Synthesis · Ultrathin Self-Assembly Two-Dimensional Metal-Organic Framework Films as Hole Transport Layers in Ideal-Bandgap Perovskite Solar Cells

3 structured synthesis routes

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

Partial recipeSource: Both

Route 1: Other

p003-p004 / SI p.3-p.4 · Synthesis of MOF · Figure 1a

Metal precursorsCu(OAc)2 in ethanol

Linker precursorsHHTT in ethanol

Solventsethanol

Atmospherenot specified

Temperaturenot specified; room-temperature immersion implied

Timesingle cycle; optimum 5 min Cu(OAc)2 immersion and 10 min HHTT immersion

Substrate orientationITO substrate cleaned and oxygen-plasma-treated to generate surface -OH groups

Work-upnot specified after each immersion

Scalability contextMain text states the self-assembly process is compatible with large-area fabrication and conformal coverage on any substrate with high uniformity and controllable thickness.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	optimized but not reported	p003-p004 / SI p.3-p.4 · Synthesis of MOF · Figure 1a
Linker	HHTT	optimized but not reported	p003-p004 / SI p.3-p.4 · Synthesis of MOF · Figure 1a
Solvent	ethanol	Not specified	p003-p004 / SI p.3-p.4 · Synthesis of MOF · Figure 1a
Other	ITO substrate	Not specified	p003-p004 / SI p.3-p.4 · Synthesis of MOF · Figure 1a

Partial recipeSource: SI

Route 2: Other

p003 / SI p.3 · Synthesis of MOF · Scheme 1

Linker precursorscompound 1; 5,6-dimethoxyanthranil derivative 2; compound 3

Solventsacetic acid; sulfolane; pyridine

Additivesammonium acetate; pyridinium hydrochloride / HCl and pyridine

Atmospherenot specified

Temperatureroom temperature; reflux; 230 C from Scheme 1

Time24 h; 96 h; 3 h from Scheme 1

Oxidant / reductanttin foil and acetic acid for partial reduction; oxidative cyclotrimerization with ammonium acetate

Work-upnot specified

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Reductant	tin foil	Not specified	p003 / SI p.3 · Synthesis of MOF · Scheme 1
Acid	acetic acid	Not specified	p003 / SI p.3 · Synthesis of MOF · Scheme 1
Additive	ammonium acetate	Not specified	p003 / SI p.3 · Synthesis of MOF · Scheme 1
Solvent	sulfolane	Not specified	p003 / SI p.3 · Synthesis of MOF · Scheme 1
Acid	pyridinium hydrochloride / HCl	Not specified	p003 / SI p.3 · Synthesis of MOF · Scheme 1
Solvent	pyridine	Not specified	p003 / SI p.3 · Synthesis of MOF · Scheme 1

Complete recipeSource: SI

Route 3: Other

p004 / SI p.4 · Device fabrication

Metal precursorsFAI, SnI2, SnF2, CsI, PbBr2, PbI2; preformed Cu3(HHTT)2 or NiOx HTL

SolventsDMF:DMSO = 4:1; diethyl ether antisolvent; PCBM and BCP solutions

Additives4-hydrazinobenzoic acid (HBA), HBA/SnI2 molar ratio 3%

AtmosphereNiOx transferred to N2 glovebox after annealing; perovskite processing atmosphere not otherwise specified

TemperatureNiOx anneal 150 C; perovskite anneal 70 C then 100 C

TimeNiOx 30 min; perovskite spin 10 s at 1000 rpm and 20 s at 5000 rpm; anneal 1 min at 70 C and 10 min at 100 C

Substrate orientationITO glass or PET/ITO for flexible devices

Oxidant / reductantHBA introduced to suppress Sn2+ oxidation

Work-upPCBM (20 mg mL-1) and BCP (0.5 mg mL-1) spin-coated; 100 nm Ag thermally evaporated

Scalability contextLarge-area ca. 1 cm2 devices and flexible PET/ITO devices fabricated using the same HTL concept.

Show 12 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	FAI	0.83 mmol	p004 / SI p.4 · Device fabrication
Metal Source	SnI2	0.35 mmol	p004 / SI p.4 · Device fabrication
Additive	SnF2	0.035 mmol	p004 / SI p.4 · Device fabrication
Other	CsI	0.17 mmol	p004 / SI p.4 · Device fabrication
Metal Source	PbBr2	0.05 mmol	p004 / SI p.4 · Device fabrication
Metal Source	PbI2	0.6 mmol	p004 / SI p.4 · Device fabrication
Additive	4-hydrazinobenzoic acid (HBA)	3 mol% versus SnI2	p004 / SI p.4 · Device fabrication
Solvent	DMF:DMSO	4:1 mixed solvent	p004 / SI p.4 · Device fabrication
Solvent	diethyl ether	dropped at 10th s	p004 / SI p.4 · Device fabrication
Other	PCBM	20 mg mL-1	p004 / SI p.4 · Device fabrication
Other	BCP	0.5 mg mL-1	p004 / SI p.4 · Device fabrication
Other	Ag electrode	100 nm	p004 / SI p.4 · Device fabrication