During brush growth, only the molecules in the seed monolayer which have been initiated by the Pd catalyst are able to grow polymer chains, though a polymer will not necessarily graft to all initiated molecules in the monolayer.63 An upper limit on the grafting density
of polymer chains in the brush film can be determined by measuring the catalyst initia- tor density. After initiating the seed monolayer, but before polymer growth, the initiated molecules in the monolayer are functionalized with a a ferrocene functional group, which can be detected through cyclic voltammetry (CV).
Using CV measurements, a catalyst initiator density of 1.3±0.2 nm 2 was determined,57 similar to previously reported results.61,63 However, during polymer growth a color change
in the growth solution was observed, with the solution changing from yellow to red and eventually precipitating insoluble P3MT oligomers. This indicates that solution polymeriza- tion outside of the desired SCI-KCTP growth occurred. In order for solution polymerization to occur, some of the catalyst must desorb from the seed monolayer before polymerization begins, or transfer from tethered polymer chains to solution during polymer growth, prema- turely halting growth for some chains. Therefore, the catalyst initiator density is an upper
limit on the density of polymer chains within the brush.
The density of the polymer near the surface of the substrate can be extracted from the Pd initiator density if it is assumed that all initiated molecules grow polymer chains. Under this assumption, the initiator density corresponds to one chain per 1.3 ± 0.2 nm2. The
spacing between monomers along a P3MT chain is 4 ˚A.81 Therefore, near the surface of the
substrate, the monomer density (monomers per unit volume) is estimated to be 3.3 ± 0.5 nm 3.
The density of the P3MT brush films was probed using RBS. The summed spectra of repeated RBS runs for a P3MT brush film is shown in figure 3.1. The thickness and composition of the SiO2 substrate as well as the areal density of the S in the brush were
simulated using SIMNRA. An areal density of 100 ± 4 atoms nm 2 was found for S, and a
thickness of 260 nm and a composition of 1:2 Si:O was found for the SiO2 layer, in agreement
with the substrates specifications. Due to a low number of counts the Br peak was not fit, instead the peak for the expected Br areal density of 4 atoms nm 2 (from CV) is shown. Trace amounts of Cl appear in the RBS spectra, which is a byproduct of polymerization that was not fully removed during post-polymerization cleaning of the film. Trace amounts of Pd are also present.
The average brush film thickness for the sample, 36 ±2 nm, was measured using scratch AFM profilometry (determining brush thickness by AFM is discussed in detail below). A P3MT brush density of 0.36 g/cm3 was determined. For the RBS result shown in Figure
3.1, the monomer density (number of monomers per unit volume) was found to be 2.8± 0.4 nm 3, compared to a monomer density of 5 nm 3 previously reported for the P3HT films.72
The degree of polymerization of P3MT brushes can not be estimated by measuring the ratio of the areal densities of S and Br as has been reported previously for P3HT films. Br atoms are not only present at the terminated end of individual polymer chains in P3MT brushes, but are also present on the uninitiated molecules in the seed monolayer, and so there is not one Br per polymer chain.
Figure 3.1: (a) The summed spectra of two RBS runs on the same 36 nm sample is shown, along with the SIMNRA fit for elemental composition on the brush and substrate. A thick- ness of 260 nm and a composition of 1:2 Si:O was found for the SiO2 layer, in agreement with
the substrates specifications. (b) The RBS spectrum zoomed into the channels correspond- ing to elements found in the brush. An areal density of 100 ± 4 atoms nm 2 was extracted
for S. The Br peak was not fit due to low statistics, instead the expected areal density of 4 atoms nm 2 is shown. Trace amounts of Cl and Pd are present. Cl is a byproduct of P3MT
polymerization, and Pd is present in the catalyst used for polymerization.
GIWAXS measurements on P3MT conjugated polymer brush (CPB) films of 30 and 120 nm thickness detected polycrystalline di↵raction arcs at reciprocal space vectors q = 1.2
and 1.8 ˚A 1, while the measurement of thinner films yielded negligible di↵raction intensities
(Figure 3.2). The two arcs can be assigned to the (020) and (110) reflections respectively, based on a crystal structure with staggered sheets (⇡-⇡ and lamellar lattice spacing of 3.5 and 7.7 ˚A, respectively).77 The ⇡-⇡ and lamellar lattice spacings extracted from GIWAXS
agree with previously reported values.77 The two lattice vectors are orthogonal to the chain
axis and exhibit a nearly isotropic distribution with a small amount of horizontal texture (Figure 3.3).
The lattice spacing of thiophene along the chain axis is 4 ˚A.81 Together with the⇡-⇡ and lamellar lattice spacing a monomer unit cell volume can be calculated for crystalline P3MT within the brush. The monomer unit cell has a volume of 0.11 nm3, and correspondingly,
Figure 3.2: GIWAXS images of 120, 30, 15, and 8 nm thick P3MT CPB films grown on ITO. The black region is the “missing wedge” that arises due to kinematic constraints in the GIWAXS geometry. White bars are missing data due to the structure of the detector. Features at 1.2 and 1.8 ˚A 1 are attributed to di↵raction from the respective (110) and
(020) reflections of P3MT. Other features are attributed to di↵raction from ITO, e.g. (222) reflection at 2.1 ˚A 1.77 Figure S4 in Ref [54], reproduced with permission.
Figure 3.3: (a) Pole figure (sin(!) weighted integral) for the (110) di↵raction feature of P3MT CPB films at 1.2 ˚A 1. Gaps are due to detector structure. Di↵raction intensities are
detected for films 30 nm thick. Dashed lines indicate the expected behaviors of isotropic systems. The 33 and 100 nm thick films exhibit light textures for orientation⇠30 from the surface normal. (b) Pole figure (sin(!) weighted integral) for the (020) di↵raction feature of P3MT CPB films at 1.8 ˚A 1. Di↵raction intensities are detected for films 30 nm thick.
Dashed lines indicate the expected behaviors of isotropic systems. The 33 and 100 nm thick films exhibit textures for orientation ⇠ 50 from the surface normal. Figures S5 and S6 in Ref [54], reproduced with permission.