Organic solar cells based on highly self-organizing semiconducting polymers

In this thesis I have studied organic solar cells (photovoltaic devices) based on a highly self-organizing polymer, regioregular poly(3-hexyIthiophene) (P3HT), because of its particular crystallization tendency leading to high charge carrier mobilities, good light-harvesting in red parts, and suitable energy band structure for an electron-donor. Prior to organic solar cell study, the pristine P3HT films have been investigated to understand their optical/electrical property and nanocrystal structure changes upon thermal annealing. As an electron-acceptor for organic solar cells, two candidates were employed: One is polymer [poly(poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT)), another is big small molecule [[6,6]-phenyl Cgi-butyric acid methyl ester (PCBM)]. The kinds of blends used for organic solar cell fabrication were P3HT:F8BT, P3HT:PCBM, and P3HT:PCBM:F8BT. Organic solar cells were fabricated by spin-coating these blend films onto transparent conductive oxide coated substrates followed by depositing metal electrodes (sometimes inserting LiF). For better understanding of device performance changes, blend films have been examined with optical absorption, photoluminescence including time-resloved system, normal reflection mode x-ray diffraction, grazing incidence x-ray diffraction (Synchrotron), atomic force microscopy, scanning electron microscopy, high resolution transmission electron microscopy with field emission gun, transient absorption spectroscopy, and time-of-flight mobility measurement. As a result, P3HT:F8BT solar cells (maximum external quantum efficiency=~3%) showed poorer efficiency than P3HT:PCBM solar cells (maximum external quantum efficiency=~73%), though both blends have P3HT components, which is attributed to the low electron mobility of F8BT compared to PCBM. The power conversion efficiency of P3HT:PCBM solar cells has reached 4.4-5.5% at 85~8.5mW/cm^ (air mass 1.5 simulated solar illumination), which is ascribed mainly to the formation of vertical phase segregation upon thermal annealing leading to pseudo layered p-n junction. This layered structure might reduce the charge recombination between P3HT positive polaron (radical cation) and PCBM negative polaron (radical anion), a parameter that has been quantitatively analysed using a new model proposed in this work

Phenanthroline diimide as an organic electron-injecting material for organic light-emitting devices

We report a diimide-type organic electron-injecting material, bis-[1,10]phenanthrolin-5-yl-pyromellitic diimide (Bphen-PMDI), for organic light-emitting devices (OLEDs), which was synthesized from its monomers, pyromellitic dianhydride (PMDA) and 1,10-phenanthrolin-5-amine (PTA). The vacuum-purified Bphen-PMDI powder showed high glass transition (∼230°C) and thermal decomposition (∼400°C) temperatures, whereas neither melting point nor particular long-range crystal nanostructures were observed from its solid samples. The optical band gap energy and the ionization potential of the Bphen-PMDI film were 3.6 eV and 6.0 eV, respectively, leading to the lowest unoccupied molecular orbital (LUMO) energy of 2.4 eV. Inserting a 1 nm thick Bphen-PMDI layer between the emission layer and the cathode layer improved the device current density by 10-fold and the luminance by 6-fold, compared to the OLED without the Bphen-PMDI layer. The result suggests that an effective electron tunnel injection process occurs through the Bphen-PMDI layer. © The Royal Society of Chemistry 2012.1

In situ-prepared composite materials of PEDOT: PSS buffer layer-metal nanoparticles and their application to organic solar cells

We report an enhancement in the efficiency of organic solar cells via the incorporation of gold (Au) or silver (Ag) nanoparticles (NPs) in the hole-transporting buffer layer of poly(3,4- ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which was formed on an indium tin oxide (ITO) surface by the spin-coating of PEDOT:PSS-Au or Ag NPs composite solution. The composite solution was synthesized by a simple in situ preparation method which involved the reduction of chloroauric acid (HAuCl4) or silver nitrate (AgNO3) with sodium borohydride (NaBH4) solution in the presence of aqueous PEDOT:PSS media. The NPs were well dispersed in the PEDOT:PSS media and showed a characteristic absorption peak due to the surface plasmon resonance effect. Organic solar cells with the structure of ITO/PEDOT:PSS-Au, Ag NPs/poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PC61BM)/LiF/Al exhibited an 8% improvement in their power conversion efficiency mainly due to the enlarged surface roughness of the PEDOT:PSS, which lead to an improvement in the charge collection and ultimately improvements in the short-circuit current density and fill factor. © 2012 Woo et al.1

Influence of thermal annealing on the deformation of a lithium fluoride nanolayer in polymer : fullerene solar cells

In this letter we attempted to examine the possible deformation of a lithium fluoride (LiF) nanolayer inserted in between a light-absorbing polymeric layer (a mix of poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6) C61 (PCBM)) and a metal (Al) electrode in polymer : fullerene solar cells. The direct annealing of devices with the LiF nanolayer resulted in a gradual decay in device performances with annealing time at an optimum temperature, after exhibiting a maximum efficiency by very short-time annealing (3 min). In contrast, the study of film annealing and post-deposition of the LiF nanolayer showed that a longer-time (120 min) annealing led to a maximum efficiency. These results indicate that the LiF nanolayer in devices is vulnerable to the deformation upon thermal annealing

Hole Injection Role of p-Type Conjugated Polymer Nanolayers in Phosphorescent Organic Light-Emitting Devices

Here, we report the hole injection role of p-type conjugated polymer layer in phosphorescent organic light-emitting devices (OLEDs). Poly(3-hexylthiophene) (P3HT) nanolayers (thickness = ~1 nm thick), which were subjected to thermal annealing at 140 °C by varying annealing time, were inserted between indium tin oxide (ITO) anodes and hole transport layers (N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine, NPB). The 1 nm-thick P3HT layers showed very weak absorption in the visible light range of 500~650 nm. The device results disclosed that the presence of P3HT layers were just able to improve the charge injection of OLEDs leading to an enhanced luminance irrespective of thermal annealing condition. The highest luminance and efficiency were achieved for the OLEDs with the P3HT layers annealed at 140 °C for 10 min. Further annealing for 30 min resulted in turn-down of device performances. The emission color was almost unchanged by the presence of P3HT layers even though the color coordinates were marginally fluctuated according to the annealing time. The present result delivers the possibility to use p-type conjugated polymers (i.e., P3HT) as a hole injection layer in OLEDs

Near-Infrared Organic Phototransistors with Polymeric Channel/Dielectric/Sensing Triple Layers

A new type of near-infrared (NIR)-sensing organic phototransistor (OPTR) was designed and fabricated by employing a channel/dielectric/sensing (CDS) triple layer structure. The CDS structures were prepared by inserting poly(methyl methacrylate) (PMMA) dielectric layers (DLs) between poly(3-hexylthiophene) (P3HT) channel layers and poly[{2,5-bis-(2-octyldodecyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2′-(2,1,3-benzothiadiazole)-5,5′-diyl}] (PODTPPD-BT) top sensing layers. Two different thicknesses of PMMA DLs (20 nm and 50 nm) were applied to understand the effect of DL thickness on the sensing performance of devices. Results showed that the NIR-OPTRs with the CDS structures were operated in a typical n-channel mode with a hole mobility of ca. 0.7~3.2 × 10−4 cm2/Vs in the dark and delivered gradually increased photocurrents upon illumination with an NIR light (905 nm). As the NIR light intensity increased, the threshold voltage was noticeably shifted, and the resulting transfer curves showed a saturation tendency in terms of curve shape. The operation of the NIR-OPTRs with the CDS structures was explained by the sensing mechanism that the excitons generated in the PODTPPD-BT top sensing layers could induce charges (holes) in the P3HT channel layers via the PMMA DLs. The optically modulated and reflected NIR light could be successfully detected by the present NIR-OPTRs with the CDS structures

Persistent electrical energy generation from organic diodes under constant pressure: Toward organic gravity nanogenerators

Summary: Here it is demonstrated that electricity can be continuously generated by pressing organic diodes with the poly(3-hexylthiophene) (P3HT) layers which are sandwiched between indium-tin oxide and aluminum (Al) electrodes. The optimized single devices with the 150-nm-thick P3HT layers are able to generate 60 μV and 45 μA by pressing, while persistent voltage (50 μV) and current (45 μA) generations are achieved by continuous pressing for 7 days. The charge generation by pressing of organic diodes is supported by the current density-voltage and capacitance measurements, while the friction of pi-orbital electrons in the P3HT chains upon pressing is proposed for the mechanism of persistent electricity generation. Organic diode modules with 14 sub-cells in series deliver ca. 0.4 V and ca. 20 μW. The present technology is expected to pave the way for next-generation energy conversion devices, organic gravity nanogenerators that enable continuous electricity generation by gravitational forces