Probing Charge Recombination Dynamics in Organic Photovoltaic Devices under Open‐Circuit Conditions

Large perturbation transient photovoltage and impedance spectroscopy measurements are used to gain insights into recombination in organic photovoltaic devices. The combination of these two simple optoelectronic techniques enables characterization of recombination order as well as mobile and trapped charge evolution over a large range of carrier densities. The data show that trapped charge is approximately equal to total charge at low carrier densities in the high efficiency devices measured. Between low and high charge carrier density, the order of recombination is observed to vary from monomolecular to bimolecular to higher order. The new techniques and methods presented can be applied to any type of photovoltage device to gain insight into device operation and limitations.     

Highly‐Tunable Nickel Cobalt Oxide as a Low‐Temperature P‐Type Contact in Organic Photovoltaic Devices

We report on the investigation of nickel cobalt oxide (Ni_xCo_3?xO₄) thin films grown by pulsed laser deposition as hole‐transport interlayers (HTL) in organic photovoltaic (OPV) devices. Films of 7 nm thickness were grown under various oxygen deposition pressures (pO₂) in the range of 2–200 mTorr. We explore both bulk and surface properties of these thin films. The workfunction (?) for each of the films was statistically similar (～4.7 eV), regardless of pO₂. There was not a strong dependence of the power conversion efficiency (η) on the conductivities of the HTLs varying between 0.009 ‐ 10 S/cm. The observed differences in OPV efficiencies (ranging from 1.16 to 2.46%) were correlated to the near surface chemical composition of the Ni_xCo_3?xO₄ HTL, as observed by differences in the relative surface hydroxyl concentration. The critical role of the near‐surface composition of the HTL at the HTL/organic interface was further explored by modifying the hydroxyl concentration using an oxygen plasma treatment. This treatment mitigated the impact of surface hydroxyl coverage, demonstrating either identical or increased values for ? and η, regardless of initial pO₂ in the creation of the Ni_xCo_3?xO₄ HTL. To further explore this we also employed a phosphonic acid surface modification agent on the HTL, increasing ? to 5.2 eV producing the best η value of 3.4%, equivalent to the PEDOT:PSS control devices. These results indicate that nickel cobalt oxide is a promising p‐type oxide for carrier‐selective interlayers in organic solar cells; however, for this to be fully realized the specific surface chemistry at the oxide/polymer interface must be controlled to increase ? and optimize device performance.     

Metal‐Oxide‐Free Methylammonium Lead Iodide Perovskite‐Based Solar Cells: the Influence of Organic Charge Transport Layers

Metal‐oxide‐free methylammonium lead iodide perovskite‐based solar cells are prepared using a dual‐source thermal evaporation method. This method leads to high quality reproducible films with large crystal domain sizes allowing for an in depth study of the effect of perovskite film thickness and the nature of the electron and hole blocking layers on the device performance. The power conversion efficiency increases from 4.7% for a device with only an organic electron blocking layer to almost 15% when an organic hole blocking layer is also employed. In addition to the in depth study on small area cells, larger area cells (approx. 1 cm^?2) are prepared and exhibit efficiencies in excess of 10%.     

Cation Substitution of Solution‐Processed Cu2ZnSnS4 Thin Film Solar Cell with over 9% Efficiency

To alleviate the limitations of pure sulfide Cu₂ZnSnS₄ (CZTS) thin film, such as band gaps adjustment, antisite defects, secondary phase and microstructure, Cadmium is introduced into CZTS thin film to replace Zn partially to form Cu₂Zn_1?xCd_xSnS₄ (CZCTS) thin film by low‐cost sol–gel method. It is demonstrated that the band gaps and crystal structure of CZCTS thin films are affected by the change in Zn/Cd ratio. In addition, the ZnS secondary phase can be decreased and the grain sizes can be improved to some degree by partial replacement of Zn with Cd in CZCTS thin film. The power conversion efficiency of CZTS solar cell device is enhanced significantly from 5.30% to 9.24% (active area efficiency 9.82%) with appropriate ratio of Zn/Cd. The variation of device parameter as a function of Zn/Cd ratio may be attributed to the change in electronic structure of the bulk CZCTS thin film (i.e., phase change from kesterite to stannite), which in turn affects the band alignment at the CZCTS/buffer interface and the charge separation at this interface.     

Relation of Nanostructure and Recombination Dynamics in a Low‐Temperature Solution‐Processed CuInS2 Nanocrystalline Solar Cell

The understanding and control of nanostructures with regard to transport and recombination mechanisms is of key importance in the optimization of the power conversion efficiency (PCE) of solar cells based on inorganic nanocrystals. Here, the transport properties of solution‐processed solar cells are investigated using photo‐CELIV (photogenerated charge carrier extraction by linearly increasing voltage) and transient photovoltage techniques; the solar cells are prepared by an in‐situ formation of CuInS₂ nanocrystals (CIS NCs) at the low temperature of 270 °C. Structural and morphological analyses reveal the presence of a metastable CuIn₅S₈ phase and a disordered morphology in the CuInS₂ nanocrytalline films consisting of polycrystalline grains at the nanoscale range. Consistent with the disordered morphology of the CIS NC thin films, the CIS NC devices are characterized by a low carrier mobility. The carrier density dynamic indicates that the recombination kinetics in these devices follows the dispersive bimolecular recombination model and does not fully behave in a diffusion‐controlled manner, as expected by Langevin‐type recombination. The mobility–lifetime product of the charge carriers properly explains the performance of the thin (200 nm) CIS NC solar cell with a high fill‐factor of 64% and a PCE of over 3.5%.     

Voltage‐Induced Formation of Accumulation Layers at Electrode Interfaces in Organic Solar Cells

This work reports on organic bulk heterojunction solar cells based on poly(3‐hexylthiophene) (P3HT) blended with [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM) in a configuration with so‐called interdigital nanoelectrodes, i.e., vertical electrodes on substrates structured in the submicrometer range. In this setup, both electrodes are in place prior to the deposition of the photoactive blend solution and therefore allow for the application of a voltage during drying of the blend. A strong correlation is observed between the photovoltaic performance of these devices and the voltage that is applied during film formation. Even the polarity of the solar cells can be controlled with this method. It is suggested that this is a consequence of a strong segregation of donor and acceptor phases at the electrode interfaces induced by the applied voltage. Further experiments on planar solar cell geometries, including a solvent‐vapor treatment and the introduction of an additional layer of pure P3HT, as well as numerical simulations, are presented. All results obtained are consistent with the suggested hypothesis.     

Linking Vertical Bulk‐Heterojunction Composition and Transient Photocurrent Dynamics in Organic Solar Cells with Solution‐Processed MoOx Contact Layers

It is demonstrated that a combination of microsecond transient photocurrent measurements and film morphology characterization can be used to identify a charge‐carrier blocking layer within polymer:fullerene bulk‐heterojunction solar cells. Solution‐processed molybdenum oxide (s‐MoO_x) interlayers are used to control the morphology of the bulk‐heterojunction. By selecting either a low‐ or high‐temperature annealing (70 °C or 150 °C) for the s‐MoO_x layer, a well‐performing device is fabricated with an ideally interconnected, high‐efficiency morphology, or a device is fabricated in which the fullerene phase segregates near the hole extracting contact preventing efficient charge extraction. By probing the photocurrent dynamics of these two contrasting model systems as a function of excitation voltage and light intensity, the optoelectronic responses of the solar cells are correlated with the vertical phase composition of the polymer:fullerene active layer, which is known from dynamic secondary‐ion mass spectroscopy (DSIMS). Numerical simulations are used to verify and understand the experimental results. The result is a method to detect poor morphologies in operating organic solar cells.     

High Efficiency (>17%) Si‐Organic Hybrid Solar Cells by Simultaneous Structural,Electrical, and Interfacial Engineering via Low‐Temperature Processes

Highly efficient organic–inorganic hybrid solar cells of Si‐poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) have been demonstrated by simultaneous structural, electrical, and interfacial engineering with low processing temperature. Si substrate has been sculpted into hierarchical structure to reduce light reflection loss and increase interfacial junction area at the same time. Regarding the electrical optimization, highly conductive organic PEDOT:PSS layer has been formulated with low sheet resistance. It is argued that the sheet resistance, rather than conductivity, is the primary parameter for the high efficiency hybrid cells, which leads to the optimization of thickness, i.e., thick enough to have low sheet resistance but transparent enough to pass the incident sunlight. Finally, siloxane oligomers have been inserted into top/bottom interfaces by contact‐printing at room ambient, which suppresses carrier recombination at interfaces and reduces contact resistance at bottom electrode. Contrary to high‐temperature doping (for the formation of front surface or back surface fields), wet solution processes or vacuum‐based deposition, the contact‐printing can be done at room ambient to reduce carrier recombination at the interfaces. The high efficiency obtained with low processing temperature can make this type of cells be a possible candidate for post‐Si photovoltaics.     

Solution‐Processed Ternary Oxides as Carrier Transport/Injection Layers in Optoelectronics

With the remarkable progress in solution‐processed optoelectronics, high performance is required of the carrier transport/injection layer. Ternary oxides containing a variety of crystal structures, and adjustable composition that results in tunable optical and electrical properties, are one of the promising class of candidates to fulfill the requirements of carrier transport/injection layers for high‐performance and stable optoelectronic devices. Solution‐processed ternary oxides have seen considerable progress in recent decades, due to their advantages in the quest to design low‐cost, high‐performance, large‐scale, and stable optoelectronic devices. Herein, the recent advances of solution‐processed ternary oxides are reviewed. The first section consists of a brief introduction to the topic. In the following section, the fundamentals of the effect of tuning ternary oxide composition are summarized. Section three briefly reviews the synthesis approaches for preparing ternary oxides. Section four discusses the recent progress of solution‐processed ternary oxide as carrier transport/injection layer in optoelectronic devices (such as organic solar cells, perovskite solar cells, organic light emitting diodes, etc.). In this section, the impact of controlling ternary oxide composition on device performance and stability is highlighted. Finally, a brief summary and an outlook are given.     

Solution‐Processed Hydrogen Molybdenum Bronzes as Highly Conductive Anode Interlayers in Efficient Organic Photovoltaics

Highly efficient and stable organic photovoltaic (OPV) cells are demonstrated by incorporating solution‐processed hydrogen molybdenum bronzes as anode interlayers. The bronzes are synthesized using a sol‐gel method with the critical step being the partial oxide reduction/hydrogenation using an alcohol‐based solvent. Their composition, stoichiometry, and electronic properties strongly correlate with the annealing process to which the films are subjected after spin coating. Hydrogen molybdenum bronzes with moderate degree of reduction are found to be highly advantageous when used as anode interlayers in OPVs, as they maintain a high work function similar to the fully stoichiometric metal oxide, whereas they exhibit a high density of occupied gap states, which are beneficial for charge transport. Enhanced short‐circuit current, open‐circuit voltage and, fill factor, relative to reference devices incorporating either PEDOT‐PSS or a solution processed stoichiometric molybdenum oxide, are obtained for a variety of bulk heterojunction mixtures based on different polymeric donors and fullerene acceptors. In particular, high power conversion efficiencies are obtained in devices that employed the s‐H_xMoO_2.75 as the hole extraction layer.     

Batch‐to‐Batch Variation of Polymeric Photovoltaic Materials: its Origin and Impacts on Charge Carrier Transport and Device Performances

A detailed investigation of the impact of molecular weight distribution of a photoactive polymer, poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PCDTBT), on photovoltaic device performance and carrier transport properties is reported. It is found that different batches of as‐received polymers have substantial differences in their molecular weight distribution. As revealed by gel permeation chromatography (GPC), two peaks can generally be observed. One of the peaks corresponds to a high molecular weight component and the other peak corresponds to a low molecular weight component. Photovoltaic devices fabricated with a higher proportion of low molecular weight component have power conversion efficiencies (PCEs) reduced from 5.7% to 2.5%. The corresponding charge carrier mobility at the short‐circuit region is also significantly reduced from 2.7 × 10^?5 to 1.6 × 10^?8 cm² V^?1 s^?1. The carrier transport properties of the polymers at various temperatures are further analyzed by the Gaussian disorder model (GDM). All polymers have similar energetic disorders. However, they appear to have significant differences in carrier hopping distances. This result provides insight into the origin of the molecular weight effect on carrier transport in polymeric semiconducting materials.     

A Self‐Doping,O2‐Stable,n‐Type Interfacial Layer for Organic Electronics

Solid films of a water‐soluble dicationic perylene diimide salt, perylene bis(2‐ethyltrimethylammonium hydroxide imide), Petma⁺OH^?, are strongly doped n‐type by dehydration and reversibly de‐doped by hydration. The hydrated films consist almost entirely of the neutral perylene diimide, PDI, while the dehydrated films contain ～50% PDI anions. The conductivity increases by five orders of magnitude upon dehydration, probably limited by film roughness, while the work function decreases by 0.74 V, consistent with an n‐type doping density increase of ～12 orders of magnitude. Remarkably, the PDI anions are stable in dry air up to 120 °C. The work function of the doped film, ? (3.96 V vs. vacuum), is unusually negative for an O₂‐stable contact. Petma⁺OH^? is also characterized as an interfacial layer, IFL, in two different types of organic photovoltaic cells. Results are comparable to state of the art cesium carbonate IFLs, but may improve if film morphology can be better controlled. The films are stable and reversible over many months in air and light. The mechanism of this unusual self‐doping process may involve the change in relative potentials of the ions in the film caused by their deshielding and compaction as water is removed, leading to charge transfer when dry.     

Electron‐Beam‐Evaporated Nickel Oxide Hole Transport Layers for Perovskite‐Based Photovoltaics

High‐quality charge carrier transport materials are of key importance for stable and efficient perovskite‐based photovoltaics. This work reports on electron‐beam‐evaporated nickel oxide (NiO_x) layers, resulting in stable power conversion efficiencies (PCEs) of up to 18.5% when integrated into solar cells employing inkjet‐printed perovskite absorbers. By adding oxygen as a process gas and optimizing the layer thickness, transparent and efficient NiO_x hole transport layers (HTLs) are fabricated, exhibiting an average absorptance of only 1%. The versatility of the material is demonstrated for different absorber compositions and deposition techniques. As another highlight of this work, all‐evaporated perovskite solar cells employing an inorganic NiO_x HTL are presented, achieving stable PCEs of up to 15.4%. Along with good PCEs, devices with electron‐beam‐evaporated NiO_x show improved stability under realistic operating conditions with negligible degradation after 40 h of maximum power point tracking at 75 °C. Additionally, a strong improvement in device stability under ultraviolet radiation is found if compared to conventional perovskite solar cell architectures employing other metal oxide charge transport layers (e.g., titanium dioxide). Finally, an all‐evaporated perovskite solar mini‐module with a NiO_x HTL is presented, reaching a PCE of 12.4% on an active device area of 2.3 cm².