Heterostructures are central to the efficient manipulation of charge carriers, excitons and photons for high-performance semiconductor devices. Although these can be formed by stepwise evaporation of molecular semiconductors, they are a considerable challenge for polymers owing to re-dissolution of the underlying layers. Here we demonstrate a simple and versatile photocrosslinking methodology based on sterically hindered bis(fluorophenyl azide)s. The photocrosslinking efficiency is high and dominated by alkyl side-chain insertion reactions, which do not degrade semiconductor properties. We demonstrate two new back-infiltrated and contiguous interpenetrating donor-acceptor heterostructures for photovoltaic applications that inherently overcome internal recombination losses by ensuring path continuity to give high carrier-collection efficiency. This provides the appropriate morphology for high-efficiency polymer-based photovoltaics. We also demonstrate photopatternable polymer-based field-effect transistors and light-emitting diodes, and highly efficient separate-confinement-heterostructure light-emitting diodes. These results open the way to the general development of high-performance polymer semiconductor heterostructures that have not previously been thought possible.

Thin films of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (C14–PBTTT) exhibit a monolayer-terraced morphology that indicates a pronounced lamellar order with π-stacks of extended polymer chains. Previously this remarkable state of order was thought to be promoted by the interdigitation of alkyl side chains between the lamellae during cooling from the liquid-crystalline (LC) phase. Here we establish that the key to this ordering in fact is the formation of unentangled π-stacks of extended polymer chains in dilute solutions of chlorobenzene (CB) or 1,2-dichlorobenzene (o-DCB), which though routinely used as the “best” solvents are in fact borderline solvents. Film formation causes these π-stacks to deposit substantially oriented in the film plane, while the subsequent anneal and cool from LC phase accentuates this incipient order to develop the monolayer-terraced morphology. This mechanism is supported by the following lines of evidence. (i) Hydrodynamic and viscometry measurements respectively of the Kuhn segment length and Mark–Houwink–Sakurada exponent of PBTTT reveal that CB is a near-Θ solvent, and PBTTT is significantly stiffer than regioregular polythiophene. (ii) Solution-state UV–vis spectroscopy reveals an early coil → rod transition in highly dilute solutions, which gives rise to unentangled π-stacks. (iii) Solid-state UV–vis spectroscopy, atomic force microscopy and variable-angle spectroscopic ellipsometry together reveal the as-deposited π-stacks are already substantially oriented in the film plane. We further demonstrate that this monolayer-terraced morphology can also be induced in regioregular poly(3-hexylthiophene) films using a borderline solvent mixture of chlorobenzene and mesitylene, and in very dilute CB where the incipient π-stacks do not entangle. Therefore, this dilute π-stacking mechanism is general. Processing with a borderline solvent or solvent additive thus provides a general route to obtain superior supramolecular order in π-stackable conjugated polymers.

Fourier-transform infrared spectroscopy of two prototypical high-mobility polymer organic semiconductors (OSCs), regioregular poly(3-hexylthiophene) (rr-P3HT) and poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno(3,2-b)thiophene] (PBTTT), reveals photoinduced doping that involves both oxygen and water dissolved in the polymer matrix when exposed to light. The equilibrium concentration of water at room temperature and 60% relative humidity in these films is $2 Â 10 19 cm À3, and exists primarily as monomers, with a small population of dimers and trimers. Photo-excitation in room light ultimately generates a polaron density of the order of a few 10 17 cm À3, which is sufficient to degrade the saturation and 'on-off' characteristics of organic field-effect transistors, and the dark current of organic photovoltaics. The dopant anion has been identified primarily to be hydroxide ion species. This process occurs to a smaller extent in wet nitrogen, but even less in dry oxygen, which points to a key role of the dissolved water. The relative stability of PBTTT over rr-P3HT is found to be largely kinetic in origin, attributed to its higher crystallinity (X-ray diffraction crystallinity 27% vs 21% in rr-P3HT), and shorter pÁÁÁp stacking distance (3.64 Å vs 3.78 Å in rr-P3HT), which gives better moisture exclusion from its thiophene backbone.Understanding the degradation mechanisms of polymer organic semiconductor (OSC) devices is an essential step to develop more robust OSC systems and their devices, whether in light-emitting diodes (LEDs), field-effect transistors (FETs), or photovoltaics (PVs). Despite decades of research, detailed spectroscopic studies have seldom been reported, [1,2] primarily because of the considerable challenges to identify chemical transformations that occur on sub-1-mol % of repeat units in the thin films. Yet changes at these levels can be electronically significant. The typical carrier density for LED operation [3] is $1 Â 10 18 cm À3 , which is approximately 0.05 mol % of repeat units, assuming a unit molecular weight of 300 g mol À1 and density of 1.1 g cm À3. For organic FETs, doping at this level can open a parallel source-drain conduction path in the bulk that degrades the shut 'off' and saturation characteristics. [4,5] A simple performance figure-of-merit is the 'on-off' ratio, which for long-channel FETs with a small drain voltage V d and an off-state defined at a gate voltage (V g ) of 0 V is given by i on / i off ¼ mC ox (V g À V th )/(sd), where m is the carrier mobility, C ox is the gate-dielectric capacitance, (V g À V th ) is the effective gate voltage, s is the shunt conductance, and d is the film thickness. For m $ 0.1 cm 2 V À1 s À1 , d $ 30 nm, and typical values for the other parameters, we require s < 10 À8 S cm À1 to give an i on /i off ratio > 10 6

Franck–Condon absorption analysis reveals the existence of several aggregate states in poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) thin films which impact their recrystallization and the attainable field-effect mobility (μFET). Poor solvents (toluene and mixed-xylenes) lock in both disordered and well-ordered states that cannot be annealed away even in the liquid crystalline phase. This reduces μFET and increases mobility activation energies compared with films from good solvents (chlorobenzene and o-dichlorobenzene). Despite its poor solubility characteristics, PBTTT can be ink-jet printed in dilute chlorobenzene, and devices can be operated unencapsulated in ambient, in the dark (&gt;105cycles over several days) with only a moderate mobility loss.

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