Accelerated Thermal Depolymerization of Cyclic Polyphthalaldehyde with a Polymeric Thermoacid Generator.

Thermally triggerable polymer films that degrade at modest temperatures (≈85 °C) are created from a blend of cyclic polyphthalaldehyde (cPPA) and a polymeric thermoacid generator, poly(vinyl tert-butyl carbonate sulfone) (PVtBCS). PVtBCS depolymerizes when heated, generating acid which initiates the depolymerization of cPPA into volatile byproducts. The mass loss onset for 2 wt% PVtBCS/cPPA is 22 °C lower than the onset for neat cPPA alone in dynamic thermogravimetric analysis experiments. Increased concentrations of PVtBCS increase the rate of depolymerization of cPPA. Raman spectroscopy reveals that the monomer, o-phthalaldehyde, is the main depolymerization product of the acid-catalyzed depolymerization of cPPA. The PVtBCS/cPPA blend is a promising material for the design and manufacture of transient electronic packaging and polymers.

Thermally triggered degradation of transient electronic devices.

Thermally triggered transient electronics using wax-encapsulated acid, which enable rapid device destruction via acidic degradation of the metal electronic components are reported. Using a cyclic poly(phthalaldehyde) (cPPA) substrate affords a more rapid destruction of the device due to acidic depolymerization of cPPA.

Tunable Thermal Degradation of Poly(vinyl butyl carbonate sulfone)s via Side-Chain Branching.

Polymeric materials that depolymerize into volatiles on command may function as vanishing substrates or packaging for transient electronics. Poly(vinyl tert-butyl carbonate sulfone) is known to afford low-boiling byproducts upon heat-activated degradation; however, the polymer is rather unstable, even to the degree of being difficult to process and handle. Understanding the origin of this instability is important for the development of robust materials capable of programmed self-destruction. In this work, we show that poly(vinyl tert-butyl carbonate sulfone)s thermally decompose via carbonate elimination as the rate-determining step, indicating that its thermal instability stems from the lability of the tert-butyl carbonate group. We further examined the effect of isomeric butyl carbonate side chains on the thermal degradation of poly(vinyl butyl carbonate sulfone)s and found that the degradation onsets range from 91 to 213 °C, yielding as little as 2.77 ± 0.53 wt % residue. Results from our findings will aid in the development of vanishing polymers with tunable thermal degradation.

Triggered transience of metastable poly(phthalaldehyde) for transient electronics.

Triggerable transient electronics are demonstrated with the use of a metastable poly(phthalaldehyde) polymer substrate and encapsulant. The rate of degradation is controlled by the concentration of the photo-acid generator and UV irradiance. This work expands on the materials that can be used for transient electronics by demonstrating transience in response to a preselected trigger without the need for solution-based degradation.

A mechanistic understanding of processing additive-induced efficiency enhancement in bulk heterojunction organic solar cells.

The addition of processing additives is a widely used approach to increase power conversion efficiencies for many organic solar cells. We present how additives change the polymer conformation in the casting solution leading to a more intermixed phase-segregated network structure of the active layer which in turn results in a 5-fold enhancement in efficiency.

Enhanced solid-state order and field-effect hole mobility through control of nanoscale polymer aggregation.

Efficient charge carrier transport in organic field-effect transistors (OFETs) often requires thin films that display long-range order and close π-π packing that is oriented in-plane with the substrate. Although some polymers have achieved high field-effect mobility with such solid-state properties, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm(2)/V·s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm(2)/V·s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably more closely, and align with a greater preference for in-plane π-π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when nonsolvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π-π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials.

Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells.

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells.

Efficient small molecule bulk heterojunction solar cells with high fill factors via pyrene-directed molecular self-assembly.

Efficient organic photovoltaic (OPV) materials are constructed by attaching completely planar, symmetric end-groups to donor-acceptor electroactive small molecules. Appending C2-pyrene as the small molecule end-group to a diketopyrrolopyrrole core leads to materials with a tight, aligned crystal packing and favorable morphology dictated by π-π interactions, resulting in high power conversion efficiencies and high fill factors. The use of end-groups to direct molecular self-assembly is an effective strategy for designing high-performance small molecule OPV devices.

Triazole bridges as versatile linkers in electron donor-acceptor conjugates.

Aromatic triazoles have been frequently used as π-conjugated linkers in intramolecular electron transfer processes. To gain a deeper understanding of the electron-mediating function of triazoles, we have synthesized a family of new triazole-based electron donor-acceptor conjugates. We have connected zinc(II)porphyrins and fullerenes through a central triazole moiety--(ZnP-Tri-C(60))--each with a single change in their connection through the linker. An extensive photophysical and computational investigation reveals that the electron transfer dynamics--charge separation and charge recombination--in the different ZnP-Tri-C(60) conjugates reflect a significant influence of the connectivity at the triazole linker. Except for the m4m-ZnP-Tri-C(60)17, the conjugates exhibit through-bond photoinduced electron transfer with varying rate constants. Since the through-bond distance is nearly the same for all the synthesized ZnP-Tri-C(60) conjugates, the variation in charge separation and charge recombination dynamics is mainly associated with the electronic properties of the conjugates, including orbital energies, electron affinity, and the energies of the excited states. The changes of the electronic couplings are, in turn, a consequence of the different connectivity patterns at the triazole moieties.

Incorporation of furan into low band-gap polymers for efficient solar cells.

The design, synthesis, and characterization of the first examples of furan-containing low band-gap polymers, PDPP2FT and PDPP3F, with substantial power conversion efficiencies in organic solar cells are reported. Inserting furan moieties in the backbone of the conjugated polymers enables the use of relatively small solubilizing side chains because of the significant contribution of the furan rings to overall polymer solubility in common organic solvents. Bulk heterojunction solar cells fabricated from furan-containing polymers and PC(71)BM as the acceptor showed power conversion efficiencies reaching 5.0%.

First triazole-linked porphyrin-fullerene dyads.

A general procedure for the synthesis of 1,2,3-triazole-linked porphyrin-fullerene dyads is described. Four of these compounds have been prepared and characterized.