Synthesis evidence

The Growth Mechanism of a Conductive MOF Thin Film in Spray-based Layer-by-layer Liquid Phase Epitaxy

Zheng R., Fu Z.-H., Deng W.-H. et al. · Angewandte Chemie - International Edition · 2022 · e202212797

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

p004 · 1.3 Fabrication of Cu-HHTP-xC films

Metal precursorsCopper acetate (Cu(OAc)2.H2O), 0.1 mM ethanolic solution
Linker precursorsHHTP (2,3,6,7,10,11-hexahydrotriphenylene / hexahydroxytriphenylene), 0.01 mM ethanolic solution
Solventsethanol for Cu acetate and HHTP spray solutions and rinse; acetone, ethanol and deionized water for substrate cleaning; piranha solution H2SO4/H2O2 for hydroxyl functionalisation
Additivesnone reported for MOF growth
Atmosphereambient spray process controlled at 25 deg C and 40 %RH; N2 stream drying between spray steps
Temperature25
TimePer growth cycle: copper acetate spray 20 s, ethanol rinse 40 s and N2 dry 20 s; HHTP spray 40 s, ethanol rinse 40 s and N2 dry 20 s; repeated x = 1-60 cycles.
Substrate orientationSapphire substrates (2 x 1 x 1 mm3), silicon wafers and SiO2 (300 nm)-coated silicon wafers; hydroxyl-functionalised before growth; Cr/Au electrodes with 10 um channel width on sapphire for device measurements.
Oxidant / reductantPiranha solution H2SO4 (95%-98%) / H2O2 (30%) = 7:3 used for substrate functionalisation; no oxidant/reductant reported in MOF spray growth.
Work-upSubstrates alternately ultrasonicated in acetone, ethanol and DI water; immersed in piranha solution at 100 deg C for 1 h; rinsed and ultrasonically cleaned 30 min in ethanol; dried under N2. During growth, ethanol spray rinses remove residual reactants after each precursor spray, followed by N2 drying.
ActivationNo general activation reported for as-grown xC series; XRD specimens received separate HHTP immersion described in route r_xrd_hhtp_crystallinity_treatment.
Scalability contextSpray LBL-LPE uses 15 sccm/min precursor flow and is repeated to tune film thickness by growth cycle number.
Show 7 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCopper acetate (Cu(OAc)2.H2O), purchased from Sigma Aldrichsprayed for 20 s per growth cycle at 15 sccm/min · 0.1 mM ethanolic solutionp004 · 1.3 Fabrication of Cu-HHTP-xC films
LinkerHHTP (2,3,6,7,10,11-hexahydrotriphenylene), purchased from TCI (Shanghai)sprayed for 40 s per growth cycle at 15 sccm/min · 0.01 mM ethanolic solutionp004 · 1.3 Fabrication of Cu-HHTP-xC films
Solventethanol40 s rinse between each spray step; also solvent for precursor solutions · pure ethanol for rinsep004 · 1.3 Fabrication of Cu-HHTP-xC films
Solventacetone, ethanol and deionized wateralternate ultrasonication substrate cleaningp004 · 1.3 Fabrication of Cu-HHTP-xC films
AcidH2SO4piranha solution H2SO4/H2O2 = 7:3, 100 deg C for 1 h · 95%-98%p004 · 1.3 Fabrication of Cu-HHTP-xC films
OxidantH2O2piranha solution H2SO4/H2O2 = 7:3, 100 deg C for 1 h · 30%p004 · 1.3 Fabrication of Cu-HHTP-xC films
OtherN2 gas20 s drying after ethanol rinsep004 · 1.3 Fabrication of Cu-HHTP-xC films
Partial recipeSource: SI

Route 2: Other

p004 · 1.3 Fabrication of Cu-HHTP-xC films

Metal precursorsCu3(HHTP)2 film from spray LBL-LPE route
Linker precursorsadditional HHTP ligand solution, 0.01 mM
Solventssolution solvent not explicitly named in treatment sentence; likely same HHTP solution context but recorded as not specified
AdditivesHHTP ligand
Atmospherenot specified
Temperature85
Time20
Substrate orientationnot separately specified for XRD film; thin-film XRD/GIXRD specimen
Work-upPrepared thin films were immersed in 0.01 mM HHTP ligand solution at 85 deg C for 20 h for XRD measurements.
ActivationPost-growth HHTP immersion to further improve crystallinity.
Scalability contextTreatment is specific to XRD measurements rather than the general device/sensing film series.
Show 2 structured reagent records
RoleReagentAmount / concentrationSource
LinkerHHTP ligandimmersion at 85 deg C for 20 h · 0.01 mMp004 · 1.3 Fabrication of Cu-HHTP-xC films
Otheras-prepared Cu3(HHTP)2 thin film200 nm film for XRD figurep004 · 1.3 Fabrication of Cu-HHTP-xC films