Synthesis · A Copper Coordination Polymer with Matching Energy Level for Modifying Hole Transport Layers to Improve the Performance of 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: Main

Route 1: Solvothermal

p008 / journal page 2770 · Experimental Section - Preparation of Cu-bix

Metal precursorsCuI (0.4 mmol)

Linker precursors1,3-bis(imidazole-1-yl-methyl)-benzene (bix, 0.2 mmol)

Solventsconcentrated KI solution (6 mL); CH3OH (2 mL)

AdditivesKI in concentrated aqueous solution

Atmospheresealed Teflon-lined autoclave; gas atmosphere not reported

Temperature140

Time72

Work-upcooled to room temperature; pale-yellow crystals obtained

Activationnot reported

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuI	0.4 mmol	p008 / journal page 2770 · Experimental Section - Preparation of Cu-bix
Linker	1,3-bis(imidazole-1-yl-methyl)-benzene (bix)	0.2 mmol	p008 / journal page 2770 · Experimental Section - Preparation of Cu-bix
Additive	concentrated KI solution	6 mL · concentrated	p008 / journal page 2770 · Experimental Section - Preparation of Cu-bix
Solvent	CH3OH	2 mL	p008 / journal page 2770 · Experimental Section - Preparation of Cu-bix

Partial recipeSource: Main

Route 2: Other

p008 / journal page 2770 · Experimental Section - Device fabrication

Metal precursorsCu-bix additive; titanium isopropoxide; PbI2 and PbBr2; Au electrode

Linker precursorsbix linker already incorporated in Cu-bix

Solventschlorobenzene, acetonitrile, isopropanol

AdditivesCu-bix in chlorobenzene; LiTFSI; TBP

Atmosphereperovskite films deposited in glovebox; HTL preparation atmosphere not reported

Temperature100 for perovskite film anneal; 500 for TiO2 anneal

Time0.25 h perovskite anneal; Cu-bix CB solution pulverised for 2 h

Substrate orientationFTO/TiO2/perovskite substrate

Work-upCu-bix chlorobenzene solution passed through a cell pulverizer for 2 h and filtered through a 0.22 um filter; HTL spin-coated at 4000 rpm for 20 s; 60-80 nm Au evaporated

Scalability contextCu 1-4, Cu 2-4, Cu 3-4 and Cu 4-4 concentrations were 0.1, 0.2, 0.3 and 0.4 mg mL-1, respectively; SI Figure S9 shows Cu 3-4 gives the best PCE distribution.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	Cu-bix	Cu 1-4, Cu 2-4, Cu 3-4, Cu 4-4: 0.1, 0.2, 0.3, 0.4 mg mL-1 · in chlorobenzene	p008 / journal page 2770 · Experimental Section - Device fabrication
Other	Spiro-OMeTAD	72.3 mg · in chlorobenzene, 1 mL	p008 / journal page 2770 · Experimental Section - Device fabrication
Additive	LiTFSI solution	17.5 uL · 520 mg mL-1 in acetonitrile	p008 / journal page 2770 · Experimental Section - Device fabrication
Additive	TBP	28.8 uL	p008 / journal page 2770 · Experimental Section - Device fabrication
Solvent	chlorobenzene	1 mL for Spiro-OMeTAD stock; 200 uL antisolvent during perovskite spin coating	p008 / journal page 2770 · Experimental Section - Device fabrication

Partial recipeSource: Main

Route 3: Other

p008 / journal page 2770 · Experimental Section - Device fabrication

Metal precursorstitanium isopropoxide for TiO2; PbI2 and PbBr2 for perovskite; Au evaporated electrode

Linker precursorsnot applicable

Solventsisopropanol, deionised water, acetone, ethanol, chlorobenzene, acetonitrile

AdditivesLiTFSI solution (17.5 uL, 520 mg mL-1 in acetonitrile), TBP (28.8 uL)

Atmosphereperovskite films deposited in glovebox; other steps not fully specified

Temperature500 for TiO2 anneal; 60 for perovskite precursor heating; 100 for perovskite film anneal

Time0.5 h for TiO2 anneal; 0.25 h for perovskite anneal

Substrate orientationFTO-coated glass, partially etched

Work-upsubstrates washed 30 min each in deionised water, acetone and ethanol; UV ozone 15 min; Au thermally evaporated

Scalability contextDevice active area 0.06 cm2.

Show 8 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	FTO-coated glass (14 ohm per square, NSG, Japan)	Not specified	p008 / journal page 2770 · Experimental Section - Device fabrication
Metal Source	titanium isopropoxide	175 uL	p008 / journal page 2770 · Experimental Section - Device fabrication
Acid	dilute HCl	17.5 uL · 3 mol L-1	p008 / journal page 2770 · Experimental Section - Device fabrication
Solvent	isopropanol	2.5 mL	p008 / journal page 2770 · Experimental Section - Device fabrication
Other	CsI, FAI, MABr, PbI2, PbBr2	1.2 M precursor solution	p008 / journal page 2770 · Experimental Section - Device fabrication
Additive	LiTFSI solution	17.5 uL · 520 mg mL-1 in acetonitrile	p008 / journal page 2770 · Experimental Section - Device fabrication
Additive	TBP	28.8 uL	p008 / journal page 2770 · Experimental Section - Device fabrication
Other	Spiro-OMeTAD	72.3 mg · in chlorobenzene, 1 mL	p008 / journal page 2770 · Experimental Section - Device fabrication