Synthesis · Charge. transport, conductivity and Seebeck coefficient in pristine and TCNQ loaded preferentially grown metal-organic framework films

6 structured synthesis routes

Completeness describes how fully the route could be reconstructed from the main article and supporting information.

Partial recipeSource: Main

Route 1: Other

article pages 2 and 4 · Introduction and Figure 2 discussion · Figure 2

Metal precursors1 mmol Cu(OAc)2 metal-containing solution

Linker precursors0.1 mmol BTC linker solution

SolventsNot fully specified for MOF growth in this article; ethanol rinse used in standard procedure but omitted for random films

AdditivesSAM layer on thin Au film for functionalized interface

Atmospherenot specified

Substrate orientationFunctionalized Au/SAM on silicon or quartz; preferential (001) orientation

Work-upStandard spray process described in earlier references; full workup not repeated here

Scalability contextLPE spray cycle count tunes thickness; later discussion notes s-ALD as future scalable route, not used for these HKUST-1 samples.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	1 mmol	article pages 2 and 4 · Introduction and Figure 2 discussion · Figure 2
Linker	BTC	0.1 mmol	article pages 2 and 4 · Introduction and Figure 2 discussion · Figure 2
Additive	self-assembled monolayer (SAM) on Au	Not specified	article pages 2 and 4 · Introduction and Figure 2 discussion · Figure 2

Partial recipeSource: Main

Route 2: Other

article pages 2 and 8 · Introduction and 1.2 Thin-film electrical conductometry · Figure 4

Metal precursors1 mmol Cu(OAc)2 metal-containing solution

Linker precursors0.1 mmol BTC linker solution

SolventsNot fully specified; pure ethanol rinse omitted to obtain random polycrystalline non-oriented films

Atmospherenot specified

Substrate orientationUntreated/non-functionalized borosilicate glass; random polycrystalline orientation

Work-upRinsing with pure ethanol omitted in modified standard spray procedure

Scalability context10 cycles gave approximately 40 nm and 40 cycles gave approximately 130 nm on borosilicate glass.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	1 mmol	article pages 2 and 8 · Introduction and 1.2 Thin-film electrical conductometry · Figure 4
Linker	BTC	0.1 mmol	article pages 2 and 8 · Introduction and 1.2 Thin-film electrical conductometry · Figure 4
Solvent	pure ethanol	rinse omitted for random polycrystalline film growth	article pages 2 and 8 · Introduction and 1.2 Thin-film electrical conductometry · Figure 4

Partial recipeSource: Main

Route 3: Other

article page 8 · 1.2 Thin-film electrical conductometry · Figure 5

Metal precursors1 mmol Cu(OAc)2 metal-containing solution

Linker precursors0.1 mmol BTC linker solution

Solventsnot fully specified

Additiveshydroxyl-terminated native oxide surface

Atmospherenot specified

Substrate orientationHydroxyl-terminated native oxide covered Si substrate

Work-upnot fully specified

Scalability contextSurface hydroxyl termination improves wetting/chemisorption and yields compact films.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	1 mmol	article page 8 · 1.2 Thin-film electrical conductometry · Figure 5
Linker	BTC	0.1 mmol	article page 8 · 1.2 Thin-film electrical conductometry · Figure 5
Additive	hydroxyl-terminated SiO2/Si substrate	Not specified	article page 8 · 1.2 Thin-film electrical conductometry · Figure 5

Partial recipeSource: Main

Route 4: Other

article page 3 · Figure 1 discussion · Figure 1

Metal precursorsHKUST-1 SURMOF precursor film

Linker precursorsTCNQ guest molecule

Solventsethanol

Atmospherenot specified

Temperature60 activation; room temperature loading

Time4 activation; 72 loading

Substrate orientationRandom polycrystalline HKUST-1 on borosilicate glass

Work-upRinsed using pure ethanol to remove surface-adsorbed TCNQ molecules

ActivationAs-synthesised MOF thin film annealed at 60 o C for 4 h before loading

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TCNQ	2 mM	article page 3 · Figure 1 discussion · Figure 1
Solvent	ethanol	Not specified	article page 3 · Figure 1 discussion · Figure 1

Partial recipeSource: Main

Route 5: Other

article pages 3 and 8 · Figure 1 discussion and 1.2 Thin-film electrical conductometry · Figures 1 and 11

Metal precursorsCompact HKUST-1 SURMOF precursor film on hydroxylated SiO2/Si

Linker precursorsTCNQ guest molecule

Solventsethanol

Atmospherenot specified

Temperature60 activation; room temperature loading

Time4 activation; 72 loading

Substrate orientationRandom polycrystalline compact HKUST-1 on hydroxyl-terminated SiO2/Si

Work-upRinsed using pure ethanol to remove surface-adsorbed TCNQ molecules

ActivationAs-synthesised MOF thin film annealed at 60 o C for 4 h before loading

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TCNQ	2 mM	article pages 3 and 8 · Figure 1 discussion and 1.2 Thin-film electrical conductometry · Figures 1 and 11
Solvent	ethanol	Not specified	article pages 3 and 8 · Figure 1 discussion and 1.2 Thin-film electrical conductometry · Figures 1 and 11

Partial recipeSource: Main

Route 6: Other

article page 3 · Figure 1 discussion · Figure 1

Metal precursorsPreferentially oriented HKUST-1 SURMOF precursor film

Linker precursorsTCNQ guest molecule

Solventsethanol

Atmospherenot specified

Temperature60 activation; room temperature loading

Time4 activation; 72 loading

Substrate orientationPreferentially (001)-oriented HKUST-1 on SAM-functionalized Au/quartz

Work-upRinsed using pure ethanol to remove surface-adsorbed TCNQ molecules

ActivationAs-synthesised MOF thin film annealed at 60 o C for 4 h before loading

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	TCNQ	2 mM	article page 3 · Figure 1 discussion · Figure 1
Solvent	ethanol	Not specified	article page 3 · Figure 1 discussion · Figure 1