RESUMO
Doping-induced solubility control (DISC) patterning is a recently developed technique that uses the change in polymer solubility upon doping, along with an optical dedoping process, to achieve high-resolution optical patterning. DISC patterning can produce features smaller than predicted by the diffraction limit; however, no mechanism has been proposed to explain such high resolution. Here, we use diffraction to spatially modulate the light intensity and determine the dissolution rate, revealing a superlinear dependence on light intensity. This rate law is independent of wavelength, indicating that patterning resolution is not dominated by an optical dedoping reaction, as was previously proposed. Instead we show here that the optical patterning mechanism is primarily controlled by the thermal profile generated by the laser. To quantify this effect, the thermal profile and dissolution rate are modeled using a finite-element model and compared against patterned line cross sections as a function of wavelength, laser intensity, and dwell time. Our model reveals that although the laser-generated thermal profile is broadened considerably beyond the profile of the laser, the highly temperature dependent dissolution rate results in selective dissolution near the peak of the thermal profile. Therefore, the key factor in achieving super-resolution patterning is a strongly temperature dependent dissolution rate, a common feature of many polymers. In addition to suggesting several routes to improved resolution, our model also demonstrates that doping is not required for optical patterning of conjugated polymers, as was previously believed. Instead, we demonstrate that superlinear resolution optical patterning should be attainable in any conjugated polymer simply by tuning the solvent quality during patterning, thus extending the applicability of our method to a wide class of materials. We demonstrate the generality of photothermal patterning by writing sub-400 nm features into undoped PffBT4T-2OD.
RESUMO
High electron affinity (EA) molecules p-type dope low ionization energy (IE) polymers, resulting in an equilibrium doping level based on the energetic driving force (IE-EA), reorganization energy, and dopant concentration. Anion exchange doping (AED) is a process whereby the dopant anion is exchanged with a stable ion from an electrolyte. We show that the AED level can be predicted using an isotherm equilibrium model. The exchange of the dopant anion (FeCl3-) for a bis(trifluoromethanesulfonamide) (TFSI-) anion in the polymers poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly[3-(2,2-bithien-5-yl)-2,5-bis(2-hexyldecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione-6,5-diyl] (PDPP-2T) highlights two cases in which the process is nonspontaneous and spontaneous, respectively. For P3HT, FeCl3 provides a high doping level but an unstable counterion, so exchange results in an air stable counterion with a marginal increase in doping. For PDPP-2T, FeCl3 is a weak dopant, but the exchange of FeCl3- for TFSI- is spontaneous, so the doping level increases by >10× with AED.
RESUMO
Organic semiconductors (OSCs) offer a new avenue to the next-generation electronics, but the lack of a scalable and inexpensive nanoscale patterning/deposition technique still limits their use in electronic applications. Recently, a new lithographic etching technique has been introduced that uses molecular dopants to reduce semiconducting polymer solubility in solvents and a direct-write laser to remove dopants locally, enabling rapid OSC etching with diffraction limited resolution. Previous publications postulated that the reaction that enables patterning is a photochemical reaction between photoexcited dopants with neutral solvent molecules. In this work, we analyze the photoinduced dissolution kinetics of F4TCNQ doped P3HT films using time-resolved in situ optical probing. We find two competing mechanisms that control de-doping and dissolution: the first is the photochemical reaction posited in the literature, and the second involves direct heating of the polymer by the laser, inducing increased solubility for both the polymer and dopant. We show that the wavelength-specific photochemical effect is dominant in low photon doses while the photothermal effect is dominant with high excitation rates regardless of laser wavelength. With sufficiently high optical intensity input, the photothermal mechanism can in principle achieve a high writing speed up to 1 m/s. Our findings bring new insights into the mechanisms behind laser direct writing of OSCs based on dopant induced solubility control and enable ultraprecise fabrications of various device configurations in large-scale manufacturing.
