cMOF Evidence Base

Synthesis evidence

Surface Morphology and Electrical Properties of Cu3BTC2 Thin Films before and after Reaction with TCNQ

Thurmer K., Schneider C., Stavila V. et al. · ACS Applied Materials and Interfaces · 2018 · 39400-39410

7 structured synthesis routes

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

Partial recipeSource: Main

Route 1: Other

p002 / 39401 · Experimental Section

Metal precursorsCu(Ac)2.H2O in ethanol, assumed same step-by-step recipe as ITO films
Linker precursorsH3BTC in ethanol, assumed same step-by-step recipe as ITO films
Solventsethanol
Atmospherenot specified
Temperature50
Time50 deposition cycles; individual cycle times as for ITO recipe unless otherwise specified
Substrate orientationSi substrate with 100 nm thermal SiO2 and prepatterned Au electrodes (500 um x 200 um)
Work-upethanol rinse after immersion steps, inferred from general Cu3BTC2 film recipe
Activationdesolvated at 100 C and 10^-6 mbar for 1 h before TCNQ infiltration
Scalability contextDevice geometry supports transport measurements over Au pads 50 um apart.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(Ac)2.H2O1.0 mmol/Lp002 / 39401 · Experimental Section
LinkerH3BTC0.1 mmol/Lp002 / 39401 · Experimental Section
SolventethanolNot specifiedp002 / 39401 · Experimental Section
Complete recipeSource: Main

Route 2: Other

p002 / 39401 · Experimental Section

Metal precursorsCu(Ac)2.H2O (Ac = acetate, 1.0 mmol/L in ethanol)
Linker precursorsH3BTC (0.1 mmol/L in ethanol)
Solventsethanol
Atmospheredry N2 drying before oxygen plasma; deposition atmosphere not specified
Temperature50
Time0.125 h Cu solution immersion + 0.25 h H3BTC immersion per cycle; 20 cycles for this sample
Substrate orientationpolycrystalline ITO; rms roughness approx. 1 nm
Oxidant / reductantoxygen plasma surface activation before deposition
Work-upethanol rinse after each immersion step
Activationfor TCNQ-converted samples: desolvated at 100 C and 10^-6 mbar for 1 h
Scalability contextStep-by-step method can be varied by deposition-cycle count; paper notes Cu3BTC2 can be grown and patterned on many substrates.
Show 4 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(Ac)2.H2O1.0 mmol/Lp002 / 39401 · Experimental Section
LinkerH3BTC0.1 mmol/Lp002 / 39401 · Experimental Section
SolventethanolNot specifiedp002 / 39401 · Experimental Section
Oxidantoxygen plasma10 minp002 / 39401 · Experimental Section
Partial recipeSource: Main

Route 3: Other

p009 / 39408 · Figure caption · Figure 10

Metal precursorsCu(Ac)2.H2O in ethanol, based on main step-by-step method
Linker precursorsH3BTC in ethanol, based on main step-by-step method
Solventsethanol
Atmospherenot specified
Temperature50
Time4 deposition cycles; per-cycle times as reported for general route
Substrate orientationamorphous SiO2/Si(001)
Work-upethanol rinsing after immersion steps, based on general route
Activationnot specified for substrate-comparison sample
Scalability contextSubstrate choice narrows crystallite-size distribution relative to polycrystalline ITO.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceCu(Ac)2.H2O1.0 mmol/Lp009 / 39408 · Figure caption · Figure 10
LinkerH3BTC0.1 mmol/Lp009 / 39408 · Figure caption · Figure 10
SolventethanolNot specifiedp009 / 39408 · Figure caption · Figure 10
Vague recipeSource: SI

Route 4: Solvothermal

p003 / S-3 · Figure captions · Figure S4

Metal precursorsnot specified for PCN-14 film in supplied SI caption
Linker precursorsnot specified for PCN-14 film in supplied SI caption
SolventsMeOH for TCNQ infiltration; solvothermal synthesis solvent not specified
Atmospherenot specified
Temperaturenot specified
Timenot specified
Substrate orientationnot specified
Oxidant / reductantTCNQ/MeOH conversion chemistry inferred by authors
Work-upnot specified
Activationnot specified
Scalability contextOnly used as supporting evidence that other Cu-paddlewheel MOFs can show Cu(TCNQ) signatures.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Othersolvothermally synthesised PCN-14 filmNot specifiedp003 / S-3 · Figure captions · Figure S4
OxidantTCNQNot specifiedp003 / S-3 · Figure captions · Figure S4
ReductantMeOHNot specifiedp003 / S-3 · Figure captions · Figure S4
Partial recipeSource: Main

Route 5: Other

p006 / 39405 · Electrical Conductivity Change · Figure 8

Metal precursors50-cycle Cu3BTC2 film on Au-patterned Si/SiO2
Linker precursorsBTC in parent Cu3BTC2; TCNQ reagent
Solventsmethanol
Atmosphereambient electrical measurement after conversion; infiltration atmosphere not specified
Temperaturenot specified for infiltration
Timenot repeated in electrical section; general film infiltration recipe uses 12 h
Substrate orientationSi wafer with 100 nm SiO2 and Au electrodes
Oxidant / reductantMeOH proposed as electron source
Work-uprinsed with methanol, inferred from general infiltration workup
Activationdesolvated before infiltration, inferred from general film protocol
Scalability contextUsed to fabricate a conductive film on an electronic-device substrate.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Other50-cycle Cu3BTC2 filmNot specifiedp006 / 39405 · Electrical Conductivity Change · Figure 8
OxidantTCNQNot specifiedp006 / 39405 · Electrical Conductivity Change · Figure 8
ReductantMeOHNot specifiedp006 / 39405 · Electrical Conductivity Change · Figure 8
Complete recipeSource: Main

Route 6: Other

p002 / 39401 · Experimental Section

Metal precursorsCu3BTC2 thin film grown by step-by-step deposition
Linker precursorsBTC in parent Cu3BTC2; TCNQ reagent for product
Solventsreagent-grade methanol
Atmospheredesolvation at 10^-6 mbar; infiltration atmosphere not otherwise specified
Temperature100 C desolvation; infiltration temperature not specified, likely ambient
Time1 h desolvation; 12 h TCNQ immersion
Substrate orientationITO substrate for morphology/structure series
Oxidant / reductantMeOH proposed as reductant/electron source; TCNQ reduced to TCNQ radical anion
Work-uprinsed with fresh methanol before characterisation
Activationdesolvated at 100 C and 10^-6 mbar for 1 h before TCNQ immersion
Scalability contextConversion was observed for 0.5-, 2-, and 20-cycle films; 20-cycle films converted fully by GIXRD/AES.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
OtherCu3BTC2 thin film0.5, 2, 20 cycles in treated seriesp002 / 39401 · Experimental Section
OxidantTCNQsaturated solution · saturatedp002 / 39401 · Experimental Section
Reductantmethanolreagent-grade solventp002 / 39401 · Experimental Section
Partial recipeSource: Main

Route 7: Other

p006 / 39405 · Partial Conversion · Figure 7

Metal precursorsactivated Cu3BTC2 powder, grain size 10-30 um
Linker precursorsBTC in parent Cu3BTC2; TCNQ reagent
Solventsmethanol
Atmosphereroom temperature; atmosphere not specified
Temperatureroom temperature
Time72 h and 168 h powder infiltration times reported
Substrate orientationnot applicable
Oxidant / reductantMeOH proposed as electron source; TCNQ radical formation indicated by solution colour changes
Work-upnot specified
Activationactivated Cu3BTC2 powder; activation details not specified
Scalability contextLarge 10-30 um powder grains convert only partially even after 7 days.
Show 3 structured reagent records
RoleReagentAmount / concentrationSource
Otheractivated Cu3BTC2 powdergrain size 10-30 ump006 / 39405 · Partial Conversion · Figure 7
OxidantTCNQsaturated solution · saturatedp006 / 39405 · Partial Conversion · Figure 7
ReductantMeOHNot specifiedp006 / 39405 · Partial Conversion · Figure 7