Space Charge at Nanoscale: Probing Injection and Dynamic Phenomena Under Dark/Light Configurations by Using KPFM and C-AFM

International audienc

Photochemical Charge Separation in Poly(3-hexylthiophene) (P3HT) Films Observed with Surface Photovoltage Spectroscopy

Surface photovoltage spectroscopy (SPS) was used to probe photon induced charge separation in thin films of regioregular and regiorandom poly(3-hexylthiophene) (P3HT) as a function of excitation energy. Both positive and negative photovoltage signals were observed under sub-band-gap (<2.0 eV) and super-band-gap (>2.0 eV) excitation of the polymer. The dependence of the spectra on substrate work function, thermal annealing, film thickness, and illumination intensity was investigated, allowing the identification of interface, charge transfer (CT), and band-gap states in the amorphous and crystalline regions of the polymer films. The ability to probe these states in polymer films will aid the development and optimization of organic electronic devices such as photovoltaics (OPVs), light-emitting diodes (OLEDs), and field effect transistors (OFETs). The direction and size of the observed photovoltage features can be explained using the depleted semiconductor model. © 2013 American Chemical Society

Connecting Scanning Tunneling Spectroscopy to Device Performance for Polymer:Fullerene Organic Solar Cells

Scanning tunneling microscopy and spectroscopy have been used to measure the local photovoltaic performance of prototypical polymer:fullerene (MDMO-PPV:PCBM) bulk heterojunction films with 10 nm resolution. Fullerene-rich clusters are found to act as sinks, extracting electrons from a shell layer of a homogeneously mixed polymer:fullerene matrix, surrounding the fullerene cluster. The experimental results were quantitatively modeled with a drift-diffusion model that in first order accounts for the specific morphology. The same model has subsequently been used to calculate performance indicators of macroscopic solar cells as a function of film composition and characteristic size of the phase separation. As such, a first step has been set toward a quantitative correlation between nanoscopic and macroscopic device photovoltaic performance

Scanning kelvin probe microscopy on bulk heterojunction polymer blends

Here, correlated AFM and scanning Kelvin probe microscopy measurements with sub-100 nm resolution on the phase-separated active layer of polymerfullerene (MDMO-PPV:PCBM) bulk heterojunction solar cells in the dark and under illumination are described. Using numerical modeling a fully quantitative explanation for the contrast and shifts of the surface potential in dark and light is provided. Under illumination an excess of photogenerated electrons is present in both the donor and acceptor phases. From the time evolution of the surface potential after switching off the light the contributions of free and trapped electrons can be identified. Based on these measurements the relative 3D energy level shifts of the sample are calculated. Moreover, by comparing devices with fine and coarse phase separation, it is found that the inferior performance of the latter devices is, at least partially, due to poor electron transport

Description of the morphology dependent charge transport and performance of polymer: fullerene bulk heterojunction solar cells

We present a combined numerical charge transport and morphology model to describe the current density – voltage (j–V) characteristics of three different, benchmark polymer:fullerene bulk heterojunction organic solar cells in which the device performance critically depends on the processing conditions or composition of the active layer. We find that an accurate description of the j–V characteristics over a broad bias range can be obtained when the actual complex, three-dimensional (3D) phase separation is represented by a simplified 2D or even 1D description. The morphological device model allows predicting the potential for increasing device performance by further optimizing the morphology. The optimal simplified morphology consists of two, relatively thin alternating vertically oriented slabs, that allow for fast lateral separation of photocreated holes and electrons. This morphology can effectively be described as 1D

Morphological device model for organic bulk heterojunction solar cells

We present a numerical model for calculating current-voltage characteristics of polymer:fullerene bulk hetrojunction solar cells at different degrees of nanoscale phase separation. We show that the short-circuit current enhancement with finer phase separation is due to a reduction in bimolecular recombination caused by lateral movement of photogenerated electrons to the fullerene-rich phase. At high bias, vertical electron transport is enhanced and lateral movement is reduced, causing a significant field-dependent carrier extraction for coarse morphologies

Description of the morphology dependent charge transport and performance of polymer: fullerene bulk heterojunction solar cells

We present a combined numerical charge transport and morphology model to describe the current density – voltage (j–V) characteristics of three different, benchmark polymer:fullerene bulk heterojunction organic solar cells in which the device performance critically depends on the processing conditions or composition of the active layer. We find that an accurate description of the j–V characteristics over a broad bias range can be obtained when the actual complex, three-dimensional (3D) phase separation is represented by a simplified 2D or even 1D description. The morphological device model allows predicting the potential for increasing device performance by further optimizing the morphology. The optimal simplified morphology consists of two, relatively thin alternating vertically oriented slabs, that allow for fast lateral separation of photocreated holes and electrons. This morphology can effectively be described as 1D

Chaos: The speed limiting phenomenon in dynamic atomic force microscopy

This paper investigates the closed-loop dynamics of the Tapping Mode Atomic Force Microscopy using a new mathematical model based on the averaging method in Cartesian coordinates. Experimental and numerical observations show that the emergence of chaos in conventional tapping mode AFM strictly limits the imaging speed. We show that, if the controller of AFM is tuned to be faster than a certain threshold, the closed-loop system exhibits a chaotic behavior. The presence of chaos in the closed-loop dynamics is confirmed via bifurcation diagrams, Poincaré sections, and Lyapunov exponents. Unlike the previously detected chaos due to attractive forces in the AFM, which can be circumvented via simple changes in operation parameters, this newly identified chaos is seemingly inevitable and imposes an upper limit for the closed-loop bandwidth of the AFM

Conductivity, work function, and environmental stability of PEDOT:PSS thin films treated with sorbitol

The electrical properties of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) thin films deposited from aqueous dispersion using different concentrations of sorbitol have been studied in detail. Although it is well known that sorbitol enhances the conductivity of PEDOT:PSS thin films by three orders of magnitude, the origin and consequences of sorbitol treatment are only partly understood and subject of further study. By thermal annealing of spin coated PEDOT:PSS/sorbitol films and simultaneously monitoring the conductivity, we demonstrate that the strong increase in conductivity coincides with evaporation of sorbitol from the film. Hence, sorbitol is a processing additive rather than a (secondary) dopant. Scanning Kelvin probe microscopy reveals that sorbitol treatment causes a reduction of the work function from 5.1 eV to 4.8-4.9 eV. Sorbitol also influences the environmental stability of the films. While the conductivity of the pristine PEDOT:PSS films increases by about one order of magnitude at ?50% RH due to an ionic contribution to the overall conductivity, films prepared using sorbitol exhibit an increased environmental stability with an almost constant conductivity up to 45% RH and a slight decrease at 50% RH. The higher stability results from a reduced tendency to take up water from the air, which is attributed to a denser packing of the PEDOT:PSS after sorbitol treatment