Charge Formation,Recombination, and Sweep‐Out Dynamics in Organic Solar Cells

This article presents a critical discussion of the various physical processes occurring in organic bulk heterojunction (BHJ) solar cells based on recent experimental results. The investigations span from photoexcitation to charge separation, recombination, and sweep‐out to the electrodes. Exciton formation and relaxation in poly[N‐9″‐hepta‐decanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and poly‐3(hexylthiophene) (P3HT) are discussed based on a fluorescence up‐conversion study. The commonly accepted paradigm describing the conversion of incident photons into charge carriers in the BHJ material is re‐examined in light of these femtosecond time‐resolved measurements. Transient photoconductivity, time‐delayed collection field, and time‐delayed dual pulse experiments carried out on BHJ solar cells demonstrate the competition between carrier sweep‐out by the internal field and the loss of photogenerated carriers by recombination. Finally, an emerging hypothesis is discussed: that bimolecular recombination accounts for the majority of recombination from short circuit to open circuit in optimized solar cells, and that bimolecular recombination is bias‐ and charge‐density‐dependent. The study of recombination loss processes in organic solar cells leads to insights into what must be accomplished to achieve the “ideal” solar cell.     

Impact of Blend Morphology on Interface State Recombination in Bulk Heterojunction Organic Solar Cells

This work is a reinvestigation of the impact of blend morphology and thermal annealing on the electrical performance of regioregular‐P3HT:PC₆₀BM bulk heterojunction organic solar cells. The morphological, structural, and electrical properties of the blend are experimentally investigated with atomic force microscopy, X‐ray diffraction, and time‐of‐flight measurements. Current–voltage characteristics of photodiode devices are measured in the dark and under illumination. Finally, the existence of exponential electronic band tails due to gap states is experimentally confirmed by measuring the device spectral response in the subband gap regime. This method reveals the existence of a large density of gap states, which is partially and systematically reduced by thermal annealing. When the band tails are properly accounted for in the drift and diffusion simulations, experimentally measured charge transport characteristics, under both dark and illuminated conditions and as a function of annealing time, can be satisfactorily reproduced. This work further confirms the critical impact of tails states on the performance of solar cells.     

Influence of Phase Segregation on Recombination Dynamics in Organic Bulk‐Heterojunction Solar Cells

The recombination dynamics of charge carriers in organic bulk‐heterojunction (BHJ) solar cells made of the blend system poly(2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[2,3‐b]thiophene) (pBTCT‐C₁₂):[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) with a donor–acceptor ratio of 1:1 and 1:4 are studied here. The techniques of charge‐carrier extraction by linearly increasing voltage (photo‐CELIV) and, as local probe, time‐resolved microwave conductivity are used. A difference of one order of magnitude is observed between the two blends in the initially extracted charge‐carrier concentration in the photo‐CELIV experiment, which can be assigned to an enhanced geminate recombination that arises through a fine interpenetrating network with isolated phase regions in the 1:1 pBTCT‐C₁₂:PC₆₁BM BHJ solar cells. In contrast, extensive phase segregation in 1:4 blend devices leads to an efficient polaron generation that results in an increased short‐circuit current density of the solar cells. For both studied ratios a bimolecular recombination of polarons is found using the complementary experiments. The charge‐carrier decay order of above two for temperatures below 300 K can be explained on the basis of a release of trapped charges. This mechanism leads to delayed bimolecular recombination processes. The experimental findings can be generalized to all polymer:fullerene blend systems allowing for phase segregation.     

Identifying a Threshold Impurity Level for Organic Solar Cells: Enhanced First‐Order Recombination Via Well‐Defined PC84BM Traps in Organic Bulk Heterojunction Solar Cells

Small amounts of impurity, even one part in one thousand, in polymer bulk heterojunction solar cells can alter the electronic properties of the device, including reducing the open circuit voltage, the short circuit current and the fill factor. Steady state studies show a dramatic increase in the trap‐assisted recombination rate when [6,6]‐phenyl C₈₄ butyric acid methyl ester (PC₈₄BM) is introduced as a trap site in polymer bulk heterojunction solar cells made of a blend of the copolymer poly[N‐9″‐hepta‐decanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the fullerene derivative [6,6]‐phenyl C₆₁ butyric acid methyl ester (PC₆₀BM). The trap density dependent recombination studied here can be described as a combination of bimolecular and Shockley–Read–Hall recombination; the latter is dramatically enhanced by the addition of the PC₈₄BM traps. This study reveals the importance of impurities in limiting the efficiency of organic solar cell devices and gives insight into the mechanism of the trap‐induced recombination loss.     

Influence of Blend Morphology and Energetics on Charge Separation and Recombination Dynamics in Organic Solar Cells Incorporating a Nonfullerene Acceptor

Nonfullerene acceptors (NFAs) in blends with highly crystalline donor polymers have been shown to yield particularly high device voltage outputs, but typically more modest quantum yields for photocurrent generation as well as often lower fill factors (FF). In this study, we employ transient optical and optoelectronic analysis to elucidate the factors determining device photocurrent and FF in blends of the highly crystalline donor polymer PffBT4T‐2OD with the promising NFA FBR or the more widely studied fullerene acceptor PC₇₁BM. Geminate recombination losses, as measured by ultrafast transient absorption spectroscopy, are observed to be significantly higher for PffBT4T‐2OD:FBR blends. This is assigned to the smaller LUMO‐LUMO offset of the PffBT4T‐2OD:FBR blends relative to PffBT4T‐2OD:PC₇₁BM, resulting in the lower photocurrent generation efficiency obtained with FBR. Employing time delayed charge extraction measurements, these geminate recombination losses are observed to be field dependent, resulting in the lower FF observed with PffBT4T‐2OD:FBR devices. These data therefore provide a detailed understanding of the impact of acceptor design, and particularly acceptor energetics, on organic solar cell performance. Our study concludes with a discussion of the implications of these results for the design of NFAs in organic solar cells.     

Nongeminate and Geminate Recombination in PTB7:PCBM Solar Cells

A combination of transient photovoltage (TPV), voltage dependent charge extraction (CE), and time delayed collection field (TDCF) measurements is applied to poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b']dithiophene‐2,6‐diyl] [3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl] thieno[3,4‐b]thiophenediyl]] (PTB7):[6,6]‐phenyl‐C71‐butyric acid (PC₇₁BM) bulk heterojunction solar cells to analyze the limitations of photovoltaic performance. Devices are processed from pure chlorobenzene (CB) solution and a subset is optimized with 1,8‐diiodooctane (DIO) as co‐solvent. The dramatic changes in device performance are discussed with respect to the dominating loss processes. While in the devices processed from CB solution severe geminate and nongeminate recombination is observed, the use of DIO facilitates efficient polaron pair dissociation and minimizes geminate recombination. Thus, from the determined charge carrier decay rate under open circuit conditions and the voltage dependent charge carrier densities n(V), the nongeminate loss current J_loss of the samples with DIO alone enables the reconstruction of the current/voltage (j/V) characteristics across the whole operational voltage range. Geminate and nongeminate losses are considered to describe the j/V response of cells prepared without additive, but lead to a clearly overestimated device performance. The deviation between measured and reconstructed j/V characteristics is attributed to trapped charges in isolated domains of pure fullerene phases.     

局部背接触结构单晶Si太阳电池的研究

报道了采用局部背接触结构的激光刻槽埋栅太阳电池的研究结果.模拟分析了局部背接触结构的作用,设计了合理的电池结构.通过工艺优化,得到了转换效率达到17.28%(大气质量AM=1.5 G,VOC=650.4mV,JSC=33.15 mA/cm2,FF=0.8014,电池面积为4 cm2)的太阳电池.     

Trap‐Assisted Recombination via Integer Charge Transfer States in Organic Bulk Heterojunction Photovoltaics

Organic photovoltaics are under intense development and significant focus has been placed on tuning the donor ionization potential and acceptor electron affinity to optimize open circuit voltage. Here, it is shown that for a series of regioregular‐poly(3‐hexylthiophene):fullerene bulk heterojunction (BHJ) organic photovoltaic devices with pinned electrodes, integer charge transfer states present in the dark and created as a consequence of Fermi level equilibrium at BHJ have a profound effect on open circuit voltage. The integer charge transfer state formation causes vacuum level misalignment that yields a roughly constant effective donor ionization potential to acceptor electron affinity energy difference at the donor–acceptor interface, even though there is a large variation in electron affinity for the fullerene series. The large variation in open circuit voltage for the corresponding device series instead is found to be a consequence of trap‐assisted recombination via integer charge transfer states. Based on the results, novel design rules for optimizing open circuit voltage and performance of organic bulk heterojunction solar cells are proposed.     

Photovoltaic Processes of Singlet and Triplet Excited States in Organic Solar Cells

This article reports the respective photovoltaic processes of singlet and triplet photoexcited states in dissociation and charge reactions based on the studies of magnetic‐field effects of photocurrents. The magnetic‐field effects of photocurrents reveal that weak donor‐acceptor interactions lead to a two‐step photovoltaic process: dissociation in polaron‐pair states evolved from singlet excitonic states and exciton‐charge reactions occurred in triplet excitonic states in the generation of the photocurrent. However, strong donor‐acceptor interactions yield a one‐step photovoltaic process: direct dissociation of both singlet and triplet excitons in bulk‐heterojunction organic solar cells. In addition, the magnetic‐field effects of photocurrents indicate that the dissociated electrons and holes form charge‐transfer complexes with singlet and triplet spin configurations at donor‐acceptor intermolecular interfaces. As a result, the magnetic‐field effects of photocurrents can deliver a critical understanding of singlet and triplet photovoltaic processes to design advanced solar‐energy materials and devices.     

The Role of Insulating Oxides in Blocking the Charge Carrier Recombination in Dye‐Sensitized Solar Cells

Electron recombination is one of the major loss factors in dye‐sensitized solar cells (DSC), especially, with single electron outer sphere redox shuttle electrolyte. Insulating sub‐nanometer oxide tunneling layers deposited by atomic layer deposition (ALD) are known to block the electron recombination, thereby leading to an increase in the open‐circuit potential and the collection efficiency of the solar cell. A general perception in the DSC community is that any insulating oxide layer can block the recombination. However, in this work, it is unraveled that the insulating property of oxides alone is not sufficient. In addition, the properties such as the conduction band position and the oxidation state of the insulating oxide, the electronic structural modification induced to the underlying TiO₂ mesoporous film, modification of surface charges (isoelectric point) and charge of the electrolyte species have to be considered. A complete photovoltaic study is done by depositing different cycles (by ALD) of four different insulating oxides (Ga₂O₃, ZrO₂, Nb₂O₅, and Ta₂O₅) and their recombination characteristics, surface electronic properties, transport rate, and injection dynamics are investigated with a standard organic dye and Co²⁺/Co³⁺ redox mediator. A comparison is made with the conventional iodide/triiodide electrolyte.     

In‐Plane Alignment in Organic Solar Cells to Probe the Morphological Dependence of Charge Recombination

Bulk heterojunction (BHJ) organic solar cells are fabricated with the polymer semiconductor aligned in the plane of the film to probe charge recombination losses associated with aggregates characterized by varying degrees of local order. 100% uniaxial strain is applied on ductile poly(3‐hexylthiophene):phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) BHJ films and characterize the resulting morphology with ultraviolet‐visible absorption spectroscopy and grazing incidence X‐ray diffraction. It is found that the strained films result in strong alignment of the highly ordered polymer aggregates. Polymer aggregates with lower order and amorphous regions also align but with a much broader orientation distribution. The solar cells are then tested under linearly polarized light where the light is selectively absorbed by the appropriately oriented polymer, while maintaining a common local environment for the sweep out of photogenerated charge carriers. Results show that charge collection losses associated with a disordered BHJ film are circumvented, and the internal quantum efficiency is independent of P3HT local aggregate order near the heterojunction interface. Uniquely, this experimental approach allows for selective excitation of distinct morphological features of a conjugated polymer within a single BHJ film, providing insight into the morphological origin of recombination losses.     

Triplet Formation in Fullerene Multi‐Adduct Blends for Organic Solar Cells and Its Influence on Device Performance

In organic solar cells, high open circuit voltages may be obtained by choosing materials with a high offset between the donor highest occupied molecular orbital (HOMO) and acceptor lowest unoccupied molecular orbital (LUMO). However, increasing this energy offset can also lead to photophysical processes that compete with charge separation. In this paper the formation of triplet states is addressed in blends of polyfluorene polymers with a series of PCBM multi‐adducts. Specifically, it is demonstrated that the formation of such triplets occurs when the offset energy between donor ionization potential and acceptor electron affinity is ～1.6 eV or greater. Spectroscopic measurements support a mechanism of resonance energy transfer for triplet formation, influenced by the energy levels of the materials, but also demonstrate that the competition between processes at the donor–acceptor interface is strongly influenced by morphology.     

Efficient Organic Tandem Solar Cells based on Small Molecules

In this paper, two vacuum processed single heterojunction organic solar cells with complementary absorption are described and the construction and optimization of tandem solar cells based on the combination of these heterojunctions demonstrated. The red‐absorbing heterojunction consists of C₆₀ and a fluorinated zinc phthalocyanine derivative (F4‐ZnPc) that leads to a 0.1–0.15 V higher open circuit voltage V_oc than the commonly used ZnPc. The second heterojunction incorporates C₆₀ and a dicyanovinyl‐capped sexithiophene derivative (DCV6T) that mainly absorbs in the green. The combination of both heterojunctions into one tandem solar cell leads to an absorption over the whole visible range of the sun spectrum. Thickness variations of the transparent p‐doped optical spacer between both subcells in the tandem solar cell is shown to lead to a significant change in short circuit current density j_sc due to optical interference effects, whereas V_oc and fill factor are hardly affected. The maximum efficiency η of about 5.6% is found for a spacer thickness of 150‐165 nm. Based on the optimized 165nm thick spacer, effects of intensity and angle of illumination, and temperature on a tandem device are investigated. Variations in illumination intensity lead to a linear change in j_sc over three orders of magnitude and a nearly constant η in the range of 30 to 310 mW cm^?2. Despite the stacked heterojunctions, the performance of the tandem device is robust against different illumination angles: j_sc and η closely follow a cosine behavior between 0° and 70°. Investigations of the temperature behavior of the tandem device show an increase in η of 0.016 percentage points per Kelvin between ?20 °C and 25 °C followed by a plateau up to 50 °C. Finally, further optimization of the tandem stack results in a certified η of (6.07 ± 0.24)% on (1.9893 ± 0.0060)cm² (Fraunhofer ISE), i.e., areas large enough to be of relevance for modules.     

The Role of Higher Lying Electronic States in Charge Photogeneration in Organic Solar Cells

The role of excess photon energy on charge generation efficiency in bulk heterojunction solar cells is still an open issue for the organic photovoltaic community. Here, the spectral dependence of the internal quantum efficiency (IQE) for a poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b]­dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)]:6,6‐phenyl‐C₆₁‐butyric acid methyl ester (PCPDTBT:PC60BM)‐based solar cell is derived combining accurate optoelectronic characterization and comprehensive optical modeling. This joint approach is shown to be essential to get reliable values of the IQE. Photons with energy higher than the bandgap of the donor material can effectively contribute to enhance the IQE of the solar cell. This holds true independently of the device architecture, reflecting an intrinsic property of the active material. Moreover, the nanomorphology of the bulk heterojunction plays a crucial role in determining the IQE spectral dependence: the coarser and more crystalline, the lesser the gain in IQE upon high energy excitation.     

有机聚合物太阳电池电极的表面性能研究

采用多种方法对有机聚合物电池的电极进行表面处理,在测量接触角的基础上,应用几何平均法计算了电极样品的表面能和极性度,研究了处理方法对电极表面润湿性能的影响。结果表明,电极表面性能与其处理方法密切相关,等离子处理具有最小的接触角、最大的表面能和极性度,有效增强了电极表面的润湿性能,这一结果对于优化电极/活性层的界面性质,改善有机聚合物太阳电池的光伏性能具有非常重要的作用。     

有机共混结构太阳电池的阴极界面修饰的研究进展

太阳电池阴极界面的有效修饰能改善器件中载流子的收集与传输,从而提高太阳电池能量转换效率。对于高效、稳定的有机光伏器件来说,合理选择界面修饰材料至关重要,它已成为有机光伏领域研究的重点内容。文章综述了近年来有机共混结构太阳电池阴极界面修饰的研究进展,介绍了各种阴极界面的修饰方法及原理,阐述了国内外有机共混结构太阳电池阴极界面修饰的研究现状及存在问题,为高性能有机太阳电池的研究提供了有价值的参考。     

等离激元共振增强多晶硅薄膜太阳电池性能研究

采用磁控溅射方法,在多晶硅薄膜太阳电池表面沉积了不同粒径大小的Au纳米粒子,利用粒径大小可调控的Au纳米粒子的局域表面等离激元共振增强效应(LSPR),对入射光中的可见光区域实现“光俘获”;采用UV-vis吸收光谱对LSPR进行了研究,结果表明,LSPR能够有效拓展Au纳米粒子的光谱响应范围(400～800 nm),并且,随着Au纳米粒子粒径的增大,LSPR共振吸收峰呈现出明显“红移”;同时,通过SERS表征,证实LSPR能够有效增强Au纳米粒子周围的局域电磁场强度;最后,多晶硅太阳电池的J-V特性曲线表明,当Au纳米粒子溅射时间为50 s时,多晶硅太阳电池光电转换效率(η)最高为14.8％,比未修饰Au纳米粒子的电池η提高了42.3％.     

Transparent Ultrathin Oxygen‐Doped Silver Electrodes for Flexible Organic Solar Cells

An effective method for depositing highly transparent and conductive ultrathin silver (Ag) electrodes using minimal oxidation is reported. The minimal oxidation of Ag layers significantly improves the intrinsic optical and structural properties of Ag without any degradation of its electrical conductivity. Oxygen‐doped Ag (AgO_x) layers of thicknesses as low as 6 nm exhibit completely 2D and continuous morphologies on ZnO films, smaller optical reflections and absorbances, and smaller sheet resistances compared with those of discontinuous and granular‐type Ag layers of the same thickness. A ZnO/AgO_x/ZnO (ZAOZ) electrode using an AgO_x (O/Ag = 3.4 at%) layer deposited on polyethylene terephthalate substrates at room temperature shows an average transmittance of 91%, with a maximum transmittance of 95%, over spectral range 400?1000 nm and a sheet resistance of 20 Ω sq^?1. The average transmittance value is increased by about 18% on replacing a conventional ZnO/Ag/ZnO (ZAZ) electrode with the ZAOZ electrode. The ZAOZ electrode is a promising bottom transparent conducting electrode for highly flexible inverted organic solar cells (IOSCs), and it achieves a power conversion efficiency (PCE) of 6.34%, whereas an IOSC using the ZAZ electrode exhibits a much lower PCE of 5.65%.     

Imaging the Electric Potential within Organic Solar Cells

The charge transport in organic solar cells is investigated by surface potential measurements via scanning Kelvin probe microscopy. Access to the solar cell's cross‐section is gained by milling holes with a focused ion beam which enables the direct scan along the charge transport path. In a study of poly(3‐hexylthiophene):1‐(3‐methoxycarbonyl)propyl‐1‐phenyl[6,6]C61 (P3HT:PCBM) bulk heterojunction solar cells, the open circuit voltage is built up at the top contact. A comparison of the potential distribution within normal and inverted solar cells under operation exhibits strongly different behaviors, which can be assigned to a difference in interface properties.     

Non‐Geminate Recombination as the Primary Determinant of Open‐Circuit Voltage in Polythiophene:Fullerene Blend Solar Cells: an Analysis of the Influence of Device Processing Conditions

The physical origin of the open‐circuit voltage in bulk heterojunction solar cells is still not well understood. While significant evidence exists to indicate that the open‐circuit voltage is limited by the molecular orbital energies of the heterojunction components, it is clear that this picture is not sufficient to explain the significant variations which often occur between cells fabricated from the same heterojunction components. We present here an analysis of the variation in open‐circuit voltage between 0.4–0.65 V observed for a range of P3HT/PCBM solar cells where device deposition conditions, electrode structure, active‐layer thickness and device polarity are varied. The analysis quantifies non‐geminate recombination losses of dissociated carriers in these cells, measured under device operating conditions. It is found that at open‐circuit, losses due to non‐geminate recombination are sufficiently large that other loss pathways may effectively be neglected. Variations in open‐circuit voltage between different devices are shown to arise from differences in the rate coefficient for non‐geminate recombination, and from differences in the charge densities in the photoactive layer of the device. The origin of these differences is discussed, particularly with regard to variations in film microstructure. By separately quantifying these differences in rate coefficient and charge density, and by application of a simple physical model based upon the assumption that open‐circuit is reached when the flux of charge photogeneration is matched by the flux of non‐geminate recombination, we are able to calculate correctly the open‐circuit voltage for all the cells studied to within an accuracy of ±5 mV.