Effects of buffer layer properties and annealing process on bulk heterojunction morphology and organic solar cell performance

The performance of polymer-fullerene bulk heterojunction (BHJ) solar cells is strongly dependent on the vertical distribution of the donor and acceptor regions within the BHJ layer. In this work, we investigate in detail the effect of the hole transport layer (HTL) physical properties and the thermal annealing on the BHJ morphology and the solar cell performance. For this purpose, we have prepared solar cells with four distinct formulations of poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) buffer layers. The samples were subjected to thermal annealing, applied either before (pre-annealing) or after (post-annealing) the cathode metal deposition. The effect of the HTL and the annealing process on the BHJ ingredient distribution - namely, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) - has been studied by spectroscopic ellipsometry and atomic force microscopy. The results revealed P3HT segregation at the top region of the films, which had a detrimental effect on all pre-annealed devices, whereas PCBM was found to accumulate at the bottom interface. This demixing process depends on the PEDOT:PSS surface energy; the more hydrophilic the surface the more profound is the vertical phase separation within the BHJ. At the same time those samples suffer from high recombination losses as evident from the analysis of the J-V measurements obtained in the dark. Our results underline the significant effect of the HTL-active and active-ETL (electron transport layer) interfacial composition that should be taken into account during the optimization of all polymer-fullerene solar cells. © 2012 The Royal Society of Chemistry.

Non-destructive optical characterization of phase separation in bulk heterojunction organic photovoltaic cells

The dithiophene donor-acceptor copolymers that are bridged either with carbon (C-PCPDTBT) or silicon atoms (Si-PCPDTBT) belong to a promising family of materials for use in photoactive layers for organic photovoltaic cells (OPVs). In this work, we implement the non-destructive Spectroscopic Ellipsometry technique in the near infrared to the far ultraviolet spectral region in combination with advanced theoretical modeling to investigate the vertical distribution of the C-PCPDTBT and Si-PCPDTBT polymer and fullerene ([6,6]-phenyl C71-butyric acid methyl ester - PC70BM) phases in the blend, as well as the effect of the polymer-to-fullerene ratio on the distribution mechanism. It was found that the C-PCPDTBT:PC70BM blends have donor-enriched top regions and acceptor-enriched bottom regions, whereas the donor and acceptor phases are more homogeneously intermixed in the Si-PCPDTBT:PC70BM blends. We suggest that the chemical incompatibility of the two phases as expressed by the difference in their surface energy, may be a key element in promoting the segregation of the lower surface phase to the top region of the photoactive layer. We found that the increase of the photoactive layer thickness reduces the polymer enrichment at the cathode, producing a more homogeneous phase distribution of donor and acceptor in the bulk that leads to the increase of the OPV efficiency. © 2014 Elsevier B.V.

Characterization of vertical Mo/diamond Schottky barrier diode from non-ideal I-V and C-V measurements based on MIS model

In this study, we investigated non-ideal characteristics of a diamond Schottky barrier diode with Molybdenum (Mo) Schottky metal fabricated by Microwave Plasma Chemical Vapour Deposition (MPCVD) technique. Extraction from forward bias I-V and reverse bias C- 2-V measurements yields ideality factor of 1.3, Schottky barrier height of 1.872 eV, and on-resistance of 32.63 mö·cm2. The deviation of extracted Schottky barrier height from an ideal value of 2.24 eV (considering Mo workfunction of 4.53 eV) indicates Fermi level pinning at the interface. We attributed such non-ideal behavior to the existence of thin interfacial layer and interface states between metal and diamond which forms Metal-Interfacial layer-Semiconductor (MIS) structure. Oxygen surface treatment during fabrication process might have induced them. From forward bias C-V characteristics, the minimum thickness of the interfacial layer is approximately 0.248 nm. Energy distribution profile of the interface state density is then evaluated from the forward bias I-V characteristics based on the MIS model. The interface state density is found to be uniformly distributed with values around 1013 eV - 1·cm- 2. © 2013 Elsevier B.V.

Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films. © 2011 Elsevier B.V. All rights reserved.