Supporting Information

Transcription

1 Supporting Information Luminescent Organic Semiconducting Langmuir Monolayers Elena V. Agina a,b, Artur A. Mannanov b,c, Alexey S. Sizov a,b, Olga Vechter d, Oleg V. Borshchev a,b, Artem V. Bakirov a, e, Maxim A. Shcherbina e,f, Sergei N. Chvalun a,e, Vladislav G. Konstantinov b, Vladimir V. Bruevich b, Oleg V. Kozlov b,c, Maxim S. Pshenichnikov c, Dmitry Yu. Paraschuk b *, and Sergei A. Ponomarenko a,b * a Institute of Synthetic Polymeric Materials of Russian Academy of Sciences, Profsoyuznaya st. 70, Moscow, Russia; b Faculty of Physics & International Laser Center, Lomonosov Moscow State University, Moscow, Russia; c Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh, Groningen AG, The Netherlands; d Department of Organic Chemistry III / Macromolecular Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany; e National Research Centre "Kurchatov Institute", Akademika Kurchatova pl. 1, Moscow, , Russia; f Moscow Institute of Physics and Technology, 4 Institutsky line, Dolgoprudny, Moscow region, Russian Federation Corresponding Authors: Sergei A. Ponomarenko, ponomarenko@ispm.ru Dmitry Paraschuk, paraschuk@gmail.com S-1

2 CONTENTS: Table S1. List of Langmuir films studied....s-3 Figure S1. AFM data of the samples investigated: topography, cross-sections and height distributions...s-3 S-4 Figure S2. In-plane grazing incidence X-ray diffraction images of LB (a) and LS (b) films S-5 Figure S3. X-Ray reflectometry curves of LB (sample 1, black curve) and LS (sample 2, red curve) films.....s-5 Figure S4. Absorption (green), and PL (blue, excitation at 3.3 ev) spectra..s-6 Table S2. Fitting parameters for the bi-exponential function [H1 exp(-t/ τ 1) + H2 exp(-t/ τ 2)] of the PL kinetics in Figure 1b... S-6 Figure S5. PL data on annealed LS films of D2-Und-PTTP-TMS prepared on bare (black, LS) and ODMS-treated (orange, LS ODMS) silicon substrates....s-7 Figure S6. Statistics of measured PL spectra for LS (a) and spin-cast (b) samples..s-8 Figure S7. Spin-cast sample depth profile of a scratch on the surface...s-8 Figure S8. DSC data of D2-Und-PTTP-TMS....S-9 S-2

3 Table S1. List of Langmuir films studied. N Technique Transfer pressure, mn/m Conditions 1 LB a g/l 2 LS b g/l 3 LB g/l (SVA c ) 4 LS g/l (SVA) 5 LS 40 ODMS d 0.5 g/l 6 LB g/l Notes: a LB Langmuir-Blodgett transfer, b LS Langmuir-Schaefer transfer, c SVA solvent vapor annealing, d ODMS transferred on the surface treated with octadecyldimethyl chlorosilane. 1 2 S-3

4 Figure S1. AFM data of the samples investigated: topography, cross-sections and height distributions. S-4

5 Figure S2. In-plane grazing incidence X-ray diffraction images of LB (sample 1) (a) and LS (sample 2) (b) films; corresponding Q XY scans are shown in (c) and (d) plots. Clear Bragg spot is observed at Q XY = 1.32 Å -1 for the LS film, indicating an interplanar stacking distance of 4.76 Å. Figure S3. X-Ray reflectometry curves of LB (sample 1, black curve) and LS (sample 2, red curve) films. The line is a fit to curve 2. S-5

6 PL intensity (arb. un.) THF solution 1.0 QY = 21% 0.5 PL spectrum Absorption Molar extinction coefficient (10 5 *L*mol -1 *cm -1 ) Figure S4. Absorption (green), and PL (blue, excitation at 3.3 ev) spectra of D2-Und-PTTP-TMS. The PL quantum yield was 21±3%. Table S2. Fitting parameters for the bi-exponential function [H 1 exp(-t/ τ 1) + H 2 exp(-t/ τ 2)] of the PL kinetics in Figure 1b. The sum of H 1 and H 2 is normalized to unity. The deviation margins are derived as uncertainty of the mean calculated over all individual transients. D2-Und-PTTP- TMS samples H 1 τ 1, ps H 2 τ 2, ps Diluted solution ± 10 Spin-cast sample 0.90 ± ± ± ± 20 LS film 0.80 ± ± ± ± 20 S-6

7 a) PL intensity (arb. un.) LS ODMS (/1.15) LS film c) 2.5 b) Normalized PL intensity (arb. un.) LS ODMS LS film τ 1 = 50±10 ps (0.8) τ 2 = 420±20 ps (0.2) LS ODMS τ 1 = 55±10 ps (0.8) τ 2 = 450±20 ps (0.2) Delay Time (ps) 2.4 LS film Delay Time (ps) Figure S5. PL data on annealed LS films of D2-Und-PTTP-TMS prepared on bare (black, LS) and ODMS-treated (orange, LS ODMS) silicon substrates. PL spectra (a), time-resolved kinetics (b) and spectral diffusions (c). In (a), scaling between the spectra of the LS film and the LS ODMS film is preserved. Thick lines in (a) indicate mean values resulted from averaging of several measurements; thin lines border the region within one standard deviation from the mean. The PL transients were obtained by integrating the PL time-resolved maps in the ev spectral region, and normalized to their maxima. The solid lines in (b) are biexponential fits convoluted with an apparatus response ~7 ps; the corresponding decay times are shown next to the transients. In (c), the time-dependent mean energy of the PL spectrum is shown together with monoexponential fits E = E 0 + E exp(-t/τ), where E 0 value was fixed (for LS film: E 0 = 2.44eV, E = 90±20 mev, τ = 140±100 ps; for LS ODMS film: E 0 = 2.45eV, E = 80±20 mev, τ = 120±50 ps). S-7

8 a) PL intensity (arb. un.) LS film statistics b) PL intensity (arb. un.) 1.0 Spin-cast statistics Figure S6. Statistics of measured PL spectra for LS (a) and spin-cast (b) samples. The PL spectra were measured from three different spots of each sample. (a) (b) Avr. height = 200±50 nm Height (nm) X-axis (µm) Figure S7. Optical microphotograph in cross-polarizers (a) and spin-cast sample depth profile (b) of a scratch on the surface (e.g. the scratch is located between 0.4 and 1.2 µm). S-8

9 Figure S8. DSC data of D2-Und-PTTP-TMS (1 st heating, cooling and 2 nd heating at 20 C/min). S-9