cMOF Evidence Base

Synthesis evidence

Emergence of Metallic Conductivity in Ordered One-Dimensional Coordination Polymer Thin Films upon Reductive Doping

Nisula M., Karttunen A.J., Solano E. et al. · ACS Applied Materials and Interfaces · 2021 · 10249-10256

3 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

p002 / article p.10250 · Experimental Section · Figure S1

Metal precursorsBis(dimethylamino-2-propoxy)copper(II) (Cu(dmap)2, >97%, Strem Chemicals)
Linker precursorsN,N'-dimethyldithiooxamide (DMD), synthesised from dithiooxamide and methylamine
SolventsNo solvent in ALD/MLD film deposition; water used only in DMD precursor synthesis/washing
AtmosphereHigh-vacuum pump-type ALD reactor; argon carrier gas
TemperatureSubstrate 80; chamber walls 85; Cu(dmap)2 bubbler 70; DMD bubbler 60
TimeCycle-dependent; pulse saturation observed above 20 s for Cu(dmap)2 and 35 s for DMD
Substrate orientationSi(100) with native oxide unless otherwise mentioned; also IDA, quartz, TiN-coated Si and Pt-coated Si for specific measurements
Oxidant / reductantNone during deposition
Work-upAfter each precursor pulse, chamber pumped back to base pressure before next pulse
ActivationNone reported for as-deposited films
Scalability contextALD/MLD described as a vapour-phase layer-by-layer method with subnanometre thickness control and uniformity over large-area substrates.
Show 5 structured reagent records
RoleReagentAmount / concentrationSource
Metal SourceBis(dimethylamino-2-propoxy)-copper(II) (Cu(dmap)2, >97%, Strem Chemicals)Not specifiedp002 / article p.10250 · Experimental Section · Figure S1
LinkerN,N'-dimethyldithiooxamide (DMD)Not specifiedp002 / article p.10250 · Experimental Section · Figure S1
OtherArgon carrier gasNot specifiedp002 / article p.10250 · Experimental Section · Figure S1
Linkerdithiooxamide (97%, Sigma Aldrich), used to synthesise DMD5 gp002 / article p.10250 · Experimental Section · Figure S1
Baseaqueous methylamine (40 wt % in H2O, Sigma Aldrich), used to synthesise DMD3 x molar excess · 40 wt % in H2Op002 / article p.10250 · Experimental Section · Figure S1
Partial recipeSource: Both

Route 2: Other

p003 / article p.10251 · Experimental Section · Figure S9b

AtmosphereFlowing O2, 0.5 mL/min, 99.999%
Temperature80-130
Substrate orientationIDA electrical-device sample
Oxidant / reductantO2 oxidant
Work-upSubsequent exposure to ambient air was monitored
ActivationThermal oxidative treatment after H2 reduction
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
OxidantO20.5 mL/min · 99.999%p003 / article p.10251 · Experimental Section · Figure S9b
Complete recipeSource: Both

Route 3: Other

p003 / article p.10251 · Experimental Section · Figure 2; Figure S12

AtmosphereFlowing 5% H2/He; 0.5 mL/min for electrical annealing and 500 sccm, 1 bar for in situ GIWAXS
Temperature170
Time2 for in situ GIWAXS; electrical annealing monitored over approximately 150 min in Figure 2a
Substrate orientationCu-DMD films on IDA electrodes for electrical transport; films on heating stage in GIWAXS chamber for structural tracking
Oxidant / reductantH2 reductant
Work-upHigh-conductance state retained on cooling; subsequent air exposure tested
ActivationThermal reductive annealing/protonation
Show 1 structured reagent record
RoleReagentAmount / concentrationSource
ReductantH2/He mixture0.5 mL/min for conductance experiments; 500 sccm for GIWAXS · 5% H2p003 / article p.10251 · Experimental Section · Figure 2; Figure S12