cMOF Evidence Base

Synthesis evidence

2D Metal–Organic Framework Cu3(HHTT)2 Films for Broadband Photodetectors from Ultraviolet to Mid-Infrared

Liu C.-K., Piradi V., Song J. et al. · Advanced Materials · 2022 · 2204140

2 structured synthesis routes

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

Complete recipeSource: Both

Route 1: Other

p003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b

Metal precursorsCopper acetate, Cu(OAc)2
Linker precursorsHHTT ligand
SolventsEthanol for optimum films; IPA and DMF used as solvent variants for both precursors
AdditivesOxygen plasma functionalisation of patterned substrate
AtmosphereSubstrates stored and devices measured in N2-filled glovebox; layer-by-layer growth described as under ambient conditions in conclusion.
TemperatureRoom temperature / ambient
Time20 min in copper acetate solution and 40 min in HHTT solution per cycle; oxygen plasma 30 min
Substrate orientation300 nm SiO2/Si or PI prepatterned substrates with 10 nm Cr / 100 nm Au electrodes; substrates functionalised to expose OH groups
Work-upWashed with corresponding solvent to remove excess precursor between each immersion step; process stopped after desired thickness.
ActivationStored in N2-filled glovebox after growth.
Scalability contextWafer-scale films on 4-inch SiO2/Si wafer; film thickness controlled by number of growth cycles at about 11 nm per cycle under optimum ethanolic conditions.
Show 6 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCopper acetate / Cu(OAc)25 mM, 1 mM, or 0.2 mM depending on conditionp003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b
LinkerHHTT0.5 mM, 0.1 mM, or 0.02 mM depending on conditionp003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b
SolventEthanolSolvent for optimum and concentration-series precursor solutionsp003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b
SolventIPASolvent-control precursor solutionsp003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b
SolventDMFSolvent-control precursor solutionsp003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b
Other300 nm SiO2/Si or PI substrate with 10 nm Cr / 100 nm Au electrodesNot specifiedp003-p004 · Pre-patterned Substrate preparation; Fabrication of Cu3(HHTT)2 thin film · Figure 1b
Complete recipeSource: SI

Route 2: Other

p001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1

Linker precursorsHHTT ligand prepared from 4,5-dimethoxy-2-nitrobenzaldehyde through 5,6-dimethoxyanthranil and 2,3,7,8,12,13-hexamethoxytricycloquinazoline intermediates.
SolventsGlacial acetic acid; sulfolane; hexanes/ethyl acetate; water; methanol
AdditivesTin powder; ammonium acetate; pyridine hydrochloride; silica gel column chromatography
AtmosphereNitrogen; standard vacuum-line and Schlenk techniques
Temperatureroom temperature for first step; reflux for second step; 240 deg C for final demethylation
Time20 h; 96 h; 3 h
Oxidant / reductantTin powder reductive cyclisation step
Work-upEther/water workup; organic layer dried over anhydrous sodium sulfate; silica gel chromatography; recrystallisation; suction filtration; washing with water and methanol; final black precipitate washed with water and dried under vacuum.
ActivationFinal HHTT dried under vacuum.
Show 7 structured reagent records
RoleReagentAmount / concentrationSource
Linker4,5-dimethoxy-2-nitrobenzaldehyde5 g, 23.7 mmolp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1
ReductantTin powder13 g, 110 mmolp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1
AcidGlacial acetic acid300 mL first step; 25 mL second stepp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1
AdditiveAmmonium acetate12 g, 156 mmolp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1
SolventSulfolane100 mLp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1
AdditivePyridine hydrochloride27 g, 234 mmolp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1
Other2,3,7,8,12,13-hexamethoxytricycloquinazoline 3800 mg, 1.6 mmolp001-p003 · Experimental Section - Synthesis procedure of HHTT ligand · Figure S1