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.     

Saccharide Blocking Layers in Solid State Dye Sensitized Solar Cells

The adsorption of saccharides on dye sensitized, nanocrystalline metal oxide films is shown to improve the efficiency of solid state dye sensitized solar cells. The function of the saccharide treatment is evaluated by transient optical studies, and correlated with device photovoltaic performance. A range of saccharides, including cyclodextrins and their linear analogue amylose, are investigated. The saccharide blocking layer is shown to retard interfacial charge recombination losses, resulting in increased device open circuit voltage. Highest device performance is achieved with linear saccharide amylose, resulting in a 60 % improvement in device efficiency relative to the non‐treated control, with a device open circuit voltage of 1 V.     

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.     

Charge Photogeneration for a Series of Thiazolo‐Thiazole Donor Polymers Blended with the Fullerene Electron Acceptors PCBM and ICBA

Photoinduced charge separation in bulk heterojunction solar cells is studied using a series of thiazolo‐thiazole donor polymers that differ in their side groups (and bridging atoms) blended with two acceptor fullerenes, phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) and a fullerene indene‐C60 bisadduct (ICBA). Transient absorption spectroscopy is used to determine the yields and lifetimes of photogenerated charge carriers, complimented by cyclic voltammetry studies of materials energetics, wide angle X‐ray diffraction and transmission electron microscopy studies of neat and blend film crystallinity and photoluminescence quenching studies of polymer/fullerene phase segregation, and the correlation of these measurements with device photocurrents. Good correlation between the initial polaron yield and the energetic driving force driving charge separation, ΔE_CS is observed. All blend films exhibit a power law transient absorption decay phase assigned to non‐geminate recombination of dissociated charges; the amplitude of this power law decay phase shows excellent correlation with photocurrent density in the devices. Furthermore, for films of one (relatively amorphous) donor polymer blended with ICBA, we observe an additional 100 ns geminate recombination phase. The implications of the observations reported are discussed in terms of the role of materials' crystallinity in influencing charge dissociation in such devices, and thus materials design requirements for efficient solar cell function.     

Nongeminate Recombination and Charge Transport Limitations in Diketopyrrolopyrrole‐Based Solution‐Processed Small Molecule Solar Cells

Charge transport and nongeminate recombination are investigated in two solution‐processed small molecule bulk heterojunction solar cells consisting of diketopyrrolopyrrole (DPP)‐based donor molecules, mono‐DPP and bis‐DPP, blended with [6,6]‐phenyl‐C71‐butyric acid methyl ester (PCBM). While the bis‐DPP system exhibits a high fill factor (62%) the mono‐DPP system suffers from pronounced voltage dependent losses, which limit both the fill factor (46%) and short circuit current. A method to determine the average charge carrier density, recombination current, and effective carrier lifetime in operating solar cells as a function of applied bias is demonstrated. These results and light intensity measurements of the current‐voltage characteristics indicate that the mono‐DPP system is severely limited by nongeminate recombination losses. Further analysis reveals that the most significant factor leading to the difference in fill factor is the comparatively poor hole transport properties in the mono‐DPP system (2 × 10^?5 cm² V^?1 s^?1 versus 34 × 10^?5 cm² V^?1 s^?1). These results suggest that future design of donor molecules for organic photovoltaics should aim to increase charge carrier mobility thereby enabling faster sweep out of charge carriers before they are lost to nongeminate recombination.     

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.     

Nanostructured Si/Organic Heterojunction Solar Cells with High Open‐Circuit Voltage via Improving Junction Quality

Nanostructured silicon (Si) can provide improved light harvest efficiencies in organic‐Si heterojunction solar cells due to its low light reflection ratio compared with planar one. However, the associated large surface/volume ratio of nanostructured Si suffers from serious surface recombination as well as poor adhesion with organics in organic‐Si heterojunction solar cells, which leads to an inferior open‐circuit voltage (V_oc). Here, we develop a simple and effective method to suppress charge recombination as well as enhancing adhesion force between nanostructured Si and organics by incorporating a silane chemical, namely 3‐glycidoxypropyltrimethoxydsilane (GOPS). GOPS can chemically graft onto nanostructured Si and improve the aqueous organic wetting properties, suppressing surface charge recombination velocity dramatically. In addition, this chemically grafted layer can enhance adhesion force between organics and Si. In such a way, a record V_oc of 640 mV associated with a power conversion efficiency of 14.1% is obtained for organic‐nanostructured Si heterojunction devices. These findings suggest a promising approach to low‐cost and simple fabrication for high‐performance organic‐Si solar cells.     

Enhancing Photovoltaic Performance Using an All‐Conjugated Random Copolymer to Tailor Bulk and Interfacial Morphology of the P3HT:ICBA Active Layer

Bulk heterojunction (BHJ) solar cells are fabricated using active material blends of poly(3‐hexylthiophene) (P3HT) donor, indene‐C₆₀ bisadduct (ICBA) acceptor, and an all‐conjugated random copolymer (RCP) additive. By optimizing RCP loading, power conversion efficiencies (PCEs) up to 20% higher than those of a binary P3HT:ICBA mixture are achieved. The improved device characteristics are rationalized in terms of the differences between the photoactive thin film morphologies. Energy‐filtered transmission electron micro­scopy reveals that incorporation of the RCP improves the degree of structural order of the BHJ fibrillar network and increases the extent of microphase separation between P3HT and ICBA. Additionally, a combination of atomic force microscopy and X‐ray photoelectron spectroscopy analysis indicates segregation of the RCP at the free interface, leading to a shift in the surface potentials measured by Kelvin probe force microscopy. These changes, both in the bulk morphology and in the interfacial composition/energetics, are correlated to improved carrier collection efficiency due to a reduction of non‐geminate recombination, which is measured by charge extraction of photo­generated carriers by linearly increasing voltage.     

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.     

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.     

Optimization and characterization of amorphous/crystalline silicon heterojunction solar cells

Amorphous hydrogenated silicon/crystalline silicon (a‐Si:H/c‐Si) heterojunction solar cells are investigated and optimized with regard to efficiency and simplicity of processing. Starting with a survey of a‐Si:H/c‐Si heterojunction solar cell results from the literature, we describe the fabrication steps of our a‐Si:H/c‐Si technology and analyze the electronic device properties by quantum efficiency, current–voltage, admittance, and capacitance–voltage measurements. The open‐circuit voltage and the fill factor of the a‐Si:H/c‐Si heterojunction solar cells under investigation are limited by recombination in the neutral zone of the crystalline Si absorber. Recombination at the a‐Si:H/c‐Si‐interface is subsidiary in respect of the limitation of the open‐circuit voltage. Our best n‐type a‐Si:H/p‐type c‐Si solar cell prepared without high‐efficiency features such as back‐surface field or surface texturing has an independently confirmed efficiency of 14.1% and an open‐circuit voltage of 655 mV. Copyright © 2001 John Wiley & Sons, Ltd.     

Organic Field‐Effect Devices as Tool to Characterize the Bipolar Transport in Polymer‐Fullerene Blends: The Case of P3HT‐PCBM

In organic bulk heterojunction solar cells (oBHJ) the blend morphology in combination with the charge transport properties of the individual components controls the extracted photocurrent. The organic field‐effect transistor (OFET) has been proved as a powerful instrument to evaluate the unipolar carrier transport properties in a wide range of cases. In our work we extend the OFET concept to the evaluation of the bipolar transport properties in polymer‐fullerenes blends and propose a method to improve the accuracy of the evaluation. The method is based on capacitance–voltage (C–V) measurements on MOS structures prepared on the same blends and delivers complementary information on the bulk heterojunction to the one obtained with FETs. The relevance for photovoltaic applications is investigated through the correlation between the current–voltage behavior of solar cells and the bipolar mobility for composites with varying polymer molecular weight and processed from different solvents. In particular the transport features of solar cells produced from o‐Xylene (oX), a non chlorinated solvent more suitable to production requirements, have been compared to the one of devices cast from Chlorobenzene (CB) solution. For the P3HT‐PCBM blend a consistent correlation between the mobility and the electrical fill factor and power performance was found. A significant asymmetry in the bipolar carrier mobility, together with low electron mobility dependent on the M_w value, affects the performances of thick o‐Xylene cast devices. In the case of devices processed from Chlorobenzene the slower carrier has higher mobility and the small electrical losses detected are eventually more related to the formation of space‐charge and eventually to surface recombination. This results in an efficient charge collection that is almost thickness independent. We report a dependence of the slow‐carrier type (electrons or holes) and their mobility on the specific combination of molecular weight and solvent. The mobility data and the solar cell performance coherently fit to the prediction of a device model only based on the drift of carriers under the built‐in electric field originated in the donor‐acceptor oBHJ.     

Thermo‐Phototronic Effect Enhanced InP/ZnO Nanorod Heterojunction Solar Cells for Self‐Powered Wearable Electronics

Enhancing interfacial charge transfer by the inner electric field is crucial for improving photovoltaic performance of heterojunction solar cells. Recent studies are focusing on how to utilize piezo‐phototronic effect (strain‐induced inner electric field) to modulate the interfacial charge transfer, whereas the preservation of solar cells from structure damage and performance decline under long‐term strain becomes increasingly challenging. Here, without use of strain, a thermo‐phototronic effect is presented to enhance the interfacial charge transfer in InP/ZnO nanorod heterojunction solar cells. Under a temperature gradient of 3.5 °C across the device, the output current and voltage of the solar cell under weak light illumination are enhanced by 27.3 and 76%, respectively. Moreover, the performance enhancement can be further regulated by applying different temperature gradients. This study serves as proof‐of‐principle for the thermo‐phototronic effect and pushes forward the maximum utilization of solar energy by a one‐circuit‐based photovoltaic‐thermoelectric system.     

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.     

Light‐enhanced surface passivation of TiO2‐coated silicon

Titanium dioxide is shown to afford good passivation to non‐diffused silicon surfaces and boron‐diffused surfaces after a low‐temperature anneal. The passivation most likely owes to the significant levels of negative charge instilled in the films, and passivation is enhanced by illumination—advantageous for solar cells—indicating that a titanium dioxide photoreaction is at least partly responsible for the low surface recombination. We demonstrate a surface recombination velocity of less than 30 cm/s, on a 5‐Ω cm n‐type silicon, and an emitter saturation current density of 90 fA/cm² on a 200‐Ω/sq boron diffusion. If these titanium dioxide passivated boron‐diffused surfaces were employed in a crystalline silicon solar cell, an open‐circuit voltage as high as 685 mV could be achieved. Given that TiO₂ has a high refractive index and was deposited with atmospheric pressure chemical vapour deposition, an inexpensive technique, it has the potential as a passivating antireflection coating for industrial boron‐diffused silicon solar cells. Copyright © 2011 John Wiley & Sons, Ltd.     

Biohybrid Photoprotein‐Semiconductor Cells with Deep‐Lying Redox Shuttles Achieve a 0.7 V Photovoltage

Photosynthetic proteins transduce sunlight into biologically useful forms of energy through a photochemical charge separation that has a close to 100% quantum efficiency, and there is increasing interest in their use as sustainable materials in biohybrid devices for solar energy harvesting. This work explores a new strategy for boosting the open circuit voltage of photoelectrochemical cells based on a bacterial photosynthetic pigment‐protein by employing highly oxidizing redox electrolytes in conjunction with an n‐type silicon anode. Illumination generates electron–hole pairs in both the protein and the silicon electrode, the two being connected by the electrolyte which transfers electrons from the reducing terminal of the protein to photogenerated holes in the silicon valence band. A high open circuit voltage of 0.6 V is achieved with the most oxidizing electrolyte 2,2,6,6‐tetramethyl‐1‐piperidinyloxy, and this is further improved to 0.7 V on surface modification of the silicon electrode to increase its surface area and reduce reflection of incident light. The photovoltages produced by these biohybrid protein/silicon cells are comparable to those typical of silicon heterojunction and dye‐sensitized solar cells.     

Effects of Nonradiative Losses at Charge Transfer States and Energetic Disorder on the Open‐Circuit Voltage in Nonfullerene Organic Solar Cells

The considerable improvement on the power conversion efficiency (PCE) for emerging nonfullerene polymer solar cells is still limited by considerable voltage losses that have become one of the most significant obstacles in further boosting desired photovoltaic performance. Here, a comprehensive study is reported to understand the impacts of charge transport, energetic disorder, and charge transfer states (CTS) on the losses in open‐circuit voltage (V_oc) based on three high performing bulk heterojunction solar cells with the best PCE exceeding 11%. It is found that the champion poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene)‐co‐(1,3‐di(5‐thiophene‐2‐yl)‐5,7‐bis(2‐ethylhexyl)‐benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione))] (PBDB‐T):IT‐M solar cell (PCE = 11.5%) is associated with the least disorder. The determined energetic disorder in part reconciles the difference in V_oc between the solar cells. A reduction is observed in the nonradiative losses (ΔV_nonrad) coupled with the increase of energy of CTS for the PBDB‐T:IT‐M device, which may be related to the improved balance in carrier mobilities, and partially can explain the gain in V_oc. The determined radiative limit for V_oc combined with the ΔV_nonrad generates an excellent agreement for the V_oc with the experimental values. The results suggest that minimizing the energetic disorder related to transport and CTS is critical for the mitigation of V_oc losses and improvements on the device performance.     

Solution‐Processed Organic Tandem Solar Cells

A solution‐processed polymer tandem cell fabricated by stacking two single cells in series is demonstrated. The two bulk‐heterojunction subcells have complementary absorption maxima at λ_max ～ 850 nm and λ_max ～ 550 nm, respectively. A composite middle electrode is applied that serves both as a charge‐recombination center and as a protecting layer for the first cell during spin‐coating of the second cell. The subcells are electronically coupled in series, which leads to a high open‐circuit voltage of 1.4 V, equal to the sum of each subcell. The layer thickness of the first (bottom) cell is tuned to maximize the optical absorption of the second (top) cell. The performance of the tandem cell is presently limited by the relatively low photocurrent generation in the small‐bandgap polymer of the top cell. The combination of our tandem architecture with more efficient small‐bandgap materials will enable the realization of highly efficient organic solar cells in the near future.     

High efficiency all‐GaAs solar cell

The reduction of surface recombination in GaAs solar cells is known to be a major concern for photovoltaic cells designers. A common technique used to reduce this effect is to cover the GaAs surface with a wide band gap window layer, therefore the creation of a heterojunction. To avoid a heterojunction with its inconveniences; interface surface states, poor photon absorption in addition to the technological exigencies, one can use an all‐GaAs solar cell. In this type of structure, a thin highly doped layer is created at the surface known as a front surface field (FSF). The main role of an FSF layer is to reduce the effect of front surface recombination and the enhancement of light‐generated free carriers' collection. This is achieved by the drastic reduction of the effective recombination at the emitter upper boundary. In this work, a simple analytical model is used to simulate the influence of the FSF layer on GaAs solar cell parameters; photocurrent, open circuit voltage and energy conversion efficiency. The effects of the FSF layer doping density and its thickness on the cell performance are discussed by using computed results. Copyright © 2010 John Wiley & Sons, Ltd.     

Electron Trapping in Higher Adduct Fullerene‐Based Solar Cells

Here, the performance of bulk‐heterojunction solar cells based on a series of bisadduct analogues of commonly used derivatives of C₆₀ and C₇₀, such PCBMs and their thienyl versions, is investigated. Due to their higher lowest unoccupied molecular orbital an increase in open‐circuit voltage and thus performance is expected. It is shown that the occurrence of a multitude of different isomers results in a decrease in the electron transport for some of the materials. Surprisingly, the solar‐cell characteristics are very similar for all materials. This apparent discrepancy is explained by a significant amount of shallow trapping occurring in the fullerene phase that does not hamper the solar cell performance due the filling of these shallow traps during illumination. Furthermore, the trisadduct analogue of [60]PCBM has been investigated, which, despite an even further increase in open‐circuit voltage, results in a significantly reduced device performance due to a strong deterioration of the electron mobility in the fullerene phase.