Organic electronics have been drawing a lot of attention over the past few decades with recent commercial applications such as organic photovoltaics, OLEDs, and flexible organic displays. One of the key components for designing organic molecules suitable for electronic devices is a fundamental understanding of excitonic behaviors. Here we report on the fabrication and photoluminescence studies of crystalline thin film organic alloy systems, metal free and metal based octabutoxyphthalocyanine (MOBPcxH2OBPc1-x), and metal-free H2OBPc and octabutoxynapthalocyanine (H2OBNc) mixtures (H2OBNcxH2OBPc1-x). Crystalline thin films of these materials were deposited using an in-house developed pen writing technique that results in macroscopic long-range order even at the ratio of x = 0.5, which is unique and important for spectroscopic studies.
Our experiments reveal that the coherent excitonic states of MOBPcxH2OBPc1-x and H2OBNcxH2OBPc1-x crystalline thin films can be tuned continuously as a function of alloy concentration (0 < x < 1). Moreover, the solution-processed technique used to fabricate these crystalline thin films provides us an unprecedented advantage in designing and controlling the bandgap tunability as well as achieving the desired exciton coherent length for variety of applications.
Organic semiconductors are emerging as a leading area of research as they are expected to overcome limitations of inorganic semiconductor devices for certain applications where low cost manufacturing, device transparency in the visible range or mechanical flexibility are more important than fast switching times. Solution processing methods produce thin films with millimeter sized crystalline grains at very low cost manufacturing prices, ideally suited for optical spectroscopy investigations of long range many-body effects in organic systems. To this end, we synthesized an entire family of organosoluble 3-d transition metal Pc’s and successfully employed a novel solution-based pen-writing deposition technique to fabricate long range ordered thin films of mixtures of metal-free (H2Pc) molecule and organometallic phthalocyanines (MPc's). Our previous studies on the parent MPc crystalline thin films identified different electronic states mediating exchange interactions in these materials. This understanding of spin-dependent exchange interaction between delocalized π-electrons with unpaired d spins enabled the further tuning of these interactions by mixing CoPc and H2Pc in different ratios ranging from 1:1 to 1000:1 H2Pc:MPc. The magnitude of the exchange is also tunable as a function of the average distance between unpaired spins in these materials. Furthermore, high magnetic field (B < 25T) MCD and magneto-photoluminescence show evidence of spin-polarized band-edge excitons in the same materials.
The selective coupling between polarized photons and electronic states in materials enables polarization-resolved spectroscopy studies of exchange interactions, spin dynamics, and collective magnetic behavior of conduction electrons in semiconductors. Here we report on Magnetic Circular Dichroism (MCD) studies of magnetic properties of electrons in crystalline thin films of small molecule organic semiconductors. Specifically, the focus was on the magnetic exchange interaction properties of d-shell ions (Cu2+, Co2+ and Mn2+) metal phthalocyanine (Pc) thin films that one may think of as organic analogues of diluted magnetic semiconductors (DMS). These films were deposited in-house using a recently developed pen-writing method that results in crystalline films with macroscopic long range ordering and improved electronic properties, ideally suited for spectroscopy techniques.
Our experiments reveal that, in analogy to DMS, the extended π-orbitals of the Pc molecule mediate the spin exchange between highly localized d-like unpaired spins. We established that exchange mechanisms involve different electronic states in each species and/or hybridization between d-like orbitals and certain delocalized π-orbitals. Unprecedented 25T MCD and PL conducted in the unique 25T Split Florida HELIX magnet at the National High Magnetic Field Laboratory (NHMFL) will prove useful in probing these exchange interactions.
Optical properties of silicon and indium phosphide nanoparticles with emission throughout the visible wavelength range are presented. The peak emission wavelength of these nanoparticles is controlled by the reaction time and by post-growth etching treatments. Ultrafast spectroscopy is used to determine the photoluminescence lifetime in order to correlate the spectral response with the structural and chemical characterization of these nanoparticles. The measured lifetimes are used to identify surfactant, surface, and core nanoparticle emission. The nanoparticles exhibit efficient emission that is quenched when embedded within particular polymeric matrices.