Synthesis · Chemical Vapor Deposition and High-Resolution Patterning of a Highly Conductive Two-Dimensional Coordination Polymer Film

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: Cvd

SI p.S4 and main p.B · CuO deposition; Cu-BHT film chemical vapor deposition · Figure 1e; Figure S6

Metal precursorsRF-sputtered CuO precursor film deposited from 3 inch sputtering targets.

Linker precursorsH6BHT powder, 15 mg, vaporised at 140 deg C.

SolventsNone during CVD.

AtmosphereDynamic vacuum to ca. 4 x 10^-3 mbar in a closed 60 mm glass tube.

Temperaturesubstrate 150; H6BHT powder 140

Time10

Substrate orientationSi/CuO, Si/SiO2/CuO or glass/CuO substrates; default characterisation substrates were Si.

Oxidant / reductantVapour-solid conversion of CuO to Cu-BHT; reduction of Cu(II) to Cu(I) occurs during reaction with H6BHT.

Work-upNo post-conversion solvent workup stated for films.

Scalability contextUniform blue coating over large centimetre-scale areas; final film thickness controlled by CuO precursor thickness.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuO precursor layer	varied film thickness	SI p.S4 and main p.B · CuO deposition; Cu-BHT film chemical vapor deposition · Figure 1e; Figure S6
Linker	H6BHT	15 mg	SI p.S4 and main p.B · CuO deposition; Cu-BHT film chemical vapor deposition · Figure 1e; Figure S6
Other	Ar plasma for RF sputtering	2 x 10^-3 mbar Ar partial pressure, 120 W	SI p.S4 and main p.B · CuO deposition; Cu-BHT film chemical vapor deposition · Figure 1e; Figure S6

Complete recipeSource: SI

Route 2: Drop Cast

SI p.S6-S7 · Fabrication and characterization of field-effect transistors (FETs) · Figure S22

Metal precursorsSi/SiO2/Cu-BHT film with evaporated Au source/drain electrodes.

AdditivesIonic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate.

Substrate orientationSi/SiO2/Cu-BHT film.

Work-upMeasured with Keysight B1500 semiconductor analyser.

Show 2 structured reagent records

Role	Reagent	Amount / concentration	Source
Electrolyte	1-ethyl-3-methylimidazolium tetrafluoroborate	drop-cast over film and electrodes · >=99%	SI p.S6-S7 · Fabrication and characterization of field-effect transistors (FETs) · Figure S22
Other	Au source and drain electrodes	90 nm	SI p.S6-S7 · Fabrication and characterization of field-effect transistors (FETs) · Figure S22

Complete recipeSource: SI

Route 3: Other

SI p.S4 and p.S6 · Bottom-up additive lithography; Hall effect measurements · Figure 4c-d

Metal precursorsCVD Cu-BHT Hall bar plus thermally evaporated Cr/Au electrodes.

SolventsAcetone for lift-off in electrode patterning.

AdditivesHMDS, AZ1505 photoresist, AZ 351 B developer.

AtmosphereElectrode evaporation with substrates maintained at 10 deg C.

Temperature10 during electrode evaporation

Substrate orientationSi/SiO2 substrates with 300 nm dry thermal silicon oxide.

Work-upContacts made with Cu wires and silver-based conductive paste for Hall measurement.

Scalability contextMinimum Hall arm feature size of 2 um enabled transport measurements.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Other	Cr adhesive layer	5 nm	SI p.S4 and p.S6 · Bottom-up additive lithography; Hall effect measurements · Figure 4c-d
Other	Au electrodes	100 nm	SI p.S4 and p.S6 · Bottom-up additive lithography; Hall effect measurements · Figure 4c-d
Additive	silver-based conductive paste	used to glue Cu wires	SI p.S4 and p.S6 · Bottom-up additive lithography; Hall effect measurements · Figure 4c-d

Complete recipeSource: Both

Route 4: Other

SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13

Metal precursorsCuO layer deposited by RF sputtering after photoresist patterning.

Linker precursorsH6BHT vapour in subsequent Cu-BHT CVD conversion.

SolventsAcetone, isopropanol and water cleaning; Remover PG for photoresist removal; acetone for electrode lift-off.

AdditivesHMDS adhesion promoter; AZ1505 positive photoresist; AZ 351 B developer.

AtmosphereNitrogen blow dry; later CVD under dynamic vacuum.

Temperature150 hotplate for drying; 100 photoresist bake; 150 substrate CVD; 140 H6BHT powder CVD; 10 substrate temperature during electrode evaporation.

Time2 min hotplate steps; 1 min development; overnight Remover PG soak; CVD exposure 10 h by main route.

Substrate orientationSi 3 x 3 cm2 pieces; Si/SiO2 substrates with 300 nm dry thermal oxide for Hall bar electrode patterning.

Oxidant / reductantCuO-to-Cu-BHT conversion as in CVD route.

Work-upPhotoresist removed by overnight Remover PG before conversion; acetone lift-off for electrode patterning.

Scalability contextHigh-fidelity bottom-up patterning; interdigitated electrodes, circles, lines and logo features demonstrated.

Show 6 structured reagent records

Role	Reagent	Amount / concentration	Source
Solvent	acetone, isopropanol, water	cleaning sonication solvents	SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13
Additive	HMDS	adhesion promoter	SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13
Additive	AZ1505 positive photoresist	spun at 3000 rpm	SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13
Additive	AZ 351 B developer	4x diluted, 1 min · 4x diluted	SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13
Solvent	Remover PG	overnight soak	SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13
Other	Cr/Au electrodes	5 nm Cr, 100 nm Au	SI p.S4 · Bottom-up additive lithography · Figure 3; Figure S13

Complete recipeSource: Both

Route 5: Other

SI p.S4 · Top-down plasma etching lithography · Figures S15-S16

Metal precursorsPreformed Cu-BHT thin film.

SolventsAcetone for final photoresist removal.

AdditivesHMDS, AZ1505 photoresist, AZ 351 B developer.

AtmosphereArgon plasma during reactive ion etching.

Temperature150 hotplate bake; 100 photoresist bake

Time2 min hotplate bake; 2 min photoresist bake; 1 min development

Work-upPhotoresist dissolved in acetone after Ar plasma etching.

Scalability contextCompared unfavourably with lift-off because of edge damage and incomplete Cu-BHT removal between lines.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Additive	HMDS and AZ1505 photoresist	spun at 3000 rpm	SI p.S4 · Top-down plasma etching lithography · Figures S15-S16
Additive	AZ 351 B developer	4x diluted, 1 min · 4x diluted	SI p.S4 · Top-down plasma etching lithography · Figures S15-S16
Other	argon plasma	20 mTorr base pressure, 50 sccm Ar, 50 W	SI p.S4 · Top-down plasma etching lithography · Figures S15-S16
Solvent	acetone	photoresist dissolution	SI p.S4 · Top-down plasma etching lithography · Figures S15-S16

Vague recipeSource: SI

Route 6: Liquid Liquid Interface

SI p.S4 · Liquid-liquid interfacial synthesis of the Cu-BHT reference

Scalability contextUsed only as a reference; detailed recipe is cited to previous work.

Complete recipeSource: Both

Route 7: Other

SI p.S4 · Solvent-free Cu-BHT powder synthesis · Figures S3-S4

Metal precursorsCopper(II) oxide nanoparticles, <50 nm particle size, 13 mg.

Linker precursorsH6BHT ligand, 15 mg.

SolventsNo synthesis solvent; chloroform used in workup wash.

AtmosphereDynamic vacuum ca. 10^-3 mbar for 20 min, flame-sealed ampoule; dried under nitrogen flow after washing.

Temperature150

Time12

Oxidant / reductantCuO is reduced during reaction with H6BHT; main text proposes thiol oxidation/disulfide formation followed by Cu-thiolate bonding.

Work-upOpened after cooling to room temperature, washed with chloroform, dried under nitrogen flow.

Scalability contextPreliminary powder reactivity test, not the main scalable film route.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	CuO NPs	13 mg	SI p.S4 · Solvent-free Cu-BHT powder synthesis · Figures S3-S4
Linker	H6BHT ligand	15 mg	SI p.S4 · Solvent-free Cu-BHT powder synthesis · Figures S3-S4
Solvent	chloroform	wash solvent	SI p.S4 · Solvent-free Cu-BHT powder synthesis · Figures S3-S4