Synthesis · Metal-organic framework nanosheets for enhanced performance of organic photovoltaic cells

7 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Solvothermal

3 · 2.2 Synthesis of bulk Zn2(Zn-TCPP)(DMF)

Metal precursorsZn(NO3)2.3H2O

Linker precursorsH2TCPP / TCPP

SolventsDMF and ethanol (3:1 v/v; 1.5 mL DMF + 0.5 mL ethanol)

Additivesnone reported

Atmosphereborosilicate vial with Teflon-faced rubber-lined cap; no gas atmosphere specified

Temperature80

Time24

Oxidant / reductantnone reported

Work-upcentrifuged at 4500 rpm for 10 min; repeatedly washed with ethanol until clear supernatant

Activationnone explicitly reported beyond washing/drying; elemental-analysis model includes H2O/DMF

Scalability contextSI reports 87% yield; main describes a simple solvothermal synthesis adapted from Choi et al.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Zn(NO3)2.3H2O	8.9 mg, 0.09 mmol	3 · 2.2 Synthesis of bulk Zn2(Zn-TCPP)(DMF)
Linker	H2TCPP	7.9 mg, 0.03 mmol	3 · 2.2 Synthesis of bulk Zn2(Zn-TCPP)(DMF)
Solvent	DMF	1.5 mL	3 · 2.2 Synthesis of bulk Zn2(Zn-TCPP)(DMF)
Solvent	ethanol	0.5 mL	3 · 2.2 Synthesis of bulk Zn2(Zn-TCPP)(DMF)

Partial recipeSource: SI

Route 2: Drop Cast

8-10 · 5.2-5.3 · Fig. S8-S9

Metal precursorspreformed Zn2(ZnTCPP) MONs

Linker precursorspreformed Zn2(ZnTCPP) MONs

Solventsethanol for UV-vis film; acetonitrile electrolyte for CV film preparation context

Additivestetrabutylammonium perchlorate electrolyte for CV measurement

Atmosphereargon during CV measurement; ambient drying for UV-vis film not otherwise specified

Temperatureroom temperature

Timenot reported

Substrate orientationquartz for UV-vis; glassy carbon for CV

Oxidant / reductantnone reported

Work-updropcast suspension and evaporate solvent

Activationsolvent evaporation/drying

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	MON suspension	not reported for CV; 5 mg/mL for UV-vis film · 5 mg/mL for UV-vis film	8-10 · 5.2-5.3 · Fig. S8-S9
Solvent	ethanol	not reported	8-10 · 5.2-5.3 · Fig. S8-S9
Electrolyte	tetrabutylammonium perchlorate	not reported · not reported	8-10 · 5.2-5.3 · Fig. S8-S9

Complete recipeSource: SI

Route 3: Other

16 · 7.3 Active layer deposition

Metal precursorsnone

Linker precursorsnone

Solventschlorobenzene

AdditivesP3HT, PCBM, PEDOT:PSS, BCP, Ag electrode, epoxy encapsulant

Atmospherenitrogen glovebox for active-layer spin coating; vacuum <2E-6 mbar for BCP/Ag evaporation

Temperaturesame method as ternary devices; PEDOT:PSS annealed at 110 deg C

Timesame method as ternary devices; solvent vapour anneal 5 min where used

Substrate orientationpre-patterned ITO glass with PEDOT:PSS

Oxidant / reductantnone reported

Work-upspin-cast 1:1 P3HT:PCBM at 2000 rpm to about 150 nm; evaporate BCP and Ag; encapsulate

Activationas-cast, thermal anneal, solvent-vapour anneal, or solvent plus thermal anneal depending on table row

Scalability contextControl device data averaged over 35 devices for each condition.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	P3HT	ratio 1 · 10 mg/mL precursor solution	16 · 7.3 Active layer deposition
Other	PCBM	ratio 1 · 99% purity	16 · 7.3 Active layer deposition
Solvent	chlorobenzene	not reported for precursor; 20 uL for solvent-vapour anneal	16 · 7.3 Active layer deposition

Partial recipeSource: SI

Route 4: Other

25-31 · 9. SCLC devices · Table S3; Fig. S19-S22

Metal precursorspreformed Zn2(ZnTCPP) MONs where present

Linker precursorspreformed Zn2(ZnTCPP) MONs where present

Solventssame active-layer procedure as photovoltaic devices

AdditivesMoO3:Ag for hole-only devices; ZnO and BCP:Ag for electron-only devices

Atmospheresame as photovoltaic devices

Temperaturesame active-layer processing as photovoltaic devices

Timesame active-layer processing as photovoltaic devices

Substrate orientationITO:PEDOT/PSS for hole-only; ITO:ZnO for electron-only

Oxidant / reductantnone reported

Work-upprepared following PV procedure except metal electrode configuration

Activationnot separately specified

Scalability contextNumber of SCLC devices tested for each thickness = 3.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	MoO3	not reported	25-31 · 9. SCLC devices · Table S3; Fig. S19-S22
Additive	ZnO	not reported	25-31 · 9. SCLC devices · Table S3; Fig. S19-S22
Additive	BCP	not reported	25-31 · 9. SCLC devices · Table S3; Fig. S19-S22
Additive	Ag	not reported	25-31 · 9. SCLC devices · Table S3; Fig. S19-S22

Complete recipeSource: SI

Route 5: Other

3 · 2.1 Synthesis

Metal precursorsnone

Linker precursors4-formylbenzoic acid; freshly distilled pyrrole

Solventspropionic acid; water wash

Additivesnone reported

Atmospheredry glassware with nitrogen overpressure for ligand syntheses; pyrrole distilled under vacuum

Temperature80 deg C pyrrole distillation; reflux in propionic acid

Time15 h reflux; 10 h chilled before filtration

Oxidant / reductantnone reported

Work-upvacuum filtration; washed with hot water (2 x 20 mL); vacuum dried

Activationvacuum drying

Scalability contextYield 3.23 g, 4.0 mmol, 80%.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Linker	4-formylbenzoic acid	3.0 g, 20 mmol	3 · 2.1 Synthesis
Other	freshly distilled pyrrole	1.4 mL, 20 mmol	3 · 2.1 Synthesis
Solvent	propionic acid	100 mL	3 · 2.1 Synthesis

Complete recipeSource: Both

Route 6: Other

16-17 · 7.1-7.5 Fabrication of devices

Metal precursorspreformed Zn2(ZnTCPP) MONs

Linker precursorspreformed Zn2(ZnTCPP) MONs

Solventschlorobenzene for active layer and solvent-vapour anneal

AdditivesP3HT, PCBM, PEDOT:PSS, BCP, Ag electrode, epoxy encapsulant

Atmospherenitrogen glovebox for active-layer spin coating; vacuum <2E-6 mbar for BCP/Ag evaporation

Temperature60 deg C P3HT solution and P3HT/MON stirring; 70 deg C after PCBM addition; 110 deg C PEDOT:PSS anneal; 120 deg C thermal anneal where used

Time10 min P3HT heating; 1 h P3HT/MON stirring; 1 h after PCBM addition; 5 min solvent-vapour anneal; 10 min thermal anneal variants

Substrate orientationpre-patterned ITO glass with PEDOT:PSS

Oxidant / reductantnone reported

Work-upspin-cast active layer at 1000 rpm; evaporate BCP 5 nm and Ag 100 nm; encapsulate with epoxy resin

Activationsolvent-vapour and/or thermal annealing depending on device condition

Scalability contextDevice data averaged over 35 devices for each condition.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	P3HT	10 mg/mL solution; effective ratio 1 · 10 mg/mL	16-17 · 7.1-7.5 Fabrication of devices
Other	ZnTCPP MONs / Zn2(ZnTCPP) MONs	5 mg; ratio 0.5	16-17 · 7.1-7.5 Fabrication of devices
Other	PCBM	10 mg; ratio 1 · 99% purity	16-17 · 7.1-7.5 Fabrication of devices
Solvent	chlorobenzene	20 uL for solvent-vapour anneal	16-17 · 7.1-7.5 Fabrication of devices
Additive	PEDOT:PSS Al4083	45 uL spin-coated	16-17 · 7.1-7.5 Fabrication of devices

Complete recipeSource: Both

Route 7: Other

3-4 · 2.3 Exfoliation of MOF into MONs

Metal precursorspreformed Zn2(ZnTCPP) MOF

Linker precursorspreformed Zn2(ZnTCPP) MOF

Solventschlorobenzene in main text; SI says desired solvent; concentration 5 mg/mL for chlorobenzene suspension

Additivesnone reported

Atmosphereambient during sonication; temperature controlled water bath at 16-20 deg C

Temperature16-20 during sonication

Time1

Oxidant / reductantnone reported

Work-upvortex 30 s; sonicate 60 min at 80 kHz and 100% power; centrifuge at 1500 rpm for 10 min to remove non-exfoliated particles

Activationnone reported

Scalability contextMain text calls the liquid-exfoliation approach simple and scalable.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Zn2(ZnTCPP) MOF	20 mg · 5 mg/mL	3-4 · 2.3 Exfoliation of MOF into MONs
Solvent	chlorobenzene or desired solvent	4 mL	3-4 · 2.3 Exfoliation of MOF into MONs