Development and Analysis of Self-Assembled Structures of Branched Colloidal Nanocrystals

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Binary Self-Assem bly of Branched Colloid al N anocrystals

𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

𝐿/𝐷 = 4.0 𝐿/𝐷 = 7.0 𝑅1= 12.5 𝑛𝑚 𝑅2= 7.1 𝑛𝑚

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𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

𝐿 𝐷 𝑙𝑝 𝑅 𝑳/𝑫 𝑳 (nm) 𝑫 (nm) 𝒍𝒑 (nm) 4.0 48 ± 5 12.0 ± 1.4 17 ± 2 7.0 74 ± 3 10.4 ± 1.5 30 ± 2 𝑆𝐶𝑟 𝑹 (nm) 𝑺𝑪𝒓 𝐿/𝐷 = 4.0 𝐿/𝐷 = 7.0 𝑺𝑪𝒓 𝑹𝟏 12.5 ± 1.1 0.52 0.32 𝑹𝟐 7.1 ± 1.0 0.29 0.19

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𝑅

1

= 12.5 ±

1.1 𝑛𝑚

𝑅

2

= 7.1 ± 1.0 𝑛𝑚

𝑆𝐶

_𝑟

2𝑅

𝐿

𝑆𝐶

_𝑟

=

2𝑅_𝐿

𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

𝐿/𝐷 = 4.0

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𝐿/𝐷 = 4.0 𝐿/𝐷 = 7.0

𝐿/𝐷 = 7.0

𝐿/𝐷 = 4.0

𝑅

1

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𝐿/𝐷 = 4.0

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𝐿/𝐷 = 4 𝐿/𝐷 = 7 𝐿/𝐷 = 4

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𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

𝑅

1

𝑅

2 𝐿/𝐷 = 7.0 𝑅1

𝑅

1

𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

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𝐿/𝐷 = 7.0

𝑅

1

𝐿/𝐷 = 7.0 𝑅1

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𝐿/𝐷 = 4.0

𝑅

₁ 𝐿/𝐷 = 4.0 𝐿/𝐷 = 7.0

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𝑅

₂

𝑅

2 𝐿/𝐷 = 4.0 𝐿/𝐷 = 7.0

𝐿/𝐷 = 4.0

𝐿/𝐷 = 7.0

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Binary Self-Assem bly of Branched Colloid al N anocrystals δ δ L (nm) D (nm) lp (nm) L/D Edge (nm) Octapods 80 ± 5 13.8 ± 1.3 34 ± 3 5.8 ± 0.6 Cubes 31 ± 2

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

•

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ζ

ζ ζ

MPA ligand DOP ligand MPS ligand ζ-potential -33.8 ± 0.4 mV +7.1 ± 0.4 mV -13.5 ± 1.3 mV

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)

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ζ

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𝐿/𝐷 = 4.0

𝑅

₁

= 12.5 𝑛𝑚

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𝐿/𝐷 = 7.0

𝑅

₂

= 7.1 𝑛𝑚

δ

ζ

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Reinforced N anocom p osites: Self-Assem bly of Branched Colloid al N anocrystals in Polym er Film s

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μ

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Synthesis and Self-Assem bly of N ew Anisotrop ic Colloid al N anocrystals - Ongoing Project

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𝑙 = 31 ± 5 𝑛𝑚

𝑤 = 5.5 ± 0.9 𝑛𝑚

𝑡 = 1.8 ± 0.2 𝑛𝑚

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𝑙

[100]

= 31 ± 5 𝑛𝑚

𝑡

[001]

= 1.8 ± 0.2 𝑛𝑚

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PL maximum

position 658 nm 661 nm 656 nm

FWHM 33 nm 39 nm 46 nm

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Ap p end ix A:

Details abou t the Cu 2-xSe Seed s Am ou nt Em p loyed in the Syntheses of Octap od s Amount of seeds (nmol) lp (nm) L (nm) D (nm) L/D Representative TEM images (s.b. 20 nm) 0.05 28 ± 3 69 ± 5 12.3 ± 1.6 5.7 ± 0.5 0.1 41 ± 2 95 ± 5 14.5 ± 1.4 6.6 ± 0.5 L/D = 6.0 0.2 37 ± 3 86 ± 6 14 ± 2 6.3 ± 0.9 0.2 31 ± 2 74 ± 4 13.0 ± 1.4 5.7 ± 0.6 0.3 30 ± 2 73 ± 5 13 ± 2 5.6 ± 0.7 L/D = 5.0 0.3 30 ± 2 73 ± 5 15 ± 2 4.9 ± 0.6 0.4 28 ± 2 69 ± 4 13 ± 2 5.3 ± 0.8 0.9 21 ± 2 55 ± 4 13.3 ± 1.5 4.2 ± 0.4 L/D = 3.5 1.1 16.6 ± 1.6 46 ± 3 13.4 ± 1.4 3.5 ± 0.3 L/D = 3.0 1.8 13.0 ± 1.5 39 ± 3 12.8 ± 1.5 3.0 ± 0.4 2.7 Edge 22 ± 2 nm

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Ap p end ix B:

Collection of Snap shots from the Monte Carlo Sim u lations of the Self-Assem bly of Octap od s into Planar Su p erlattices

L/D = 3.0 𝜀S

𝜀T

kBT

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L/D = 3.0 𝜀S 𝜀T kBT p NkBTL−3 0.01NkBTL−3

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Ap p end ix B:

L/D = 4.0 𝜀S

𝜀T

kBT

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L/D = 4.0 𝜀S 𝜀T kBT p NkBTL−3 0.01NkBTL−3 𝜀T= −2 kBT 𝜀T= −1 kBT

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Ap p end ix B:

L/D = 5.0 𝜀S 𝜀T kBT 𝜀T= −1 𝑜𝑟 − 2 𝑘𝐵𝑇 𝜀s≥ 3 𝑘𝐵𝑇 𝜀T= −1 𝑜𝑟 0 𝑘𝐵𝑇 𝜀s≤ −3 𝑘𝐵𝑇

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L/D = 5.0 𝜀S 𝜀T kBT p NkBTL−3 0.01 NkBTL−3 0.06 NkBTL−3 𝜀T= −1 kBT

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Ap p end ix B:

L/D = 6.0 𝜀S 𝜀T kBT L/D = 5.0 𝜀T= −1 𝑘𝐵𝑇 𝜀s≥ 4 𝑘𝐵𝑇 0 𝑘𝐵𝑇 ≤ 𝜀T≤ 2 𝑘𝐵𝑇 𝜀s= −2 𝑘𝐵𝑇 𝜀T≥ 0 𝑘𝐵𝑇 𝜀s≤ −2 𝑘𝐵𝑇

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L/D = 6.0 𝜀S 𝜀T kBT p NkBTL−3 0.01 NkBTL−3 0.03 NkBTL−3

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Ap p end ix B:

L/D = 7.0 𝜀S 𝜀T kBT 𝜀T≤ −1 𝑘𝐵𝑇 𝜀s≥ 0 𝑘𝐵𝑇 𝜀T≥ 1 𝑘𝐵𝑇 𝜀s= −1 𝑜𝑟 − 2 𝑘𝐵𝑇 𝜀T≥ 0 𝑘𝐵𝑇 𝜀s≤ −1 𝑘𝐵𝑇

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L/D = 7.0 𝜀S 𝜀T kBT p NkBTL−3 0.01 NkBTL−3 0.022 NkBTL−3 𝜀T= −1 kBT 0.011 NkBTL−3≤ 𝑝 ≤ 0.022 NkBTL−3

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Ap p end ix B:

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Ap p end ix C: List of Chem icals

≥

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Ap p end ix D:

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fi

ff

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Ap p end ix D:

Characterization Techniqu es

β



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Ap p end ix D:

Characterization Techniqu es

ζ

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Ap p end ix D:

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List of Scientific Contribu tion

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