Synthesis · Ultrafast in Situ Synthesis of Large-Area Conductive Metal-Organic Frameworks on Substrates for Flexible Chemiresistive Sensing

3 structured synthesis routes

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

Complete recipeSource: Main

Route 1: Liquid Liquid Interface

p002; article page 57236 · 2.4 Sensor Fabrication

Metal precursorsCu(NO3)2 aqueous solution (1 mM)

Linker precursorsBHT/chlorobenzene solution (0.1 mM in methods)

SolventsWater and chlorobenzene during synthesis; chlorobenzene/ethanol/water/acetone rinses

AdditivesCr/Au interdigitated electrodes pre-deposited on Si/SiO2

AtmosphereAmbient during growth; N2 blow-drying for substrate preparation; vacuum drying after growth

Temperature60 drying; Si/SiO2 cleaning/drying steps at 80-100 deg C

Time0.0333 h reaction (2 min); 12 h drying

Substrate orientationSi/SiO2 wafer on spin-coater vacuum chuck with interdigitated electrodes facing up

Oxidant / reductantNone reported

Work-upSpin-off and sequential 10 s rinses as in general SCIS route

ActivationVacuum oven at 60 deg C for 12 h

Scalability contextSensor prepared in one step by in situ growth on pre-deposited Au electrodes; 1.7 x 1.7 cm Si/SiO2 wafer geometry reported.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2 aqueous solution	100 uL in general SCIS method · 1 mM	p002; article page 57236 · 2.4 Sensor Fabrication
Linker	BHT in chlorobenzene	covered aqueous layer · 0.1 mM	p002; article page 57236 · 2.4 Sensor Fabrication
Other	Cr adhesion layer	5 nm evaporated	p002; article page 57236 · 2.4 Sensor Fabrication
Other	Au electrodes	100 nm evaporated	p002; article page 57236 · 2.4 Sensor Fabrication

Partial recipeSource: Both

Route 2: Liquid Liquid Interface

p006; article page 57240 · 3.4 Mechanical Stability · Figure 4

Metal precursorsCu(NO3)2 aqueous solution (1 mM)

Linker precursorsBHT/chlorobenzene solution (0.1 mM in methods)

SolventsWater, chlorobenzene, ethanol and acetone

AdditivesPre-deposited Au interdigitated electrodes on PET substrate

AtmosphereAmbient growth; vacuum drying

Temperature60 drying

TimeApprox. 0.0333 h reaction for 10 nm film inferred from 2 min optimal film; 12 h drying

Substrate orientationPET/Au electrode substrate on vacuum chuck

Oxidant / reductantNone reported

Work-upPET substrate ozone-cleaned at 100 W for 1 min; SCIS film rinsed and dried as above

ActivationVacuum oven at 60 deg C for 12 h

Scalability contextDemonstrates flexible large-area device compatibility and 1000 bending cycles at 3 mm radius.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2 aqueous solution	100 uL in general SCIS method · 1 mM	p006; article page 57240 · 3.4 Mechanical Stability · Figure 4
Linker	BHT in chlorobenzene	covered aqueous layer · 0.1 mM	p006; article page 57240 · 3.4 Mechanical Stability · Figure 4
Other	PET substrate with Au interdigitated electrodes	Not specified	p006; article page 57240 · 3.4 Mechanical Stability · Figure 4

Complete recipeSource: Both

Route 3: Liquid Liquid Interface

p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1

Metal precursors100 uL Cu(NO3)2 aqueous solution (1 mM)

Linker precursorsBHT in chlorobenzene, 0.1 mM in the methods text; Figure 1 sketch labels 0.2 mM BHT solution

SolventsWater; chlorobenzene; rinse sequence chlorobenzene, ethanol, water and acetone

AdditivesNone reported

AtmosphereAmbient clean-room/spin-coating conditions; final drying under vacuum

Temperature60 for final drying; substrate treatments at 80-100 deg C as specified

TimeReaction from 5 s to 16 min; final drying 12 h

Substrate orientationHydroxyl-rich substrate placed horizontally on a vacuum chuck/spin coater

Oxidant / reductantNone added; Cu2+ coordinates rapidly with BHT at the aqueous-organic interface

Work-upSpin off solution (500 rpm 10 s then 1500 rpm 45 s); immerse sequentially in chlorobenzene, ethanol, water and acetone for 10 s each to remove unreacted ligand and Cu2+ ions

ActivationVacuum oven drying at 60 deg C for 12 h

Scalability contextCentimetre-sized films on glass, Si, Si/SiO2 and PET/Au substrates; film thickness tunable over 5-35 nm by reaction time.

Show 7 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(NO3)2 aqueous solution	100 uL · 1 mM	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1
Linker	BHT (benzenehexathiol) in chlorobenzene	dropped until organic layer completely covered aqueous layer · 0.1 mM (methods); 0.2 mM in Figure 1 sketch	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1
Solvent	DI water	aqueous metal solution and rinse	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1
Solvent	chlorobenzene	organic linker solution and 10 s rinse	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1
Solvent	ethanol	10 s rinse	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1
Solvent	acetone	10 s rinse	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1
Acid	piranha solution H2SO4 (95-98%)/H2O2 (30%) = 2:1	substrate treatment at 80 deg C for 2 h	p002; article page 57236 · 2.2 In Situ Synthesis of Cu-BHT · Figure 1