Xavier A. Jeanbourquin

Enhancing the Thermal Stability of Solution‐Processed Small‐Molecule Semiconductor Thin Films Using a Flexible Linker Approach

Using flexible aliphatic chains to link conjugated molecular semiconductors affords a polymeric material that possesses defined conjugated segments but extended covalent connectivity, which enhances crystallinity and thermal stability in field-effect transistors and bulk heterojunction solar-cell devices when used as an additive.

Templating Sol-Gel Hematite Films with Sacrificial Copper Oxide: Enhancing Photoanode Performance with Nanostructure and Oxygen Vacancies

Nanostructuring hematite films is a critical step for enhancing photoelectrochemical performance by circumventing the intrinsic limitations on minority carrier transport. Herein, we present a novel sol-gel approach that affords nanostructured hematite films by including CuO as sacrificial templating agent. First, by annealing in air at 450 °C a film comprising an intimate mixture of CuO and Fe2O3 nanoparticles is obtained. The subsequent treatment with NaCl and annealing at 700 °C under Argon reveals a nanostructured highly crystalline hematite film devoid of copper. Photoelectrochemical investigations reveal that the incorporation of CuO as templating agent and the inert conditions employed during the annealing play a crucial role in the performance of the hematite electrodes. Mott-Schottky analysis shows a higher donor concentration when annealing in inert conditions, and even higher when combined with the NaCl treatment. These findings agree well with the presence of an oxygen-deficient shell on the materials surface evidenced by FT-IR and XPS measurements. Likewise, the incorporation of the CuO enhances the photocurrent obtained at 1.23 V from 0.55 to 0.8 mA·cm(-2) because of an improved nanostructure. Optimized films demonstrate an incident photon-to-current efficiency (IPCE) of 52% at 380 nm when applying 1.23 V versus RHE, and a faradaic efficiency for water splitting close to unity.

Evaluating spinel ferrites MFe2O4 (M = Cu, Mg, Zn) as photoanodes for solar water oxidation: prospects and limitations

The search for ideal semiconductors for photoelectrochemical solar fuel conversion has recently recognized the spinel ferrites as promising candidates due to their optoelectronic tunability together with superb chemical stability. However, a systematic understanding of the main material factors limiting their performance is currently lacking. Herein, nanostructured thin-film electrodes of three representative spinels, namely CuFe2O4 (CFO), MgFe2O4 (MFO) and ZnFe2O4 (ZFO), are prepared by a solution-based approach and their photoelectrochemical (PEC) properties are comprehensively characterized. Annealing post-treatments together with the deposition of NiFeOx overlayers are found to improve the native n-type response, although a dominant bulk recombination (especially in MFO) limits the saturation photocurrents (below 0.4 mA cm−2 at 1.23 V vs. RHE). Likewise, prominent Fermi level pinning due to surface states at around 0.9 V vs. RHE in all cases appears to limit the photovoltage (to ca. 300 mV). Rapid-scan voltammetry is used to gain insight into the surface states and the operation of the overlayer. Interestingly, the NiFeOx is ineffective at mitigating Fermi level pinning, but clearly participates as an electrocatalyst to improve the overall performance. Generally, these results evidence the potential and current intrinsic limitations of the spinel ferrites—establishing a roadmap for the optimization of these materials as photoanodes for solar water oxidation.

Morphology stabilization strategies for small-molecule bulk heterojunction photovoltaics

The greater crystallinity of solution-processed small-molecule organic semiconductors, compared to their polymer counterparts, renders the bulk heterojunction (BHJ) more susceptible to phase separation under thermal stress, decreasing device performance. Here we demonstrate and compare strategies to stabilize the donor:acceptor BHJ in DPP(TBFu)2:PC61BM solar cells using molecular additives designed to either afford compatiblization (CP) of the bulk heterojunction, or to in situ link (ISL) the components using a functional azide group. Both additives were found to stop phase segregation of the BHJ under thermal stress. At 5 wt% loading the ISL additive prevents phase segregation, while altering the azide reaction mechanism by using UV-induced linking versus thermal induced linking was found to significantly affect the device performance. Including 5 wt% of the CP additive slowed phase segregation and devices retained 80% of their optimum performance after 3000 min of thermal treatment at 110 °C (compared to 50% with the control). The CP additive at 10 wt% changed drastically the kinetics of phase segregation leading to devices with no decrease in performance over 3000 min thermal treatment. Thin film morphology characterization together with photoluminescence and impedance spectroscopy give further insight into the performance differences between the additives. These results reinforce the conclusion that the compatiblization method is the most promising strategy to engineer highly-efficient thermally-stable organic photovoltaics based on solution-processed small molecules.

Robust Hierarchically Structured Biphasic Ambipolar Oxide Photoelectrodes for Light-Driven Chemical Regulation and Switchable Logic Applications

Tunable ambipolar photoelectrochemical behavior emerges from microdomains of nanostructured p-type CuFeO2 and n-type Fe2 O3 that arise from a single facile solution-processed thin film. The switchable operation of this system is controlled by chemical, optical, or electronic inputs with a uniquely high photocurrent response (on the order of 1 mA cm-2 ), suitable for robust practical application as an oxygen photoregulator.

Semiconducting alternating multi-block copolymers via a di-functionalized macromonomer approach

The development of fully-conjugated semiconducting block-copolymers is an important goal for organic electronics, but to date has been almost exclusively limited to materials containing poly(3-alkylthiophenes). Here we present the prototype of a class of fully-conjugated semiconducting block copolymers (prepared using a versatile route based on conjugated macromonomers and a cross-coupling polycondensation) that exhibit hole mobility in field effect transistors of the order of 0.1 cm2 V−1 s−1 and nanoscopic phase domain separation.

Amorphous Ternary Charge-Cascade Molecules for Bulk Heterojunction Photovoltaics

Ternary bulk heterojunctions with cascade-type energy-level configurations are of significant interest for further improving the power conversion efficiency (PCE) of organic solar cells. However, controlling the self-assembly in solution-processed ternary blends remains a key challenge. Herein, we leverage the ability to control the crystallinity of molecular semiconductors via a spiro linker to demonstrate a simple strategy suggested to drive the self-assembly of an ideal charge-cascade morphology. Spirobifluorene (SF) derivatives with optimized energy levels from diketopyrrolopyrrole (DPP) or perylenediimide (PDI) components, coded as SF-(DPP)4 and SF-(PDI)4, are synthesized and investigated for application as ternary components in the host blend of poly(3-hexylthiophene-2,5-diyl):[6,6]phenyl-C61-butyric acid methyl ester (P3HT:PCBM). Differential scanning calorimetry and X-ray/electron diffraction studies suggest that at low loadings (up to 5 wt %) the ternary component does not perturb crystallization of the donor:acceptor host blend. In photovoltaic devices, up to 36% improvement in the PCE (from 2.5% to 3.5%) is found when 1 wt % of either SF-(DPP)4 or SF-(PDI)4 is added, and this is attributed to an increase in the fill factor and open-circuit voltage, while at higher loadings, the PCE decreased because of a lower short-circuit current density. A comparison of the quantum efficiency measurements [where light absorption of SF-(DPP)4 was found to give up to 95% internal conversion] suggests that improvement due to enhanced light absorption or to better exciton harvesting via resonance energy transfer is unlikely. These data, together with the crystallinity results, support the inference that the SF compounds are excluded to the donor:acceptor interface by crystallization of the host blend. This conclusion is further supported by impedance spectroscopy and a longer measured charge-carrier lifetime in the ternary blend.