The Effect of Polymer Optoelectronic Properties on the Performance of Multilayer Hybrid Polymer/TiO2 Solar Cells

We report a study of the effects of polymer optoelectronic properties on the performance of photovoltaic devices consisting of nanocrystalline TiO₂ and a conjugated polymer. Three different poly(2‐methoxy‐5‐(2′‐ethylhexoxy)‐1,4‐phenylenevinylene) (MEH‐PPV)‐based polymers and a fluorene–bithiophene copolymer are compared. We use photoluminescence quenching, time‐of‐flight mobility measurements, and optical spectroscopy to characterize the exciton‐transport, charge‐transport, and light‐harvesting properties, respectively, of the polymers, and correlate these material properties with photovoltaic‐device performance. We find that photocurrent is primarily limited by the photogeneration rate and by the quality of the interfaces, rather than by hole transport in the polymer. We have also studied the photovoltaic performance of these TiO₂/polymer devices as a function of the fabrication route and device design. Including a dip‐coating step before spin‐coating the polymer leads to excellent polymer penetration into highly structured TiO₂ networks, as was confirmed through transient optical measurements of the photoinduced charge‐transfer yield and recombination kinetics. Device performance is further improved for all material combinations studied, by introducing a layer of poly(ethylene dioxythiophene) (PEDOT) doped with poly(styrene sulfonic acid) (PSS) under the top contact. Optimized devices incorporating the additional dip‐coated and PEDOT:PSS layers produced a short‐circuit current density of about 1 mA cm^–2, a fill factor of 0.50, and an open‐circuit voltage of 0.86 V under simulated AM 1.5 illumination (100 mW cm^–2, 1 sun). The corresponding power conversion efficiency under 1 sun was ≥ 0.4 %.     

Polymer Solar Cells Based on a Low‐Bandgap Fluorene Copolymer and a Fullerene Derivative with Photocurrent Extended to 850 nm

Polymer solar cells have been fabricated from a recently synthesized low band‐gap alternating polyfluorene copolymer, APFO‐Green2, combined with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) from organic solutions. External quantum efficiencies (EQEs) of the solar cells show an onset at 850 nm and a peak of > 10 % located at 650 nm, which corresponds to the extended absorption spectrum of the polymer. Photocurrent of 3.0 mA cm^–2, photovoltage of 0.78 V, and power conversion efficiency of 0.9 % have been achieved in solar cells based on this new low‐bandgap polymer under the illumination of air mass 1.5 (AM 1.5) (1000 W m^–2) from a solar simulator.     

Highly Efficient Hybrid Solar Cells Based on an Octithiophene–GaAs Heterojunction

We report a new type of hybrid heterojunction solar cell based on rod‐like octithiophene (8T) as the organic p‐type semiconductor and GaAs(111) as the inorganic n‐type semiconductor. By using a semitransparent gold layer as the front contact deposited onto the 8T films, solar‐energy conversion efficiencies of up to 4.2 % could be obtained. The reduction in the contact resistance at the Au/8T interface induced by iodine doping is found to be a very crucial factor for the high efficiency. Furthermore, we demonstrate that hybrid solar cells can be successfully used to investigate the photovoltaic properties of organic semiconductors in detail. By means of external quantum efficiency (EQE) measurements, the influence of film morphology on the photocurrent collection length in 8T films is studied. The results show that, in hybrid solar cells using highly ordered microcrystalline 8T films, an active contribution of the organic‐layer semiconductor to the total photocurrent exists. A very large photocurrent collection length of up to 100 nm has been estimated from EQE measurements, indicating that exciton diffusion is very efficient in microcrystalline 8T. On the other hand, the use of nanocrystalline 8T leads to high photocurrent losses in the organic part of the hybrid solar cell. The strong influence of the film morphology on the photocurrent collection in 8T is attributed to a reduction in the exciton diffusion length due to a high trap density in nanocrystalline 8T films. Thus, our results reveal the importance of high crystalline order for obtaining efficient photocurrent collection in 8T films.     

Effect of Temperature and Illumination on the Electrical Characteristics of Polymer–Fullerene Bulk‐Heterojunction Solar Cells

The current–voltage characteristics of ITO/PEDOT:PSS/OC₁C₁₀‐PPV:PCBM/Al solar cells were measured in the temperature range 125–320 K under variable illumination, between 0.03 and 100 mW cm^–2 (white light), with the aim of determining the efficiency‐limiting mechanism(s) in these devices, and the temperature and/or illumination range(s) in which these devices demonstrate optimal performance. (ITO: indium tin oxide; PEDOT:PSS: poly(styrene sulfonate)‐doped poly(ethylene dioxythiophene); OC₁C₁₀‐PPV: poly[2‐methoxy‐5‐(3,7‐dimethyl octyloxy)‐1,4‐phenylene vinylene]; PCBM: phenyl‐C₆₁ butyric acid methyl ester.) The short‐circuit current density and the fill factor grow monotonically with temperature until 320 K. This is indicative of a thermally activated transport of photogenerated charge carriers, influenced by recombination with shallow traps. A gradual increase of the open‐circuit voltage to 0.91 V was observed upon cooling the devices down to 125 K. This fits the picture in which the open‐circuit voltage is not limited by the work‐function difference of electrode materials used. The overall effect of temperature on solar‐cell parameters results in a positive temperature coefficient of the power conversion efficiency, which is 1.9 % at T = 320 K and 100 mW cm^–2 (2.5 % at 0.7 mW cm^–2). The almost‐linear variation of the short‐circuit current density with light intensity confirms that the internal recombination losses are predominantly of monomolecular type under short‐circuit conditions. We present evidence that the efficiency of this type of solar cell is limited by a light‐dependent shunt resistance. Furthermore, the electronic transport properties of the absorber materials, e.g., low effective charge‐carrier mobility with a strong temperature dependence, limit the photogenerated current due to a high series resistance, therefore the active layer thickness must be kept low, which results in low absorption for this particular composite absorber.     

Hybrid electrochromic film based on polyaniline and TiO2 nanorods array

Titanium dioxide (TiO₂) nanorods (NRs) array was successfully prepared via hydrothermal method on fluorine doped tinoxide (FTO) coated transparent conductive glass substrate. The hybrid film of polyaniline (PANI)/TiO₂ NRs was achieved through electrochemical polymerization of aniline onto the TiO₂ NRs array film. The electrochromic and optical properties of the hybrid film were investigated by cyclic voltammetry (CV), amperometric i–t and UV–vis spectroscopy. The results indicate that the hybrid film has long term stability and reversible color changes after cyclic voltammetry scans for 200 circles. The PANI/TiO₂ NRs hybrid film can show three different colors. Response time of PANI/TiO₂ NRs hybrid film is about 0.7 s and 2.6 s at different states, respectively. The TiO₂ NRs array and the loose, porous surface among the hybrid film facilitate charge transmission and also provide large surface area for electrochemical reaction.     

Accurate Measurement and Characterization of Organic Solar Cells

Methods to accurately measure the current–voltage characteristics of organic solar cells under standard reporting conditions are presented. Four types of organic test cells and two types of silicon reference cells (unfiltered and with a KG5 color filter) are selected to calculate spectral‐mismatch factors for different test‐cell/reference‐cell combinations. The test devices include both polymer/fullerene‐based bulk‐heterojunction solar cells and small‐molecule‐based heterojunction solar cells. The spectral responsivities of test cells are measured as per American Society for Testing and Materials Standard E1021, and their dependence on light‐bias intensity is reported. The current–voltage curves are measured under 100 mW cm^–2 standard AM 1.5 G (AM: air mass) spectrum (International Electrotechnical Commission 69094‐1) generated from a source set with a reference cell and corrected for spectral error.     

The Effect of Annealing on the Charge‐Carrier Dynamics in a Polymer/Polymer Bulk Heterojunction for Photovoltaic Applications

The effect of annealing blends of poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO‐PPV) and a poly(cyanoether phenylenevinylene) (PCNEPV) on the photoconductivity is studied. Charge carriers are generated by pulsed‐laser excitation and their mobility and decay kinetics are monitored using time‐resolved microwave conductivity (TRMC) measurements. Photoexcitation leads to the formation of an exciton, which can undergo charge separation at an interface between the electron‐donating MDMO‐PPV and the electron‐accepting PCNEPV. The electrons and holes formed in this way must escape from each other to contribute to the photoconductivity. The photoconductivity of the blends is found to increase by almost two orders of magnitude upon thermal annealing for three hours at 100 °C. This increase is attributed to the occurrence of phase separation in the polymer/polymer film, resulting in PCNEPV‐rich parts. The formation of PCNEPV‐rich parts allows the electron to diffuse away from the interface, which favors escape from geminate recombination, leading to a higher photoconductivity.     

Hybrid Solar Cells Using HgTe Nanocrystals and Nanoporous TiO2 Electrodes

HgTe nanocrystals are demonstrated to increase the photon‐harvesting efficiency of hybrid solar cells over a broad spectral region between 350 and 1500 nm. Devices combining two solar cell concepts, a solid‐state nanocrystal‐sensitized solar cell and a nanocrystal/polymer‐blend solar cell, are described. These devices give incident photon to current efficiencies up to 10 % at around 550 nm monochromatic irradiation and short‐circuit current densities of 2 mA cm^–2 under simulated AM1.5 (100 mW cm^–2) illumination (AM: air mass).     

Cyclobutadiene–C60 Adducts: N‐Type Materials for Organic Photovoltaic Cells with High VOC

New tetraalkylcyclobutadiene–C₆₀ adducts are developed via Diels–Alder cycloaddition of C₆₀ with in situ generated cyclobutadienes. The cofacial π‐orbital interactions between the fullerene orbitals and the cyclobutene are shown to decrease the electron affinity and thereby increase the lowest unoccupied molecular orbital (LUMO) energy level of C₆₀ significantly (ca. 100 and 300 meV for mono‐ and bisadducts, respectively). These variations in LUMO levels of fullerene can be used to generate higher open‐circuit voltages (V_OC) in bulk heterojunction polymer solar cells. The tetramethylcyclobutadiene–C₆₀ monoadduct displays an open‐circuit voltage (0.61 V) and a power conversion efficiency (2.49%) comparable to the widely used P3HT/PCBM (poly(3‐hexylthiophene/([6,6]‐phenyl‐C61‐butyric acid methyl ester) composite (0.58 V and 2.57%, respectively). The role of the cofacial π‐orbital interactions between C₆₀ and the attached cyclobutene group was probed chemically by epoxidation of the cyclobutene moiety and theoretically through density functional theory calculations. The electrochemical, photophysical, and thermal properties of the newly synthesized fullerene derivatives support the proposed effect of functionalization on electron affinities and photovoltaic performance.     

Device Operation of Conjugated Polymer/Zinc Oxide Bulk Heterojunction Solar Cells

Solar cells based on a poly(p‐phenylene vinylene) (PPV) derivative and zinc oxide nanoparticles can reach a power conversion efficiency of 1.6 %. The transport of electrons and holes in these promising devices is characterized and it is found that the electron mobility is equal to 2.8 × 10^–9 m² V^–1 s^–1, whereas the hole mobility amounts to 5.5 × 10^–10 m² V^–1 s^–1. By modeling the current–voltage characteristics under illumination it is found that the performance of PPV/zinc oxide solar cells is limited by the charge‐carrier mobilities. Subsequently, how to further improve the efficiency is discussed.     

有机层／阴极界面修饰对体异质结聚合物太阳能电池性能的影响

通过制备四种不同结构的器件,详细分析研究了活性层／阴极界面修饰对P3HT:PCBM聚合物体异质结太阳能电池性能的影响。当在P3HT:PCBM薄膜上旋涂一层PCBM,并蒸镀0.5 nm LiF时所制备的器件的填充因子和光电转换效率都得到较大的提高。对器件的光电性能和薄膜的形貌进行深入分析,阐明界面修饰的作用机理。     

Efficient Photosensitization and High Optical Gain in a Novel Quantum‐Dot‐Sensitized Hybrid Photorefractive Nanocomposite at a Telecommunications Wavelength

A high‐performance hybrid polymeric photorefractive nanocomposite operating at the telecommunications wavelength of 1.34 μm is presented. The photorefractive nanocomposite is sensitized with PbS nanocrystals synthesized via a hot colloidal route. Photoconductivity experiments confirm and quantify the photocharge‐generation quantum efficiency of the nanocrystals. A pronounced two‐beam coupling effect at the operation wavelength is observed, leading to very high optical gains. Temporal evolution of the photorefractive growth process is also studied.     

Room‐Temperature Synthesis of Porous Nanoparticulate TiO2 Films for Flexible Dye‐Sensitized Solar Cells

A novel room‐temperature method for the preparation of porous TiO₂ films with high performance in dye‐sensitized solar cells (DSSCs) has been developed. In this method a small amount of Ti^IV tetraisopropoxide (TTIP) is added to an ethanolic paste of TiO₂ nanoparticles, where it hydrolyzes in situ and connects the TiO₂ particles to form a homogenous and mechanically stable film of up to 10 μm thickness without crack formation. Residual organics originating from the TTIP were removed by UV–ozone treatment of the films, leading to a remarkable improvement of the cell efficiency. Intensity‐modulated photocurrent/voltage spectroscopy (IMPS/IMVS) showed that the main effect of the UV–ozone treatment is to suppress the recombination of photogenerated electrons, thereby extending their lifetime. The efficiency was further increased by preheating the TiO₂ nanoparticles before the paste preparation to remove contaminants originating from the preparation process of the particles. Solar‐to‐electric energy conversion efficiencies of 4.00 and 3.27 % have been achieved for cells with conductive glass and plastic film substrates, respectively, under illumination with AM 1.5 (100 mW cm^–2) simulated sunlight.     

Polymer/Nanocrystal Hybrid Solar Cells: Influence of Molecular Precursor Design on Film Nanomorphology,Charge Generation and Device Performance

In this work, molecular tuning of metal xanthate precursors is shown to have a marked effect on the heterojunction morphology of hybrid poly(3‐hexylthiophene‐2,5‐diyl) (P3HT)/CdS blends and, as a result, the photochemical processes and overall performance of in situ fabricated hybrid solar cells. A series of cadmium xanthate complexes is synthesized for use as in situ precursors to cadmium sulfide nanoparticles in hybrid P3HT/CdS solar cells. The formation of CdS domains is studied by simultaneous GIWAXS (grazing incidence wide‐angle X‐ray scattering) and GISAXS (grazing incidence small‐angle X‐ray scattering), revealing knowledge about crystal growth and the formation of different morphologies observed using TEM (transmission electron microscopy). These measurements show that there is a strong relationship between precursor structure and heterojunction nanomorphology. A combination of TAS (transient absorption spectroscopy) and photovoltaic device performance measurements is used to show the intricate balance required between charge photogeneration and percolated domains in order to effectively extract charges to maximize device power conversion efficiencies. This study presents a strong case for xanthate complexes as a useful route to designing optimal heterojunction morphologies for use in the emerging field of hybrid organic/inorganic solar cells, due to the fact that the nanomorphology can be tuned via careful design of these precursor materials.     

Solar‐Energy Conversion in TiO2/CuInS2 Nanocomposites

The search for low‐cost thin‐film solar cells, to replace silicon multi‐crystalline cells in due course, calls for new combinations of materials and new cell configurations. Here we report on a new approach, based on semiconductor nanocomposites, towards what we refer to as the three‐dimensional (3D) solar‐cell concept. Atomic layer chemical vapor deposition is employed for infiltration of CuInS₂ inside the pores of nanostructured TiO₂. In this way it is possible to obtain a nanometer‐scale interpenetrating network between n‐type TiO₂ and p‐type CuInS₂. X‐ray diffraction, Raman spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, transmission electron microscopy, and current–voltage measurements are used to characterize the nanostructured devices. The 3D solar cells obtained show photovoltaic activity with a maximum monochromatic incident photon‐to‐current conversion efficiency of 80 % and have an energy‐conversion efficiency of 4 %.     

基于高效体异质结的聚合物太阳电池研究

介绍了体异质结聚合物太阳电池的基本原理,并分析了限制体异质结有机太阳电池转化效率的因素。从提高激子的产生效率及其解离效率、电极对电荷的引出效率、电池的稳定性以及电池的光谱吸收范围四个方面,综述了提高体异质结聚合物太阳电池能量转化效率的方法。     

Synthesis and Assembly of Gold Nanoparticles in Quasi‐Linear Lysine–Keggin‐Ion Colloidal Particles

The formation of fiber‐like colloidal particles of the amino acid lysine complexed with Keggin ions is demonstrated. The lysine–phosphotungstic acid (PTA) colloidal particles act as excellent templates for the synthesis and assembly of gold nanoparticles wherein the lysine‐PTA complex acts as a UV‐switchable reducing agent for gold ions. This novel bio‐organic–inorganic template shows excellent potential as a regulated nanoreactor for application in programmed nanoparticle synthesis and assembly in a single step.     

The Influence of TiO2 Particle Size in TiO2/CuInS2 Nanocomposite Solar Cells

The recently developed CuInS₂/TiO₂ 3D nanocomposite solar cell employs a three‐dimensional, or “bulk”, heterojunction to reduce the average minority charge‐carrier‐transport distance and thus improve device performance compared to a planar configuration. 3D nanocomposite solar‐cell performance is strongly influenced by the morphology of the TiO₂ nanoparticulate matrix. To explore the effect of TiO₂ morphology, a series of three nanocomposite solar‐cell devices are studied using 9, 50, and 300 nm TiO₂ nanoparticles, respectively. The photovoltaic efficiency increases dramatically with increasing particle size, from 0.2 % for the 9 nm sample to 2.8 % for the 300 nm sample. Performance improvements are attributed primarily to greatly improved charge transport with increasing particle size. Other contributing factors may include increased photon absorption and improved interfacial characteristics in the larger‐particle‐size matrix.     

Recent Developments of Polymer Solar Cells with Photovoltaic Performance over 17%

With the emergence of ADA'DA-type (Y-series) non-fullerene acceptors (NFAs), the power conversion efficiencies (PCEs) of organic photovoltaic devices have been constantly refreshed and gradually reached 20% in recent years (19% for single junction and 20% for tandem device). The acceptors possess specific design concept, which greatly enrich the NFA types and have excellent compatibility with many donor materials. It is gratifying to note that the previously underperforming donor materials combine with these regulated acceptors to shine again. Nowadays, the concept of modular design is widely used in the research of acceptors and donors, injecting new vitality into the field of organic photovoltaics. Furthermore, these acceptors also promote the research of multicomponent devices, tandem devices, bilayer devices, processing solvent engineering, and additive engineering. Herein, the latest progresses of polymer solar cells with efficiency over 17% are briefly reviewed from the aspects of active material design, interface material development, and device technology. At last, the opportunities and challenges of organic photovoltaic commercialization in the future are discussed.