Laser-induced crystallization and conformation control of poly(3-hexylthiophene) for improving the performance of organic solar cells

Femto-second laser irradiation on P3HT:PCBM solutions have been demonstrated to have a significant impact on the conformational structures and photovoltaic performance of the resultant thin films. The crystallinity and edge-on/face-on conformations of P3HT and the aggregation of PCBM can be manipulated by controlling the wavelength (400–800 nm) and illumination duration (1–3 h) of the lasers. Grazing incidence wide- and small-angle X-ray scattering (GIWAXS and GISAXS) have been simultaneously utilized to characterize the nanostructures of the P3HT:PCBM blend films spin-cast from pristine and laser-irradiated solutions. The results show that the crystallinity, π-π* stacking and face-on conformations of P3HT can be enhanced as a result of the laser irradiation at 500 nm for 3 h. Furthermore, the diffusion and aggregation of PCBM molecules are suppressed by the photo-induced dimerization, as evidenced by the Raman spectra of the films cast from laser-irradiated PCBM solutions. The time-resolved fluorescence decay profiles show the charge transfer efficiency is improved, which may correlate to the supramolecular ordering of the polythiophene chains and the optimized phase separation in P3HT:PCBM composite. In the P3HT:PCBM active layer of the organic solar cells, more efficient charge transport and fine interpenetrating networks can be achieved due to the improved conformational microstructures. Consequently, the short-circuit current densities and power conversion efficiencies can be enhanced in organic solar cells based on the laser-irradiation processed P3HT:PCBM solutions.     

Modular construction of P3HT/PCBM planar-heterojunction solar cells by lamination allows elucidation of processing–structure–function relationships

Contrary to polymer solar cells with bulk-heterojunction active layers, devices with planar-heterojunction active layers allow the decoupling of active layer phase separation from constituent crystallization, and their relative influence on device performance. We fabricated planar-heterojunction devices by first processing the electron donor and electron acceptor in isolation; they were subsequently laminated across the donor–acceptor interface to establish electrical contact. Thermal annealing was intentionally avoided after lamination to maintain the pristine charge transfer interface. Lamination thus obviates the need for solvent orthogonality; more importantly, it provides independent process tuning of individual organic semiconductor layers, ultimately allowing control over constituent structural development. We found the short-circuit current density of planar-heterojunction solar cells comprising poly(3-hexyl thiophene), P3HT, and [6,6]-phenyl-C₆₁-butyric acid methyl ester, PCBM, as the electron donor and acceptor, respectively, to be generally independent of the annealing history of P3HT. On the contrary, thermal annealing PCBM prior to lamination mainly led to a reduction in short-circuit current density. This deterioration is correlated with the development of preferentially oriented PCBM crystals that hinders electron transport in the vertical direction.     

退火方式及PCBM阴极修饰层对聚合物太阳电池的影响

研究了不同退火方式及PCBM阴极修饰层对聚合物太阳电池性能的影响。与前退火相比,后退火的器件性能显著提高,电池的开路电压Voc由0.36V增加到0.60V,能量转换效率η从0.85%提高到1.93%,短路电流密度Jsc和填充因子FF也有不同程度的改善;在电池的活性层与Al电极间沉积一定厚度的PCBM阴极修饰层也能改善电池的性能,当PCBM厚度为3nm时,聚合物太阳电池在100mW.cm-2强度光照下,Voc为0.59V,Jsc为6.43mA.cm-2,FF为55.1%,η为2.09%。     

Electrical and interfacial properties of Au/P3HT:PCBM/n-Si Schottky barrier diodes at room temperature

In this study, a gold/poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester/n-type silicon (Au/P3HT:PCBM/n-Si) metal-polymer-semiconductor (MPS) Schottky barrier diode (SBD) was fabricated. To accomplish this, a spin-coating system and a thermal evaporation were used for preparation of a P3HT/PCBM layer system and for deposition of metal contacts, respectively. The forward- and reverse-bias current–voltage (I–V) characteristics of the MPS SBD at room temperature were studied to investigate its main electrical parameters such as ideality factor (n), barrier height (Φ_B), series resistance (R_s), shunt resistance (R_sh), and density of interface states (N_ss). The I–V characteristics have nonlinear behavior due to the effect of R_s, resulting in an n value (3.09) larger than unity. Additionally, it was found that n, Φ_B, R_s, R_sh, and N_ss have strong correlation with the applied bias. All results suggest that the P3HT/PCBM interfacial organic layer affects the Au/P3HT:PCBM/n-Si MPS SBD, and that R_s and N_ss are the main electrical parameters that affect the Au/P3HT:PCBM/n-Si MPS SBD. Furthermore, a lower N_ss compared with that of other types of MPS SBDs in the literature was achieved by using the P3HT/PCBM layer. This lowering shows that high-quality electronic and optoelectronic devices may be fabricated by using the Au/P3HT:PCBM/n-Si MPS SBD.     

金属表面等离激元增强聚合物太阳电池

研究了Au纳米颗粒表面等离激元增强聚噻吩(P3HT)与富勒烯衍生物(PCBM)共混体系聚合物太阳电池的光电转换效率。Au纳米颗粒表面由双十烷基二甲基溴化铵(DDAB)修饰,能够均匀分散在活性层中。研究了Au纳米颗粒的质量分数对电池性能的影响,发现质量分数为1.2%时,电池性能最佳,转换效率高达3.76%,较未掺杂的参比电池相对提高约20%。掺入Au纳米颗粒后P3HT和PCBM共混膜光吸收显著增强,从而使电池外量子效率大大增加。电池效率的提升主要归结于Au纳米颗粒表面等离激元激发所引起的近场增强。     

Fabricating the solution-processable inverted photovoltaic devices by the dip-coating method

All solution processable photovoltaic (PV) devices have been great interests in the past decade and different processing methods have been explored to produce the PV devices. In this paper, the dip-coating method was studied to fabricate core layers in the inverted polymer photovoltaic devices, which demonstrates that the dip-coating technology has its potential to produce large area PV devices. The crystallinity of the active layers by the dip-coating method can be improved under the condition of the extended drying rate. Light absorption spectra and X-ray diffraction (XRD) patterns of the active layers were investigated to confirm the improved crystallinity of the active layers. Various morphologies of the dip-coated layers were observed by the atomic force microscopy (AFM). The best PV device achieved ∼3.4% power conversion efficiency.     

Performance improvement mechanisms of P3HT:PCBM inverted polymer solar cells using extra PCBM and extra P3HT interfacial layers

A novel P3HT:PCBM inverted polymer solar cell (IPSC) was fabricated and investigated. An extra PCBM and an extra P3HT interfacial layers were inserted into the bottom side and the top side of the P3HT:PCBM absorption layer of the IPSCs to respectively enhance electron transport and hole transport to the corresponding electrodes. According to the surface energy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurement results, the extra PCBM interfacial layer could let more P3HT to form on the top side of the P3HT:PCBM blends. It revealed that the non-continuous pathways of P3HT in the P3HT:PCBM absorption layer could be reduced. Consequently, the carrier recombination centers were reduced in the absorption layer of IPSCs. The power conversion efficiency (PCE) of the P3HT:PCBM IPSCs with an extra PCBM interfacial layer greatly increased from 3.39% to 4.50% in comparison to the P3HT:PCBM IPSCs without an extra PCBM interfacial layer. Moreover, the performance of the P3HT:PCBM IPSCs with an extra PCBM interfacial layer could be improved by inserting an extra P3HT interfacial layer between the absorption layer and the MoO₃ layer. The PCE of the resulting IPSCs increased from 4.50% to 4.97%.     

溶液加工条件对聚合物体相异质结太阳能电池性能的影响

由于有机太阳能电池具有成本低、易加工、可以制作在柔性衬底上等优点备受人们关注。文中采用了溶液旋涂的加工方法,研究了基于聚3-乙基噻吩(P3HT)与富勒烯衍生物(PCBM)共混的有机聚合物体相异质结太阳能电池。在大气条件下完成了器件的制备与测试,通过旋涂条件、质量分数、退火条件等优化提升了器件的光电特性,获得开路电压(V_oc)为0.62V,短路电流密度(J_sc)为14.97mA/cm²,填充因子(FF)为42.21%,电池效率(PCE)为3.92%的高效聚合物体相异质结太阳能电池。因此,通过对溶液加工条件的优化,可以提高薄膜质量,促进载流子传输和分离的能力。不仅可以提升有机聚合物体相异质结太阳能电池的效率,也为推进有机太阳能电池的量产化奠定了基础。     

A thermodynamic and kinetic description of PCBM phase segregation and aggregation in P3HT:PCBM blends

The kinetics and thermodynamics of PCBM phase segregation and aggregation in P3HT:PCBM blends has been studied. We develop a thermodynamic model for PCBM phase segregation in P3HT:PCBM blends which explains the formation of nanoscale crystallites which subsequently diffuse and coalesce into larger PCBM aggregates. We show that the formation of nanoscale crystallites during the film making process prevents spinodal decomposition of the P3HT:PCBM blends even at PCBM weight fractions above the spinodal decomposition boundary for the system. Finally, we demonstrate that the observed aggregate morphology can be understood in terms of a kinetic model based on the diffusional flux lines of PCBM crystallite which, in turn, govern the evolution of the macroscopic growth front.     

Probing film solidification dynamics in polymer photovoltaics

Semiconducting conjugated polymers have drawn a great deal of attention over the past decade due to their solution processability and potential use in roll to roll fabrication of organic solar cells. Here, we report the effect of solvent vapor pressure on poly(3-hexylthiophene):[6,6]-phenyl C₆₁-butyric acid methyl ester (P3HT:PCBM) blade coated inverted solar cells using ZnO as the electron transporting layer and MoO₃ as the hole transporting layer. The resultant morphology and device performance are investigated for devices processed from solvents with varied vapor pressure and a mixed solvent. We report that the use of a mixed solvent system is advantageous for controlling the initial vapor pressure of the processing solution, thereby controlling the phase separated morphology between P3HT and PCBM which impacts ultimate solar cell performance.     

Effects of exciton blocking layer and cathode electrode work function on the performance of polymer solar cells

In this study the effects of some important processing and post-processing treatments on the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester ([60]PCBM) solar cells were investigated. These parameters included the active layer film formation period, thermal annealing, electrical treatment, cathode work function modification, and exciton blocking layer type and thickness. Polymer bulk heterojunction solar cells having a glass/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM/(Ca or LiF)/Al structure were fabricated. The morphology of the active layer was investigated using atomic force microscopy. The results showed that the morphology state of the active layer exactly after spin coating process was very important parameter, which could dictate different responses of solar cells to a certain treatment. Using solvent additives to prolong the film formation period and storing in small dish could reach the morphology of the active layer near its best state in which there was no need to apply common post-treatment processes. A thickness at about 20 nm was required for Ca layer to effectively act as exciton blocking layer while LiF with 1 nm thickness worked better.     

Detecting 6 MV X-rays using an organic photovoltaic device

An organic photovoltaic (OPV) device has been used in conjunction with a flexible inorganic phosphor to produce a radiation tolerant, efficient and linear detector for 6 MV X-rays. The OPVs were based on a blend of poly(3-hexylthiophene-2,5-diyl) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM). We show that the devices have a sensitivity an order of magnitude higher than a commercial silicon detector used as a reference. Exposure to 360 Grays of radiation resulted in a small (2%) degradation in performance demonstrating that these detectors have the potential to be used as flexible, real-time, in vivo dosimeters for oncology treatments.