R. Clayton Shallcross

Photoelectrochemical Processes in Polymer-Tethered CdSe Nanocrystals

We demonstrate the electrochemical capture of CdSe semiconductor nanocrystals (NCs), with thiophene-terminated carboxylic acid capping ligands, at the surfaces of electrodeposited poly(thiophene) films (i) poly((diethyl)propylenedixoythiophene), P(Et)(2)ProDOT; (ii) poly(propylenedioxythiophene), PProDOT; and (iii) poly(ethylenedioxythiophene), PEDOT, coupled with the exploration of their photoelectrochemical properties. Host polymer films were created using a kinetically controlled electrodeposition protocol on activated indium-tin oxide electrodes (ITO), producing conformal films that facilitate high rates of electron transfer. ProDOT-terminated, ligand-capped CdSe-NCs were captured at the outer surface of the host polymer films using a unique pulse-potential step electrodeposition protocol, providing for nearly close-packed monolayers of the NCs at the host polymer/solution interface. These polymer-confined CdSe NCs were used as sensitizers in the photoelectrochemical reduction of methyl viologen (MV(+2)). High internal quantum efficiencies (IQEs) are estimated for photoelectrochemical sensitized MV(+2) reduction using CdSe NCs ranging from 3.1 to 7.0 nm diameters. Cathodic photocurrent at high MV(+2) concentrations are limited by the rate of hole-capture by the host polymer from photoexcited NCs. The rate of this hole-capture process is determined by (a) the onset potential for reductive dedoping of the host polymer film; (b) the concentration ratio of neutral to oxidized forms of the host polymer ([P(n)]/[P(ox)]); and (c) the NC diameter, which controls its valence band energy, E(VB). These relationships are consistent with control of photoinduced electron transfer by Marcus-like excess free energy relationships. Our electrochemical assembly methods provide an enabling route to the capture of functional NCs in conducting polymer hosts in both photoelectrochemical and photovoltaic energy conversion systems.

Planar Fiber-Optic Chips for Broadband Spectroscopic Interrogation of Thin Films

A planar fiber-optic chip (FOC) has been developed using side-polished optical fibers and characterized for broadband absorbance and fluorescence detection of molecular films. FOC technology combines the sensitivity of an attenuated total reflection (ATR) element with the ease of use of fiber-optic-based spectrometers and light sources to create an improved platform for spectroscopic analysis of molecular adsorbates. A multi-mode optical fiber (core diameter = 50 μm, numerical aperture = 0.22, stepped refractive index profile) mounted in a glass V-groove block was side-polished to create a planar platform that allows access to the evanescent field escaping from the fiber core. For this generation of FOC technology, the exposed evanescent field has an interaction length of approximately 17.2 mm. The FOC platform was independently characterized through measurements of thin-film and bulk absorbing samples. The device performance was compared to the existing ATR technology and methods for increasing sensitivity of the FOC were investigated and validated. Additionally, we have demonstrated the ability of the FOC to both evanescently excite and collect fluorescence through guided modes of the optical fiber for a surface-confined luminescent semiconductor nanoparticle film (4 nm diameter, ligand capped, CdSe core). The FOC described here with a supported planar interface can facilitate the use of conventional planar deposition technologies and provide a robust planar platform that is amenable for incorporation into various sensor technologies.

Simple Fabrication of an Organic Laser by Microcontact Molding of a Distributed Feedback Grating

Lasing from an organic polymer is demonstrated in a device utilizing a distributed feedback (DFB) grating, manufactured by microcontact molding of CdSe nanocrystals (NCs) directly on top of the emitter layer. Besides the simpler fabrication in comparison with a reference device based on a photolithographically prepared DFB grating in a bottom dielectric layer, a much higher DFB strength for NC-gratings is observed, resulting in reduced lasing threshold and a fourfold differential lasing efficiency.

Determining Band-Edge Energies and Morphology-Dependent Stability of Formamidinium Lead Perovskite Films Using Spectroelectrochemistry and Photoelectron Spectroscopy

We show for the first time that the frontier orbital energetics (conduction band minimum (CBM) and valence band maximum (VBM)) of device-relevant, methylammonium bromide (MABr)-doped, formamidinium lead trihalide perovskite (FA-PVSK) thin films can be characterized using UV-vis spectroelectrochemistry, which provides an additional and straightforward experimental technique for determining energy band values relative to more traditional methods based on photoelectron spectroscopy. FA-PVSK films are processed via a two-step deposition process, known to provide high efficiency solar cells, on semitransparent indium tin oxide (ITO) and titanium dioxide (TiO2) electrodes. Spectroelectrochemical characterization is carried out in a nonsolvent electrolyte, and the onset potential for bleaching of the FA-PVSK absorbance is used to estimate the CBM, which provides values of ca. -4.0 eV versus vacuum on both ITO and TiO2 electrodes. Since electron injection occurs from the electrode to the perovskite, the CBM is uniquely probed at the buried metal oxide/FA-PVSK interface, which is otherwise difficult to characterize for thick films. UPS characterization of the same FA-PVSK thin films provide complementary near-surface measurements of the VBM and electrode-dependent energetics. In addition to energetics, controlled electrochemical charge injection experiments in the nonsolvent electrolyte reveal decomposition pathways that are related to morphology-dependent heterogeneity in the electrochemical and chemical stability of these films. X-ray photoelectron spectroscopy of these electrochemically treated FA-PVSK films shows changes in the average near-surface stoichiometry, which suggests that lead-rich crystal termination planes are the most likely sites for electron trapping and thus nanometer-scale perovskite decomposition.

Understanding the role of titanium dioxide (TiO 2 ) surface chemistry on the nucleation and energetics of hybrid perovskite films (Conference Presentation)

We demonstrate how amino-terminated silane monolayers alter the chemical and energetic composition of the TiO2 surface, which controls the interfacial nucleation, growth and energetics of device-relevant, hybrid perovskite (PVSK) thin films. The surface chemistry and energetics of compact TiO2 thin films are modified with a 3-aminopropyltriethoxysilane (APTES) monolayer that can either weakly coordinate Pb2+ ions (–NH2/free base form) or act as a surrogate organic cation (–NH3+/acid form) at the TiO2/PVSK interface, providing for significant differences in the nucleation free energy for the PVSK active layer as a function of NH3+/NH2 ratio. XPS spectra of amine-modified TiO2 surfaces (N 1s core level) demonstrate that we can achieve NH3+/NH2 ratios of between 3:1 and 1:3 depending upon subsequent acid and base treatment, respectively. Methylammonium lead triiodide (MAPbI3) films are incrementally co-evaporated on TiO2, TiO2/APTES-NH3+ and TiO2/APTES-NH2 interfaces, and the chemical composition, growth dynamics and energetics are systematically investigated using in situ X-ray photoelectron spectroscopy (XPS) and UV photoelectron spectroscopy (UPS). The XPS and UPS results reveal that initial nucleation and subsequent growth of the MAPbI3 PVSK film strongly depends on the chemical functionality of the TiO2 surface. The evaporated films display island-like growth on the bare TiO2 surface, which hinders nucleation of the PVSK phase until ca. 15 nm of precursor material is deposited. Conversely, film growth is more layer-by-layer on the amine-modified TiO2 interfaces, which promote nucleation of the PVSK phase within the first ca. 5 nm of deposition. In addition to vacuum evaporated thin films, we show how these TiO2 surface modifications control the morphology and crystallinity of solution-processed PVSK films based on formamidinium and methylammonium organic cations. These studies elucidate the role of TiO2 surface chemistry on the formation mechanism of hybrid PVSK active layers and the interfacial and bulk energetics, which have significant consequences related to the processing and operation of next-generation optoelectronic device platforms.

Effect of substrate surface free energy on the optoelectronic and morphological properties of organolead halide perovskite solar cell materials (Presentation Recording)

Here, we show how the surface free energy of the electron-collecting oxide contact has a very pronounced effect on the nucleation free energy of solution-processed organolead halide perovskite thin films, which influences the crystal size/orientation, band-edge energies, conductivity and, ultimately, the performance of solar cell devices. While a great deal of the research community’s attention has been focused on the perovskite deposition methodology (e.g., starting precursors, annealing conditions, etc.), we demonstrate how the surface free energy of the oxide contact itself can be modified to control morphology and optoelectronic properties of the resulting hybrid perovskite thin films. The surface free energy of high-quality oxide contacts deposited by chemical vapor deposition (CVD) and atomic layer deposition (ALD) is modified by functionalization with a variety of self-assembled monolayers. We explore a number of deposition methodologies (e.g., a variety of single step and sequential step approaches) and their effect on the morphological and electronic properties of the resulting perovskite thin films deposited on these modified oxide contacts. Standard atomic force microscopy (AFM) and its conductive analog (cAFM) show how the oxide surface free energy ultimately affects the nanoscale morphology and charge transport characteristics of these semiconductor films. Photoelectron spectroscopy is used to elucidate the chemical composition (e.g., X-ray photoelectron spectroscopy - XPS), band edge energies (e.g., ultraviolet photoelectron spectroscopy - UPS), and the presence of gap states above the valence band (high sensitivity UPS measurements near the Fermi energy) of the hybrid perovskite materials as a function of the oxide surface free energy.