ToF-SIMS imaging of the nanoscale phase separation in polymeric light emitting diodes: effect of nanostructure on device efficiency.

The nanostructure of the light emissive layer (EL) of polymer light emitting diodes (PLEDs) was investigated using force modulation microscopy (FMM) and scanning time-of-flight secondary ion mass spectrometry (ToF-SIMS) excited with focused Bi(3)(2+) primary beam. Three-dimensional nanostructures were reconstructed from high resolution ToF-SIMS images acquired with different C(60)(+) sputtering times. The observed nanostructure is related to the efficiency of the PLED. In poly(9-vinyl-carbazole) (PVK) based EL, a high processing temperature (60 °C) yielded less nanoscale phase separation than a low processing temperature (30 °C). This nanostructure can be further suppressed by replacing the host polymer with poly[oxy(3-(9H-9-carbazol-9-ilmethyl-2-methyltrimethylene)] (SL74) and poly[3-(carbazol-9-ylmethyl)-3-methyloxetane] (RS12), which have similar chemical structures and energy levels as PVK. The device efficiency increases when the phase separation inside the EL is suppressed. While the spontaneous formation of a bicontinuous nanostructure inside the active layer is known to provide a path for charge carrier transportation and to be the key to highly efficient polymeric solar cells, these nanostructures are less efficient for trapping the carrier inside the EL and thus lower the power conversion efficiency of the PLED devices.

Extraordinarily high efficiency improvement for OLEDs with high surface-charge polymeric nanodots.

The efficiency of highly efficient blue, green, red, and white organic light-emitting diodes (OLEDs) has been substantially advanced through the use of high surface-charge nanodots embedded in a nonemissive layer. For example, the blue OLED's markedly high initial power efficiency of 18.0 lm W(-1) at 100 cd m(-2) was doubled to 35.8 lm W(-1) when an amino-functionalized polymeric nanodot was employed. At high luminance, such as 1000 cd m(-2) used for illumination applications, the efficiency was improved from 12.4 to 21.2 lm W(-1), showing a significant enhancement of 71%. The incorporated highly charged nanodots are capable of effectively modulating the transportation of holes via a blocking or trapping mechanism, preventing excessive holes from entering the emissive layer and the resulting carrier-injection imbalance. Furthermore, in the presence of a high-repelling or dragging field arising from the highly charged nanodots, only those holes with sufficient energy are able to overcome the included barriers, causing them to penetrate deeper into the emissive layer. This penetration leads to carrier recombination over a wider region and results in a brighter emission and, therefore, higher efficiency.

Effect of fabrication parameters on three-dimensional nanostructures and device efficiency of polymer light-emitting diodes.

By using 10 kV C(60)(+) and 200 V Ar(+) ion co-sputtering, a crater was created on the light-emitting layer of phosphorescent polymer light-emitting diodes, which consisted of a poly(9-vinyl carbazole) (PVK) host doped with a 24 wt % iridium(III)bis[(4,6-difluorophenyl)pyridinato-N,C(2)] (FIrpic) guest. A force modulation microscope (FMM) was used to analyze the nanostructure at the flat slope near the edge of the crater. The three-dimensional distribution of PVK and FIrpic was determined based on the difference in their mechanical properties from FMM. It was found that significant phase separation occurred when the luminance layer was spin coated at 30 degrees C, and the phase-separated nanostructure provides a route for electron transportation using the guest-enriched phase. This does not generate excitons on the host, which would produce photons less effectively. On the other hand, a more homogeneous distribution of molecules was observed when the layer was spin coated at 60 degrees C. As a result, a 30% enhancement in device performance was observed.

Effect of fabrication parameters on three-dimensional nanostructures of bulk heterojunctions imaged by high-resolution scanning ToF-SIMS.

Solution processable fullerene and copolymer bulk heterojunctions are widely used as the active layers of solar cells. In this work, scanning time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to examine the distribution of [6,6]phenyl-C61-butyric acid methyl ester (PCBM) and regio-regular poly(3-hexylthiophene) (rrP3HT) that forms the bulk heterojunction. The planar phase separation of P3HT:PCBM is observed by ToF-SIMS imaging. The depth profile of the fragment distribution that reflects the molecular distribution is achieved by low energy Cs(+) ion sputtering. The depth profile clearly shows a vertical phase separation of P3HT:PCBM before annealing, and hence, the inverted device architecture is beneficial. After annealing, the phase segregation is suppressed, and the device efficiency is dramatically enhanced with a normal device structure. The 3D image is obtained by stacking the 2D ToF-SIMS images acquired at different sputtering times, and 50 nm features are clearly differentiated. The whole imaging process requires less than 2 h, making it both rapid and versatile.

Depth profiling of organic films with X-ray photoelectron spectroscopy using C60+ and Ar+ co-sputtering.

By sputtering organic films with 10 kV, 10 nA C60+ and 0.2 kV, 300 nA Ar+ ion beams concurrently and analyzing the newly exposed surface with X-ray photoelectron spectroscopy, organic thin-film devices including an organic light-emitting diode and a polymer solar cell with an inverted structure are profiled. The chemical composition and the structure of each layer are preserved and clearly observable. Although C60+ sputtering is proven to be useful for analyzing organic thin-films, thick organic-devices cannot be profiled without the low-energy Ar+ beam co-sputtering due to the nonconstant sputtering rate of the C60+ beam. Various combinations of ion-beam doses are studied in this research. It is found that a high dosage of the Ar+ beam interferes with the C60+ ion beam, and the sputtering rate decreases with increasing the total ion current. The results suggest that the low-energy single-atom projectile can disrupt the atom deposition from the cluster ion beams and greatly extend the application of the cluster ion-sputtering. By achievement of a steady sputtering rate while minimizing the damage accumulation, this research paves the way to profiling soft matter and organic electronics.

X-ray photoelectron spectrometry depth profiling of organic thin films using C60 sputtering.

A buckminsterfullerene (C(60)) ion beam was used for X-ray photoelectron spectrometry depth profiling of various organic thin films. Specimens representing different interfaces in organic light-emitting diode devices, including hole-conducting poly(ethylenedioxythiophene), poly(styrenesulfonic acid) (PEDOT:PSS) thin films on ITO with and without polysilicic acid doping, light-emitting Ir-containing 4,4'-bis(carbazol-9-yl)biphenyl (CBP) molecules on PEDOT:PSS, and electron-conducting 2,2',2' '(1,3,5-benzinetriyl)tris(1-phenyl-1-H-benzimidazole) (TPBi) molecules on CBP, were studied. In all cases, a clear multilayer structure was observed. The chemical composition and elemental state were preserved after C(60+) ion sputtering. The sputter rate was found to decrease with sputtering time. This is due to the deposition of amorphous carbon on the surface, with the rate of implantation highly dependent on the surface interacting with the ion beam.