Supporting Information
R/RF
pnd10-n 1M NaCl 40deg PEI/(PSS/PAH)n-1/PSS/(PAH/PSSd)10-n 10
5
10
4
10
3
10
2
10
1
10
0
p7d3(b) p5d5(a) p3d7(b)
-1
10 0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
-1
Qz [Å ] pnd10-n 1M NaCl 40deg PEI/(PSS/PAH)n-1/PSS/(PAH/PSSd)10-n
4.5
p7d3(b) p5d5(a) p3d7(b)
4.0 -2
3.0
-6
SLD [10 Å ]
3.5
2.5 2.0 1.5 1.0 0.5 0.0 -100
0
100
200
300
400
500
-1
z [Å ] Fig. S1: Normalized reflectivity curves of PAH/PSS films consisting of 10 polyelectrolyte bilayers with corresponding scattering length density profiles. Depicted are the p3d7 (dark red), p5d5 (green) and p7d3 (blue) architecture, all films are prepared at 40°C and 1 M NaCl.
1
R/RF
pnd18-n 1M NaCl 40deg PEI/(PSS/PAH)n-1/PSS/(PAH/PSSd)18-n 10
7
10
5
10
3
10
p15d3 (b) p13d5 (a) p11d7 (a) p9d9 (a) p7d11 (c) p5d13 (a) p3d15 (b)
1
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
-1
Qz [Å ]
4.0
pnd18-n 1M NaCl 40deg PEI/(PSS/PAH)n-1/PSS/(PAH/PSSd)18-n
-6
-2
SLD [10 Å ]
3.5
p15d3 (b) p13d5 (a) p11d7 (a) p9d9 (a) p7d11 (c) p5d13 (a) p3d15 (b)
3.0 2.5 2.0 1.5 1.0 0.5 0.0 -200
0
200
400
600
800
1000
1200
-1
z [Å ] Fig. S2: Normalized reflectivity curves of PAH/PSS films consisting of 18 polyelectrolyte bilayers with corresponding scattering length density profiles. All films are prepared at 40°C and 1 M NaCl.
2
R/RF
10
5
10
4
10
3
10
2
10
1
10
0
10
dnp14-n 0.1M NaCl 20deg PEI/(PSSd/PDADMAC)n-1/PSSd/(PDADMAC/PSS)14-n
d11p3 d9p5 d7p7 d5p9 d2p12
-1
0.00
0.02
0.04
0.06
0.08
0.10
0.12
-1
Qz [Å ]
3.5
pnd14-n 0.1M NaCl 20deg PEI/(PSSd/PDADMAC)n-1/PSSd/(PDADMAC/PSS)14-n
-6
-2
SLD [10 Å ]
3.0
d11p3 d9p5 d7p7 d5p9 d2p12
2.5 2.0 1.5 1.0 0.5 0.0 -200
0
200
400
600
800
-1
z [Å ] Fig. S3: Normalized reflectivity curves of PDADMAC/PSS films consisting of 14 polyelectrolyte bilayers with corresponding scattering length density profiles. Depicted are the d2d12 (dark red), d5p9 (green), d7p7 (blue), d9p5 (black) and d11p3 (violet) architecture, all films are prepared at 20°C and 0.1 M NaCl.
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Parameter Tables 210kDa PDADMAC: @ 0.1M NaCl, 20°C
p3d11 DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint σair
prot. 64.46 21.48 1.780 -3.2 32.23
deut. 521.50 47.41 2.633 1.6 15.33
p5d9 prot. 102.4 20.48 1.361 -1 51.20
deut. 464.6 51.62 2.669 1.5 14.03
p7d7 prot. 184.2 26.31 1.266 -0.3 52.69
deut. 377.9 53.99 2.666 1.5 14.93
p9d5 prot. 270.7 30.08 1.22 0 47.95
deut. 283.8 56.76 2.633 1.6 14.02
p11d3 prot. deut. 364.5 177.7 33.14 59.23 1.164 2.557 0.5 2 40.74 12.99
p12d2 DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint σair
prot. 407.7 33.97 1.167 0.5 34.56
deut. 118.9 59.45 2.594 1.9 11.89
Table S1: Parameter tables for the Fits depicted in Figure 1, bottom. The free parameters are the thickness for the protonated and deuterated block (DPEM), the corresponding scattering length densities SLD, and the internal roughness σint and the film/air roughness σair. The water content and the average bilayer thickness in the respective blocks are derived quantities. PAH/PSS @ 1M NaCl, 40°C 14 BL DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint σair
p5d9 prot. 180.7 36.14 1.63 -0.3 19.07
deut. 488.8 54.31 3.32 1.8 8.82
p7d7 prot. 287.9 41.13 1.69 -0.5 16.4
deut. 373.4 53.34 3.38 1.6 8.07
p9d5 prot. 392.5 43.57 1.60 -0.2 13.16
deut. 256.7 51.34 3.36 1.7 9.47
p11d3 prot. deut. 495.3 153.7 45.02 51.23 1.50 3.41 0.3 1.5 12.48 8.78
Table S2: Parameter tables for the Fits depicted in Figure 1, center. The symbols are explained in the Caption to Table 1. PAH/PSS @ 1M NaCl, 40°C 10BL p3d7 prot. deut. DPEM [Ǻ] 75.4 333.6 DBL [Ǻ] 25.12 47.66 SLD [10-6Ǻ-2] 1.31 3.27 nWater 1.4 2.0 σint σair 13.81 8.21
p 5d 5 prot. 161.3 32.26 1.37 1.0 18.02
deut. 246.3 49.26 3.43 1.5 7.27
p7d3 prot. 262.0 37.43 1.27 1.6 14.49
deut. 148.3 49.43 3.52 1.2 8.30
Table S3: Parameter tables for the Fits depicted in Figure S1. The symbols are explained in the Caption to Table S1.
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PAH/PSS @ 1M NaCl, 40°C
p3d15
18 BL prot. 102.8 34.26 1.70 -0.6 25.62
DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint σair
p5d13 deut. 774.7 51.64 3.37 1.6 8.07
prot. 167.6 33.52 1.10 2.8 23.44
p7d11
σint
prot. 266.3 38.04 1.43 0.7 6.53
DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater 20.49
p9d9 deut. 597.8 54.34 3.16 2.3 20.49
prot. 266.3 38.04 1.43 0.7 6.53
p11d7
18 BL prot. 505.5 45.95 1.62 -0.2 13.56
DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint 14.72
deut. 688.8 52.98 3.31 1.8 9.35 deut. 597.8 54.34 3.16 2.3 9.22
p13d5 prot. 267.0 46.73 1.48 0.4 13.56
prot. 267.0 46.73 1.48 0.4 13.56
deut. 607.5 53.40 3.27 1.9 8.58
p15d3
18 BL DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint 13.97
prot. 740 49.33 1.69 -0.5 13.97
prot. 740 49.33 1.69 -0.5
Table S4: Parameter tables for the Fits depicted in Figure S2. The symbols are explained in the Caption to Table S1. 210kDa PDADMAC: @ 0.1M NaCl, 20°C 14BL DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint σair
d5p9 deut. 96.19 19.23 2.569 1.5 48.95
prot. 454.8 50.53 1.047 1.5 15.0
d7p7 deut. 171.3 24.47 2.639 1.6 59.18
prot. 378.1 54.01 1.052 1.9 7.92
d9p7 deut. 294.6 32.77 2.633 1.6 57.36
prot. 385.9 55.08 1.075 1.2 10.72
d9p5 deut. 277.9 30.81 2.628 1.8 41.49
prot. 277.3 55.58 1.016 1.7 6.71
d11p3 deut. 390.8 35.52 2.634 1.6 37.23
prot. 180.7 60.23 0.958 3.8 6.72
Table S5: Parameter tables for the Fits depicted in Figure S3. The symbols are explained in the Caption to Table S1.
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PAH/PSS @ 1 M NaCl, 40°C 19BL DPEM [Ǻ] DBL [Ǻ] SLD [10-6Ǻ-2] nWater σint σair
p3(d1p3)4 p3 127 42.33 1.26 1.7 16.3
d1 p3 49.97 149.91 49.97 49.97 3.33 1.40 1.8 0.9 17.3
Table S6: Parameter assignment for the fit to the superstructure with a constant internal roughness, cf. Fig. 4. Another assumption is that each bilayer has the same thickness except the precursor zone. Free parameters are given in the first, third and last row.
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