Identification of the Origin of Ultralow Dark Currents in Organic Photodiodes.

Organic bulk heterojunction photodiodes (OPDs) attract attention for sensing and imaging. Their detectivity is typically limited by a substantial reverse bias dark current density (Jd ). Recently, using thermal admittance or spectral photocurrent measurements, Jd has been attributed to thermal charge generation mediated by mid-gap states. Here, the temperature dependence of Jd in state-of-the-art OPDs is reported with Jd down to 10-9  mA cm-2 at -0.5 V bias. For a variety of donor-acceptor bulk-heterojunction blends it is found that the thermal activation energy of Jd is lower than the effective bandgap of the blends, by ca. 0.3 to 0.5 eV, but higher than expected for mid-gap states. Ultra-sensitive sub-bandgap photocurrent spectroscopy reveals that the minimum photon energy for optical charge generation in OPDs correlates with the dark current thermal activation energy. The dark current in OPDs is attributed to thermal charge generation at the donor-acceptor interface mediated by intra-gap states near the band edges.

Monolithic All-Perovskite Tandem Solar Cells with Minimized Optical and Energetic Losses.

Perovskite-based multijunction solar cells are a potentially cost-effective technology that can help surpass the efficiency limits of single-junction devices. However, both mixed-halide wide-bandgap perovskites and lead-tin narrow-bandgap perovskites suffer from non-radiative recombination due to the formation of bulk traps and interfacial recombination centers which limit the open-circuit voltage of sub-cells and consequently of the integrated tandem. Additionally, the complex optical stack in a multijunction solar cell can lead to losses stemming from parasitic absorption and reflection of incident light which aggravates the current mismatch between sub-cells, thereby limiting the short-circuit current density of the tandem. Here, an integrated all-perovskite tandem solar cell is presented that uses surface passivation strategies to reduce non-radiative recombination at the perovskite-fullerene interfaces, yielding a high open-circuit voltage. By using optically benign transparent electrode and charge-transport layers, absorption in the narrow-bandgap sub-cell is improved, leading to an improvement in current-matching between sub-cells. Collectively, these strategies allow the development of a monolithic tandem solar cell exhibiting a power-conversion efficiency of over 23%.

Ultralow dark current in near-infrared perovskite photodiodes by reducing charge injection and interfacial charge generation.

Metal halide perovskite photodiodes (PPDs) offer high responsivity and broad spectral sensitivity, making them attractive for low-cost visible and near-infrared sensing. A significant challenge in achieving high detectivity in PPDs is lowering the dark current density (JD) and noise current (in). This is commonly accomplished using charge-blocking layers to reduce charge injection. By analyzing the temperature dependence of JD for lead-tin based PPDs with different bandgaps and electron-blocking layers (EBL), we demonstrate that while EBLs eliminate electron injection, they facilitate undesired thermal charge generation at the EBL-perovskite interface. The interfacial energy offset between the EBL and the perovskite determines the magnitude and activation energy of JD. By increasing this offset we realized a PPD with ultralow JD and in of 5 × 10-8 mA cm-2 and 2 × 10-14 A Hz-1/2, respectively, and wavelength sensitivity up to 1050 nm, establishing a new design principle to maximize detectivity in perovskite photodiodes.

Thin Thermally Evaporated Organic Hole Transport Layers for Reduced Optical Losses in Substrate-Configuration Perovskite Solar Cells.

Parasitic optical absorption is one of the root causes of the moderate efficiency of metal halide perovskite solar cells (PSCs) with an opaque substrate configuration. Here, we investigate the reduction of these optical losses by using thin (7-10 nm), undoped, thermally evaporated 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD), N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) (NPB), and tris(4-carbazoyl-9-ylphenyl)amine) (TCTA) hole transport layers (HTLs). Of these, NPB is found to offer the best compromise between efficiency and stability. In semitransparent n-i-p configuration PSCs with an indium tin oxide bottom and a MoO3/thin-Au/ZnS dielectric-metal-dielectric top electrode, NPB gives 14.9% and 10.7% efficiency for bottom and top illumination, respectively. The corresponding substrate-configuration PSC fabricated on an Au bottom electrode has 13.1% efficiency. Compared to a 14.0% efficient PSC with a thick spin-coated doped spiro-OMeTAD layer, the cell with NPB provides an improved short-circuit current density but has slightly lower open-circuit voltage and fill factor. Detailed analysis of the optical losses in the opaque devices demonstrates that evaporated NPB offers negligible parasitic absorption compared to solution-processed spiro-OMeTAD. The optical losses that remain are due to absorption and reflection of the transparent top electrode.

Enhancement-Mode PEDOT:PSS Organic Electrochemical Transistors Using Molecular De-Doping.

Organic electrochemical transistors (OECTs) show great promise for flexible, low-cost, and low-voltage sensors for aqueous solutions. The majority of OECT devices are made using the polymer blend poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), in which PEDOT is intrinsically doped due to inclusion of PSS. Because of this intrinsic doping, PEDOT:PSS OECTs generally operate in depletion mode, which results in a higher power consumption and limits stability. Here, a straightforward method to de-dope PEDOT:PSS using commercially available amine-based molecular de-dopants to achieve stable enhancement-mode OECTs is presented. The enhancement-mode OECTs show mobilities near that of pristine PEDOT:PSS (≈2 cm2 V-1 s-1 ) with stable operation over 1000 on/off cycles. The electron and proton exchange among PEDOT, PSS, and the molecular de-dopants are characterized to reveal the underlying chemical mechanism of the threshold voltage shift to negative voltages. Finally, the effect of the de-doping on the microstructure of the spin-cast PEDOT:PSS films is investigated.

The effect of oxygen on the efficiency of planar p-i-n metal halide perovskite solar cells with a PEDOT:PSS hole transport layer.

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is frequently used as hole transport layer in planar p-i-n perovskite solar cells. Here we show that processing of a metal halide perovskite layer on top of PEDOT:PSS via spin coating of a precursor solution chemically reduces the oxidation state of PEDOT:PSS. This reduction leads to a lowering of the work function of the PEDOT:PSS and the perovskite layer on top of it. As a consequence, the solar cells display inferior performance with a reduced open-circuit voltage and a reduced short-circuit current density, which increases sublinearly with light intensity. The reduced PEDOT:PSS can be re-oxidized by thermal annealing of the PEDOT:PSS/perovskite layer stack in the presence of oxygen. As a consequence, thermal annealing of the perovskite layer in air provides solar cells with increased open-circuit voltage, short-circuit current density and high efficiency.