making a‐SiO_x:H are investigated systematically in order to obtain a high band gap material. We found that at given optical band gap, a‐SiO_x:H with favorable opto‐electronic properties can be obtained when deposited using low CO₂ flow rates and deposition pressures. We also found that a low radio frequency power density is required in order to limit the effect of ion bombardment on the material properties of i‐a‐SiO_x:H and thereby the solar cell performance. In addition, by decreasing the heater temperature from 300 to 200°C when making the i‐a‐SiO_x:H, the V_oc can be increased. We employed optimized p‐doped and n‐doped a‐SiO_x:H films into the p‐i‐n solar cells, and as a consequence, a high V_oc of over 1 V and high fill factor (FF) are obtained. When depositing on texture‐etched ZnO:Al substrates, a high efficiency a‐SiO_x:H single junction solar cell having a high V_oc × FF product of 0.761 (V_oc: 1.042 V, J_sc: 10.3 mA/cm², FF: 0.73, efficiency: 7.83%) was obtained. The a‐SiO_x:H solar cell shows comparable light degradation characteristics to standard a‐Si:H solar cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Bithienopyrroledione‐Based Copolymers,Versatile Semiconductors for Balanced Ambipolar Thin‐Film Transistors and Organic Solar Cells with V oc > 1 V

Conjugated polymer semiconductors P1 and P2 with bithienopyrroledione (bi‐TPD) as acceptor unit are synthesized. Their transistor and photovoltaic performances are investigated. Both polymers display high and balanced ambipolar transport behaviors in thin‐film transistors. P1‐ based devices show an electron mobility of 1.02 cm² V^?1 s^?1 and a hole mobility of 0.33 cm² V^?1 s^?1, one of the highest performance reported for ambipolar polymer transistors. The electron and hole mobilities of P2 transistors are 0.36 and 0.16 cm² V^?1 s^?1, respectively. The solar cells with PC₇₁BM as the electron acceptor and P1/P2 as the donor exhibit a high V _oc about 1.0 V, and a power conversion efficiency of 6.46% is observed for P1‐ based devices without any additives and/or post treatment. The high performance of P1 and P2 is attributed to their crystalline films and short π–π stacking distance (<3.5 Å). These results demonstrate (1) bi‐TPD is an excellent versatile electron‐deficient unit for polymer semiconductors and (2) bi‐TPD‐based polymer semiconductors have potential applications in organic transistors and organic solar cells.     

Device characteristics of a 10.1% hydrazine‐processed Cu2ZnSn(Se,S)4 solar cell

A power conversion efficiency record of 10.1% was achieved for kesterite absorbers, using a Cu₂ZnSn(Se,S)₄ thin‐film solar cell made by hydrazine‐based solution processing. Key device characteristics were compiled, including light/dark J–V, quantum efficiency, temperature dependence of V_oc and series resistance, photoluminescence, and capacitance spectroscopy, providing important insight into how the devices compare with high‐performance Cu(In,Ga)Se₂. The record kesterite device was shown to be primarily limited by interface recombination, minority carrier lifetime, and series resistance. The new level of device performance points to the significant promise of the kesterites as an emerging and commercially interesting thin‐film technology. Copyright © 2011 John Wiley & Sons, Ltd.     

Current transport studies of amorphous n/p junctions and its application in a‐Si:H/HIT‐type tandem cells

This paper presents an understanding of the fundamental carrier transport mechanism in hydrogenated amorphous silicon (a‐Si:H)‐based n/p junctions. These n/p junctions are, then, used as tunneling and recombination junctions (TRJ) in tandem solar cells, which were constructed by stacking the a‐Si:H‐based solar cell on the heterojunction with intrinsic thin layer (HIT) cell. First, the effect of activation energy (E_a) and Urbach parameter (E_u) of n‐type hydrogenated amorphous silicon (a‐Si:H(n)) on current transport in an a‐Si:H‐based n/p TRJ has been investigated. The photoluminescence spectra and temperature‐dependent current–voltage characteristics in dark condition indicates that the tunneling is the dominant carrier transport mechanism in our a‐Si:H‐based n/p‐type TRJ. The fabrication of a tandem cell structure consists of an a‐Si:H‐based top cell and an HIT‐type bottom cell with the a‐Si:H‐based n/p junction developed as a TRJ in between. The development of a‐Si:H‐based n/p junction as a TRJ leads to an improved a‐Si:H/HIT‐type tandem cell with a better open circuit voltage (V_oc), fill factor (FF), and efficiency. The improvements in the cell performance was attributed to the wider band‐tail states in the a‐Si:H(n) layer that helps to an enhanced tunneling and recombination process in the TRJ. The best photovoltage parameters of the tandem cell were found to be V_oc = 1430 mV, short circuit current density = 10.51 mA/cm², FF = 0.65, and efficiency = 9.75%. Copyright © 2015 John Wiley & Sons, Ltd.     

Toward Faster Organic Photodiodes: Tuning of Blend Composition Ratio

The ability of a light-sensor to detect fast variation in incident light intensity is a vital feature required in imaging and data transmission applications. Solution-processed bulk heterojunction (BHJ) type organic photodiodes (OPDs) have gone through key developments, including dark current mitigation and longer linear dynamic range. In contrast, there has been less focus on increasing OPD response speed (f_–3dB). Here, bulk heterojunction OPDs based on electron-donating polymer poly[thiophene-2,5-diyl-alt-5,10-bis((2-hexyldecyl)oxy)dithieno[3,2-c:3′,2′-h][1,5]naphthyridine-2,7-diyl] (or PTNT) and electron-accepting phenyl-C₇₁-butyric acid methyl ester (or PC₇₁BM) are reported. The intrinsic charge transport characteristics required for fast speed OPDs are discussed, and an analytical model for the same is developed. The OPDs present 0.8 MHz f_–3dB under no applied voltage bias for a typical blend ratio of 1:1 by weight. It is shown that balanced electron and hole mobility is a critical criterion for faster speed OPDs, which can be realized by tuning the composition ratio of the bulk heterojunction. By tuning PTNT and PC₇₁BM blend ratio, the f_–3dB was successfully raised by more than quadruple to 4.5 MHz. The findings provide a tool to set device architecture for faster next-generation light sensors.     

Self‐Doping Cathode Interfacial Material Simultaneously Enabling High Electron Mobility and Powerful Work Function Tunability for High‐Efficiency All‐Solution‐Processed Polymer Light‐Emitting Diodes

A variety of N ‐hydrogenated/N ‐methylated pyridinium salts are elaborately designed and synthesized. Thermogravimetric and X‐ray photoelectron spectra analysis indicate the intensities of the N? H covalent bonds are strengthened step‐by‐step from 3,3′‐(5′‐(3‐(pyridin‐3‐yl)phenyl)‐[1,1′:3′,1″‐terphenyl]‐3,3″‐diyl)dipyridine (Tm)‐HCl to Tm‐HBr and then Tm‐TfOH, which results in gradually improved cathode interfacial modification abilities. The larger dipole moments of N⁺? H containing moieties compared to those of the N⁺? CH₃ endow them with more preferable interfacial modification abilities. Electron paramagnetic resonance signals reveal the existence of radical anions in the solid state of Tm‐TfOH, which enables its self‐doping property and high electron mobility up to 1.67 × 10^?3 cm² V^?1 s^?1. Using the Tm‐TfOH as the cathode interfacial layers (CILs), the phenyl‐substituted poly(para ‐phenylene vinylene)‐based all‐solution‐processed polymer light‐emitting diodes (PLEDs) achieve more preferable device performances than the poly[(9,9‐bis(3′‐(N ,N ‐dimethylamino)propyl)‐2,7‐fluorene)‐alt ‐2,7‐(9,9‐dioctylfluorene)]‐based ones, i.e., high current density of nearly 300 mA cm^?2, very high luminance over 15 000 cd m^?2 at a low bias of 5 V. Remarkably, the thickness of the CILs has little impact on the device performance and high efficiencies are maintained even at thicknesses up to 85 nm, which is barely realized in PLEDs with small‐molecule‐based electron transporting layers.