Optical Characterization of the Hole Polaron in a Series of Diketopyrrolopyrrole Polymers Used for Organic Photovoltaics

Abstract: A strategy that is often used for designing low band gap polymers involves the incorporation of electron-rich (donor) and electron-deficient (acceptor) conjugated segments within the polymer backbone. In this paper we investigate such a series of Diketopyrrolopyrrole (DPP)-based co-polymers. The co-polymers consisted of a DPP unit attached to a phenylene, naphthalene, or anthracene unit. Additionally, polymers utilizing either the thiophene-flanked DPP or the furan-flanked DPP units paired with the naphthalene comonomer were compared. As these polymers have been used as donor materials and subsequent hole transporting materials in organic solar cells, we are specifically interested in characterizing the optical absorption of the hole polaron of these DPP based copolymers. We employ chemical doping, electrochemical doping, and photoinduced absorption (PIA) studies to probe the hole polaron absorption spectra. While some donor-acceptor polymers have shown an appreciable capacity to generate free charge carriers upon photoexcitation, no polaron signal was observed in the PIA spectrum of the polymers in this study. The relations between molecular structure and optical properties are discussed. Keywords: organic solar cell; organic photovoltaic; diketopyrrolopyrrole; chemical doping; spectroelectrochemistry; photoinduced absorption; hole polaron

dc reactive magnetron sputtering of titanium‐structural and optical characterization of TiO2 films

This paper deals with the reactive sputtering of titanium in an argon and oxygen mixture. The variation in cathode potential as a function of oxygen partial pressure has been explained in terms of cathode poisoning effects. The titania films deposited during this process have been studied for their structural and optical characteristics. The effect of substrate temperature (from 25 to 400 °C) and annealing (from 250 to 700 °C) on the packing density, refractive index, extinction coefficient, and crystallinity has been investigated. The refractive index varied from 2.24 to 2.46 and extinction coefficient from 2.6 × 10-3 to 10.4× 10-3 at 500 nm as the substrate temperature increased from 25 to 400 °C. The refractive index increased from 2.19 to 2.35 and extinction coefficient changed from 3.2× 10-3 to 11.6 × 10-3 at 500 nm as the annealing temperature was increased from 250 to 700 °C. Anatase and rutile phases have been observed in the films deposited at 400 °C substrate temperature and annealed at 300 °C. The changes in the optical constants at higher substrate temperature have been attributed to an increase in packing density, oxygen content, and crystallinity of the films.

Electrical and optical characterization of conducting polymers by THz time-domain spectroscopy

The absorption and index of refraction of polypyrrole (PPy) and poly-3-methylthiophene (PMeT), from low frequencies up to 4 THz, have been measured by tera-Herz (THz) time-domain spectroscopy. The complex conductance was obtained over this range of frequency. Highly conducting metallic samples follow the Drude model, whereas less conducting ones fit the localization-modified Drude model. The carrier scattering time and mobility in conducting polymers can be directly determined from these measurements.

Structural and optical characterization of nonpolar (10-10) m-InN/m-GaN epilayers grown by PAMBE

Plasma-assisted molecular beam epitaxy growth of (10-10) m-InN/(10-10) m-GaN was carried out on bare (10-10) m-sapphire substrate. The high resolution X-ray diffraction studies confirmed the orientation of the as-grown films. Nonpolar InN layer was grown at different growth temperatures ranging from 390 degrees C to 440 degrees C and the FWHM of rocking curve revealed good quality film at low temperatures. An in-plane relationship was established for the hetrostructures using phi-scan and a perfect alignment was found for the epilayers. Change of morphology of the films grown at different temperatures was observed using an atomic force microscopy technique showing the smoothest film grown at 400 degrees C. InN optical band gap was found to be vary from 0.79-0.83 eV from absorption spectra. The blue-shift of absorption edge was found to be induced by excess background electron concentration. (C) 2015 Elsevier B.V. All rights reserved.

Electrical, electrochemical, and optical characterization of ceria films

Acceptor-doped ceria has been recognized as a promising intermediate temperature solid oxide fuel cell electrode/electrolyte material. For practical implementation of ceria as a fuel cell electrolyte and for designing model experiments for electrochemical activity, it is necessary to fabricate thin films of ceria. Here, metal-organic chemical vapor deposition was carried out in a homemade reactor to grow ceria films for further electrical, electrochemical, and optical characterization. Doped/undoped ceria films are grown on single crystalline oxide wafers with/without Pt line pattern or Pt solid layer. Deposition conditions were varied to see the effect on the resultant film property. Recently, proton conduction in nanograined polycrystalline pellets of ceria drew much interest. Thickness-mode (through-plane, z-direction) electrical measurements were made to confirm the existence of proton conductivity and investigate the nature of the conduction pathway: exposed grain surfaces and parallel grain boundaries. Columnar structure presumably favors proton conduction, and we have found measurable proton conductivity enhancement. Electrochemical property of gas-columnar ceria interface on the hydrogen electrooxidation is studied by AC impedance spectroscopy. Isothermal gas composition dependence of the electrode resistance was studied to elucidate Sm doping level effect and microstructure effect. Significantly, preferred orientation is shown to affect the gas dependence and performance of the fuel cell anode. A hypothesis is proposed to explain the origin of this behavior. Lastly, an optical transmittance based methodology was developed to obtain reference refractive index and microstructural parameters (thickness, roughness, porosity) of ceria films via subsequent fitting procedure.

Structural and optical characterization of vertical GaAs/GaP core-shell nanowires grown on Si substrates

GaAs nanowires were grown on Si (111) substrates. By coating a thin GaAs buffer layer on Si surface and using a two-temperature growth, the morphology and crystal structure of GaAs nanowires were dramatically improved. The strained GaAs/GaP core-shell nanowires, based on the improved GaAs nanowires with a shell thickness of 25 nm, showed a significant shift in emission energy of 260 meV from the unstrained GaAs nanowires. © 2010 IEEE.

Thermo-optical characterization of fluorescent rhodamine B based temperature-sensitive nanosensors using a CMOS MEMS micro-hotplate

A custom designed microelectromechanical systems (MEMS) micro-hotplate, capable of operating at high temperatures (up to 700 C), was used to thermo-optically characterize fluorescent temperature-sensitive nanosensors. The nanosensors, 550 nm in diameter, are composed of temperature-sensitive rhodamine B (RhB) fluorophore which was conjugated to an inert silica sol-gel matrix. Temperature-sensitive nanosensors were dispersed and dried across the surface of the MEMS micro-hotplate, which was mounted in the slide holder of a fluorescence confocal microscope. Through electrical control of the MEMS micro-hotplate, temperature induced changes in fluorescence intensity of the nanosensors was measured over a wide temperature range. The fluorescence response of all nanosensors dispersed across the surface of the MEMS device was found to decrease in an exponential manner by 94%, when the temperature was increased from 25 C to 145 C. The fluorescence response of all dispersed nanosensors across the whole surface of the MEMS device and individual nanosensors, using line profile analysis, were not statistically different (p < 0.05). The MEMS device used for this study could prove to be a reliable, low cost, low power and high temperature micro-hotplate for the thermo-optical characterisation of sub-micron sized particles. The temperature-sensitive nanosensors could find potential application in the measurement of temperature in biological and micro-electrical systems. The Authors. © 2013 Published by Elsevier B.V. All rights reserved.

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.

Fabrication and optical characterization of GaN-based nanopillar light emitting diodes

InGaN/GaN-multiple-quantum-well-based light emitting diode ( LED) nanopillar arrays with a diameter of approximately 200nm and a height of 700nm are fabricated by inductively coupled plasma etching using Ni self-assembled nanodots as etching mask. In comparison to the as-grown LED sample an enhancement by a factor of four of photoluminescence ( PL) intensity is achieved after the fabrication of nanopillars, and a blue shift and a decrease of full width at half maximum of the PL peak are observed. The method of additional wet etching with different chemical solutions is used to remove the etch-induced damage. The result shows that the dilute HCl ( HCl:H2O=1:1) treatment is the most effective. The PL intensity of nanopillar LEDs after such a treatment is about 3.5 times stronger than that before treatment.

Structural and optical characterization of Zn1-xCdxO thin films deposited by dc reactive magnetron sputtering

Zn1-xCdxO crystal thin films with different compositions were prepared on silicon and sapphire substrates by the dc reactive magnetron sputtering technique. X-ray diffraction measurements show that the Zn1-xCdxO films are of completely (002)-preferred orientation for x less than or equal to 0.6. For x = 0.8, the Elm is a mixture of ZnO hexagonal wurtzite crystals and CdO cubic crystals. For pure CdO, it is highly (200) preferential-oriented. Photoluminescence spectrum measurement shows that the Zn1-xCdxO (x = 0.2) thin film has a redshift of 0.14 eV from that of ZnO reported previously.

Structural and optical characterization of InAs nanostructures grown on (001) and high index InP substrates

The effects of InP substrate orientations on self-assembled InAs quantum dots (QDs) have been investigated by molecular beam epitaxy (MBE). A comparison between atomic force microscopy (AFM) and photoluminescence (PL) spectra shows that a high density of smaller InAs islands can be obtained by using such high index substrates. On the other hand, by introducing a lattice-matched underlying In0.52Al0.24Ga0.24As layer, the InAs QDs can be much more uniform in size and have a great improvement in PL properties. More importantly, 1.55-mu m luminescence at room temperature (RT) can be realized in InAs QDs deposited on (001) InP substrate with underlying In0.52Al0.24Ga0.24As layer. (C) 2000 Elsevier Science B.V. All rights reserved.

X-ray diffraction and optical characterization of interdiffusion in self-assembled InAs/GaAs quantum-dot superlattices

We report on the characterization of thermally induced interdiffusion in InAs/GaAs quantum-dot superlattices with high-resolution x-ray diffraction and photoluminescence techniques. The dynamical theory is employed to simulate the measured x-ray diffraction rocking curves of the InAs/GaAs quantum-dot superlattices annealed at different temperatures. Excellent agreement between the experimental curves and the simulations is achieved when the composition, thickness, and stress variations caused by interdiffusion are taken in account. It is found that the significant In-Ga intermixing occurs even in the as-grown InAs/GaAs quantum dots. The diffusion coefficients at different temperatures are estimated. (C) 2000 American Institute of Physics. [S0003-6951(00)02440-2].

Optical characterization of high-purity cubic GaN grown on GaAs (001) substrate by metalorganic chemical vapor deposition

The optical properties of cubic GaN films have been investigated in the temperature range of 10-300 K. Five peaks were observed at 10 K. From the dependence of photoluminescence emissions on the temperature and excitation intensity, we have assigned two of the five peaks (2.926 and 2.821 eV) to donor-acceptor pair (DAP) transitions. Furthermore, these two peaks were found to be related to a common shallow donor involved in the peak position previously reported at 3.150 eV. The intensities of DAP transitions were much weaker than that of excitonic emission even at low temperature, indicating a relatively high purity of our samples. (C) 2000 American Institute of Physics. [S0003-6951(00)00921-9].