Hybrid polymer/nanoparticle solar cells: preparation, principles and challenges

Hybrid polymer/nanoparticle solar cells have a light harvesting layer composed of semiconducting inorganic nanoparticles and a semiconducting conjugated polymer. They have potential to give high power conversion efficiencies (PCE). However, the PCE values reported for these solar cells are not currently as high as anticipated. This article reviews the main methods currently used for preparing hybrid polymer/nanoparticle solar cells from the colloid perspective. PCE data for the period of 2005-2011 are presented for hybrid polymer/nanoparticle solar cells and compared to those from polymer/fullerene cells. The key reasons for the relatively low PCE values for hybrid polymer/nanoparticle solar cells are uncontrolled aggregation and residual insulating ligands at the nanoparticle surface. Two hybrid polymer/nanoparticle systems studied at Manchester are considered in which the onset of aggregation and its affect on composite film morphology were studied from the colloidal perspective. It is concluded that step-change approaches are required to increase the PCEs of hybrid polymer/nanoparticle solar cells and move them toward the 10% value required for widespread commercialisation. A range of nanoparticles that have potential for application in possible longer term terawatt solar energy production are discussed.     

Effect of polydispersity on the bulk‐heterojunction morphology of P3HT:PCBM solar cells

Bulk heterojunctions (BHJs) based on semiconducting electron–donor polymer and electron–acceptor fullerene have been extensively investigated as potential photoactive layers for organic solar cells (OSCs). In the experimental studies, poly‐(3‐hexyl‐thiophene) (P3HT) polymers are hardly monodisperse as the synthesis of highly monodisperse polymer mixture is a near impossible task to achieve. However, the majority of the computational efforts on P3HT: phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM)‐based OSCs, a monodisperse P3HT is usually considered. Here, results from coarse‐grained molecular dynamics simulations of solvent evaporation and thermal annealing process of the BHJ are shared describing the effect of variability in molecular weight (also known as polydispersity) on the morphology of the active layer. Results affirm that polydispersity is beneficial for charge separation as the interfacial area is observed to increase with higher dispersity. Calculations of percolation and orientation tensors, on the other hand, reveal that a certain polydispersity index ranging between 1.05 and 1.10 should be maintained for optimal charge transport. Most importantly, these results point out that the consideration of polydispersity should be considered in computational studies of polymer‐based OSCs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 895–903     

Nanocomposites composed of P3HT:PCBM and nanoparticles synthesized by laser ablation of a bulk PbS target in liquid

Nanoparticles synthesized by laser ablation of bulk target materials in liquids have ligand-free surfaces since no chemical precursors are used for their synthesis, and thus, they are ideally suited for applications in the fabrication of organic solar cells in which the properties of the interface between the nanoparticles and the polymer blend matrix largerly determine the exciton splitting and transport of carriers to the external electrodes, properties crucial for the device operation and performance. Narrow band gap semiconducting quantum dots can act as sensitizers, increasing the absorption of the device active layer in the infrared part of the solar spectrum. In this work, a bulk PbS target was laser ablated (450 fs, 1,064 nm, 1 kHz) in ethanol for the synthesis of nanoparticle colloidal solutions. The solutions exhibit a broad absorption which extends at the longest wavelength measured of ~1,700 nm and beyond. The nanoparticles were directly mixed with the blend P3HT:PCBM for the formation of nanocomposites. The nanocomposites with the nanoparticles exhibit lower transmission in the whole spectral range as compared to the blend without the nanoparticles.     

Interplay of three-dimensional morphologies and photocarrier dynamics of polymer/TiO2 bulk heterojunction solar cells

In this study, we investigated the interplay of three-dimensional morphologies and the photocarrier dynamics of polymer/inorganic nanocrystal hybrid photoactive layers consisting of TiO(2) nanoparticles and nanorods. Electron tomography based on scanning transmission electron microscopy using high-angle annular dark-field imaging was performed to analyze the morphological organization of TiO(2) nanocrystals in poly(3-hexylthiophene) (P3HT) in optimal solar cell devices. The Three-dimensional (3D) morphologies of these hybrid films were correlated with the photocarrier dynamics of charge separation, transport, and recombination, which were comprehensively probed by various transient techniques. Visualization of these 3D bulk heterojunction morphologies clearly reveals that elongated and anisotropic TiO(2) nanorods in P3HT not only can significantly reduce the probability of the interparticle hopping transport of electrons by providing better connectivity with respect to the TiO(2) nanoparticles, but also tend to form a large-scale donor-acceptor phase-separated morphology, which was found to enhance hole transport. The results support the establishment of a favorable morphology for polymer/inorganic hybrid solar cells due to the presence of the dimensionality of TiO(2) nanocrystals as a result of more effective mobile carrier generation and more efficient and balanced transport of carriers.     

Designing Nonfullerene Acceptors with Oligo(Ethylene Glycol) Side Chains: Unraveling the Origin of Increased Open-Circuit Voltage and Balanced Charge Carrier Mobilities

Despite the recent rapid development of organic solar cells (OSCs), the low dielectric constant (ϵ_r=3–4) of organic semiconducting materials limits their performance lower than inorganic and perovskite solar cells. In this work, we introduce oligo(ethylene glycol) (OEG) side chains into the dicyanodistyrylbenzene-based non-fullerene acceptors (NIDCS) to increase its ϵ_r up to 5.4. In particular, a NIDCS acceptor bearing two triethylene glycol chains (NIDCS-EO3) shows V_OC as high as 1.12 V in an OSC device with a polymer donor PTB7, which is attributed to reduced exciton binding energy of the blend film. Also, the larger size grain formation with well-ordered stacking structure of the NIDCS-EO3 blend film leads to the increased charge mobility and thus to the improved charge mobility balance, resulting in higher J_SC, FF, and PCE in the OSC device compared to those of a device using the hexyl chain-based NIDCS acceptor (NIDCS-HO). Finally, we fabricate NIDCS-EO3 devices with various commercial donors including P3HT, DTS-F, and PCE11 to show higher photovoltaic performance than the NIDCS-HO devices, suggesting versatility of NIDCS-EO3.     

Elaboration of nanohybrid materials by photopolymerisation of 3,4-ethylenedioxythiophene on TiO2

A method for the elaboration of a heterojunction composed on n-type inorganic semiconducting nanoparticles, TiO(2), and a p-type organic semiconducting polymer poly(3,4-ethylene dioxythiophene) by UV illumination is described.     

Nanoparticles in solutions of adsorbing polymers: pair interactions, percolation, and phase behavior

We study the polymer adsorption characteristics, pair-interaction potentials, and phase and percolation behavior in nanoparticle-polymer mixtures. We propose a "saturable" adsorption model to capture the effect of the finite surface saturation capacity for adsorption, and use polymer self-consistent field theory in combination with a McMillan-Mayer framework [McMillan, W. G., Jr.; Mayer, J. E. J. Chem. Phys. 1945, 13, 276] to compute the pair-interaction potentials. Our results demonstrate novel size effects that distinguish the adsorption characteristics of nanoparticles from that of larger particles. Specifically, we predict that the nanoparticle regime is characterized by a significant adsorbance of polymers, albeit distributed predominantly in the form of tails. We also demonstrate that an interplay between the surface saturation, polymer-to-particle size ratios, and the polymer concentrations governs the overall effective interactions between nanoparticles in the presence of an adsorbing polymer. We use simple, mean-field models to relate these characteristics to the phase and percolation behavior in such systems. Our results show that the percolation thresholds for smaller particles are significantly smaller (and, overall, correspond only to a few volume percent) compared to that of the larger particles. Further, with a decrease in the size of the particles, we also predict a considerable increase in the miscibility of the polymer-particle mixtures. Our results are qualitatively in accord with many experimental observations in the nanoparticle regime.     

Controlling the self-assembly structure of magnetic nanoparticles and amphiphilic block-copolymers: from micelles to vesicles

We report how to control the self-assembly of magnetic nanoparticles and a prototypical amphiphilic block-copolymer composed of poly(acrylic acid) and polystyrene (PAA-b-PS). Three distinct structures were obtained by controlling the solvent-nanoparticle and polymer-nanoparticle interactions: (1) polymersomes densely packed with nanoparticles (magneto-polymersomes), (2) core-shell type polymer assemblies where nanoparticles are radially arranged at the interface between the polymer core and the shell (magneto-core shell), and (3) polymer micelles where nanoparticles are homogeneously incorporated (magneto-micelles). Importantly, we show that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. As a consequence, the self-assembly of micelle-forming block-copolymers typically produces magneto-polymersomes instead of magneto-micelles. On the other hand, vesicle-forming polymers tend to form magneto-micelles due to the solubilization of nanoparticles in polymer assemblies. The nanoparticle-polymer interaction also controls the nanoparticle arrangement in the polymer matrix. In N,N-dimethylformamide (DMF) where PS is not well-solvated, nanoparticles segregate from PS and form unique radial assemblies. In tetrahydrofuran (THF), which is a good solvent for both nanoparticles and PS, nanoparticles are homogeneously distributed in the polymer matrix. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their magnetic relaxation properties, emphasizing the importance of the self-assembly structure and nanoparticle arrangement as well as the size of the assemblies.     

聚合物/无机纳米粒子复合膜在气体分离中的研究进展

由于聚合物膜具有可高度设计、机械性能好、易于加工 等优点,是理想的气体分离材料。然而,聚合物膜在气体选择性和渗透性方面存在平衡限制,在聚合物中引入纳米粒子,是提高气体分离性能的一种有效手段。本文基于聚合物/无机纳米粒子复合膜在气体分离领域的研究现状,重点阐述了零维纳米粒子（二氧化硅、二氧化钛）、一维纳米粒子（碳纳米管）、二维纳米粒子（氧化石墨烯、二维过渡金属氧化物）、三维纳米粒子（金属有机框架、沸石）对气体分离性能的影响,并展望了聚合物复合分离膜的发展趋势,为未来高效分离膜的研发提供了参考。     

Preparation and Characterization of the Hybrids Containing Silica Nanoparticles by Sol-Gel Crosslinking Process

The organic/inorganic hybrid nanomaterials containing silica nanoparticles are synthesized by sol-gel crosslinking process. The tetraethoxysilane (TEOS) and γ-aminopropyltriethoxylsilane as coupling agents are used as a precursor. The 2,4,6-tri [(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) as crosslinking agent is used to form covalent bonds among the inorganic nanoparticles. The chemical and morphological structures of the organic/inorganic hybrid are characterized with FTIR spectra, ²⁹Si-NMR, x-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and atomic force microscope (AFM). The results show that the organic/inorganic hybrid forms covalent bond between the inorganic nanoparticle and Tri-EBAC. The network organic/inorganic hybrid can form good film with even nanometer particles. The network organic/inorganic hybrids nanomaterial not only exhibits the thermal properties of inorganic compounds, but also exhibits the thermal properties of organic polymer.     

Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size

This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.     

基于富勒烯和噻吩聚合物的本体异质结太阳电池

随着全球能源需求量的逐年增加,对可再生能源的有效利用成为亟待解决的问题。现在使用的能源多来自矿物燃料的开采,其中包括石油、天然气和煤等,而这些资源是非常有限的。因此,发展新能源和新能源材料是我国进入21世纪必须解决的重大课题,其中太阳能被认为是清洁可再生新能源的代表之一。基于噻吩跟富勒烯的异质结太阳能电池是目前太阳能电池的重要发展方向之一。该种太阳能电池因其制备简单、成本低廉、重量轻和可制成柔性器件等优点近年来受到多方的广泛重视。经过努力,该种太阳能电池的光电转化性能已经得到了一定提高,最高光电转化效率已达到7%左右,但是跟无机半导体硅和染料敏化太阳能电池相比还有一定差距。因此,这方面的研究任重而道远,研究空间也非常大。本文从材料合成的角度,简要综述了近年来国内外在基于富勒烯和噻吩的异质结太阳能电池方面所取得的最新研究进展,并对下一步需要研究的热点问题作了展望。     

An Unconventional Route to Monodisperse and Intimately Contacted Semiconducting Organic–Inorganic Nanocomposites

We developed an unconventional route to produce uniform and intimately contacted semiconducting organic–inorganic nanocomposites for potential applications in thermoelectrics. By utilizing amphiphilic star‐like PAA‐b‐PEDOT diblock copolymer as template, monodisperse PEDOT‐functionalized lead telluride (PbTe) nanoparticles were crafted via the strong coordination interaction between PAA blocks of star‐like PAA‐b‐PEDOT and the metal moieties of precursors (i.e., forming PEDOT–PbTe nanocomposites). As the inner PAA blocks are covalently connected to the outer PEDOT blocks, the PEDOT chains are intimately and permanently tethered on the PbTe nanoparticle surface, thereby affording a well‐defined PEDOT/PbTe interface, which prevents the PbTe nanoparticles from aggregation, and more importantly promotes the long‐term stability of PEDOT–PbTe nanocomposites. We envision that the template strategy is general and robust, and offers easy access to other conjugated polymer–inorganic semiconductor nanocomposites for use in a variety of applications.     

喷涂法制备高效率三元体系聚合物太阳能电池

采用喷涂技术制备了能量转化效率为9.06%的三元体系聚合物太阳能电池,该太阳能电池在卷对卷印刷和规模化生产中具有极大的应用潜力。     

制备二氧化钛分枝纳米棒阵列结构以提高聚合物杂化太阳电池的性能

分别采用一步水热法和两步水热法在导电玻璃(FTO)上制备了二氧化钛(TiO₂)纳米棒(NR)阵列和TiO₂分枝纳米棒(B-NR)阵列。 利用低温化学浴沉积法(CBD)在TiO₂纳米棒阵列(NRA)和TiO₂分枝纳米棒阵列(B-NRA)基底上沉积Sb₂S₃纳米粒子(NPs)。 接着分别旋涂聚-3已基噻吩(P3HT)和2,2'7,7'-四-(二甲氧基二苯胺)螺芴(Spiro-OMeTAD)组装成TiO₂(NRA)/Sb₂S₃/P3HT/Spiro-OMeTAD和TiO₂(B-NRA)/Sb₂S₃/P3HT/ Spiro-OMeTAD为光活性层的杂化太阳电池。 结果表明,由TiO₂(NRA)/Sb₂S₃/P3HT/Spiro-OMeTAD复合膜结构组装的杂化太阳电池的光电转换效率(PCE)是2.92%,而由TiO₂(B-NRA)/Sb₂S₃/P3HT/Spiro-OMeTAD复合膜结构组装的杂化太阳电池的PCE提高到了4.67%。     

Using light to covalently immobilize and pattern nanoparticles onto surfaces

There is considerable current interest in developing methods to integrate nanoparticles into optical, electronic, and biological systems due to their unique size-dependent properties and controllable shape. We report herein a versatile new approach for covalent immobilization of nanoparticles onto substrates modified with photoactive, phthalimide-functional, self-assembled monolayers. Upon illumination with UV radiation, the phthalimide group abstracts a hydrogen atom from a neighboring organic molecule, leading to radical-based photografting reactions. The approach is potentially "universal" since virtually any polymeric or organic-inorganic hybrid nanoparticle can be covalently immobilized in this fashion. Because grafting is confined to illuminated regions that undergo photoexcitation, masking provides a simple and direct method for nanoparticle patterning. To illustrate the technique, nanoparticles formed from diblock copolymers of poly(styrene-b-polyethylene oxide) and laden with Hostasol Red dye are photografted and patterned onto glass and silicon substrates modified with photoactive phthalimide-silane self-assembled monolayers. Atomic force microscopy and X-ray photoelectron spectroscopy are applied to characterize the grafted nanoparticle films while confocal fluorescence microscopy is used to image patterned nanoparticle deposition.     

Semiconducting nanocrystals,conjugated polymers,and conjugated polymer/nanocrystal nanohybrids and their usage in solar cells

As one of the major renewable energy sources, solar energy has the potential to become an essential component of future global energy production. With the increasing demand in energy, the harvesting of solar energy using inexpensive materials and manufacturing methods has attracted considerable attention. Organic/inorganic (i.e., conjugated polymer/nanocrystal (CP/NC)) nanohybrid solar cell, including both physically mixed CP/NC composites and covalently linked CP-NC nanocomposites, is one of the several most promising alternative, cost-effective concepts for solar-to-electric energy conversion that has been offered to challenge conventional Si solar cells over the past decade. It has low fabrication cost and capability of large-scale production. However, to date, the highest power conversion efficiency (PCE) of organic/inorganic nanohybrid solar cells has been reported to be only 5.5%, which is still lower than the theoretical prediction of more than 10%. Several problems, i. e., microscopic phase separation of semiconducting CPs and NCs, low charge injection, and low carrier collection, have not been well addressed. More research remains to be done to improve the efficiency of CP/NC nanohybrid solar cells. In this review article, the recent advances in solving these problems were discussed. For the CP/NC solar cells prepared by physically mixing electron donating CP and electron accepting NC (i.e., forming CP/NC composites), methods involving the use of solvent mixtures and ligand modification to control the phase separation at the nanoscale are discussed; the implications of intriguing anisotropic NCs as well as their assemblies (i.e., NC arrays) on improving the charge collection are presented. For newly developed CP/NC solar cells prepared by chemically tethering CP chains on the NC surface (i.e., yielding CP-NC nanocomposites, thereby preventing microscopic phase separation of CP and NC and improving their electronic interaction), recent strategies on the synthesis of such nanocomposites and their photovoltaic performance are discussed.     

Tethered nanoparticle-polymer composites: phase stability and curvature

Phase behavior of poly(ethylene glycol) (PEG) tethered silica nanoparticles dispersed in PEG hosts is investigated using small-angle X-ray scattering. Phase separation in dispersions of densely grafted nanoparticles is found to display strikingly different small-angle X-ray scattering signatures in comparison to phase-separated composites comprised of bare or sparsely grafted nanoparticles. A general diagram for the dispersion state and phase stability of polymer tethered nanoparticle-polymer composites incorporating results from this as well as various other contemporary studies is presented. We show that in the range of moderate to high grafting densities the dispersion state of nanoparticles in composites is largely insensitive to the grafting density of the tethered chains and chemistry of the polymer host. Instead, the ratio of the particle diameter to the size of the tethered chain and the ratio of the molecular weights of the host and tethered polymer chains (P/N) are shown to play a dominant role. Additionally, we find that well-functionalized nanoparticles form stable dispersions in their polymer host beyond the P/N limit that demarcates the wetting/dewetting transition in polymer brushes on flat substrates interacting with polymer melts. A general strategy for achieving uniform nanoparticle dispersion in polymers is proposed.     

Controlled dispersion of polystyrene‐capped Au nanoparticles in P3HT:PC61BM and consequences upon active layer nanostructure

Numerous recent publications detail higher absorption and photovoltaic performance within organic photovoltaic (OPV) devices which are loaded with Au or Ag nanoparticles to leverage the light management properties of the localized surface plasmon resonance (LSPR). This report details the impact upon film morphology and polymer/nanoparticle interactions caused by incorporation of polystyrene‐coated Au nanoparticles (Au/PS) into the P3HT:PC₆₁BM bulk heterojunction film. Nanostructural analysis by transmission electron microscopy and X‐ray scattering reveals tunable Au/PS particle assembly that depends upon the choice of casting solvent, polymer chain length, film drying time, and Au/PS particle loading density. This Au/PS particle assembly has implications on the spectral position of the Au nanoparticle LSPR, which shifts from 535 nm for individually dispersed particles in toluene to 650 nm for particles arranged in large clusters within the P3HT:PC₆₁BM matrix. These results suggest a critical impact from PS/P3HT phase separation, which causes controlled assembly of a separate Au/PS phase in the nanoparticle/OPV composite; controlled Au/PS phase formation provides a blueprint for designing AuNP/OPV hybrid films that impart tunable optical behavior and potentially improve photovoltaic performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 709–720