Nisula M., Karttunen A.J., Solano E. et al. · ACS Applied Materials and Interfaces · 2021 · 10249-10256
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
ALD/MLD enables high-quality, well-ordered Cu-DMD coordination-polymer thin films with controlled thickness suitable for conductive thin-film studies.
Caveat: Growth-per-cycle numerical plateau is estimated from Figure S1 rather than directly tabulated.
p002 / article p.10250 · Introduction · Linked to 4 structured results
The conductivity increase is assigned as intrinsic to Cu-DMD rather than formation of CuS, metallic copper, or another conductive secondary phase.
Caveat: The conclusion rests on absence of new crystalline phases and spectroscopic consistency; very small amorphous impurities cannot be fully ruled out from extracted text alone.
p005 / article p.10253 · Results and Discussion · Figure S12-S18 · Linked to 4 structured results
The deposited material is assigned as 1D Cu-DMD chains arranged in a sheet-like secondary structure with strong out-of-plane orientation.
Caveat: The authors note that a definitive crystal structure for Cu-DMD is lacking in the literature; the structural assignment is model-supported.
p004 / article p.10252 · Results and Discussion · Figure 1 · Linked to 5 structured results
DFT links reduction/protonation to formation of in-gap bands crossing the Fermi level, providing a mechanism for the observed metallic behaviour.
Caveat: The authors caution that the model is idealised with perfectly aligned chains and reduction sites, whereas the real sample is likely more random.
p006 / article p.10254 · Results and Discussion · Figure 3 · Linked to 4 structured results
Cu-DMD ordering and preferred orientation depend on the substrate, with native-oxide Si giving stronger ordering than TiN- or Pt-coated substrates.
Caveat: Substrate comparison is qualitative in the paper and SI figures.
p004 / article p.10252 · Results and Discussion · Figure S6 · Linked to 1 structured result
Open Cu sites catalyse H-H cleavage, leading to partial Cu-DMD reduction and proton localisation on nitrogen as secondary amines.
Caveat: The authors present this as a mechanistic interpretation/speculation supported by spectroscopy and DFT, not as direct observation of H-H cleavage.
p014 / SI p.13 · Supporting Information · Figure S19 · Linked to 3 structured results
The high-conductance H2-reduced Cu-DMD state exhibits metal-like electrical resistance over 2-300 K.
Caveat: Resistance values are two-terminal device values; the authors state this geometry was necessary because of low overall conductance.
p005 / article p.10253 · Results and Discussion · Figure 2b · Linked to 2 structured results
Oxidative O2 heat treatment decreases the high-conductance state toward low conductivity.
Caveat: The exact timing of each O2 step is graphical in Figure S9b, not fully tabulated in text.
p005 / article p.10253 · Results and Discussion · Figure S9b · Linked to 1 structured result
H2/He annealing reductively dopes/protonates Cu-DMD and increases conductivity by about eight orders of magnitude.
Caveat: The maximum 10^-2 S cm^-1 value occurs after short ambient-air exposure following H2 treatment, not solely at the end of the H2 anneal.
p006 / article p.10254 · Conclusions · Linked to 7 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| N,N'-dimethyl dithiooxamidato-copper (Cu-DMD) | Expected CuC4S2N2; measured nominal as-deposited ratio CuC4.1S2.3N1.8Cu centres in one-dimensional copper dithiooxamide chains; Cu(II)/Cu(I) signatures by XPS, with increased Cu(I) after H2 treatment. · N,N'-dimethyldithiooxamide / dimethyl dithiooxamidato (DMD). | 1D · Pristine1D Cu-DMD polymer chains aligned into sheet-like secondary structures; strong out-of-plane orientation by GIWAXS and a single prominent diffraction peak at d = 8.2 A. | p001 / article p.10249 · Abstract |
| Cu-DMD DFT model systems | Pristine Cu-DMD; reduced models with 2H+/2e- per 8 Cu and 4H+/4e- per 8 CuMagnetic Cu(II) centres in pristine and partially reduced models; reduced Cu(I) centres treated as nonmagnetic. · DMD ligands in idealised aligned Cu-DMD chains. | 1D · Model SystemPeriodic 3D and 1D model systems optimised with DFT-PBE0/TZVP in CRYSTAL17; CIF/CRYSTAL coordinate listings are given in the SI. | p003 / article p.10251 · Computational Details |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| As-deposited Cu-DMD thin film on Si(100) with native oxideresearch_0610__mat__mat_cu_dmd | Thin Film · Target Sample · Pristine Framework | As-deposited oxidised state3 cm x 3 cm Si(100) with native oxide · Variable by deposition cycles; example 15 nm films used for several optical/electrical measurements | p002 / article p.10250 · Experimental Section |
| H2/He-reduced Cu-DMD film on interdigitated electrode arrayresearch_0610__mat__mat_cu_dmd | Electrode · Target Sample · Doped | Annealed under flowing 5% H2/He at 170 deg C; high-conductance reduced/protonated stateInterdigitated Au electrode arrays · 15 nm | p004 / article p.10252 · Results and Discussion · Figure 2a |
| As-deposited Cu-DMD film on interdigitated Au electrode arrayresearch_0610__mat__mat_cu_dmd | Electrode · Target Sample · Pristine Framework | As-deposited low-conductivity stateInterdigitated Au electrode arrays; 5 um electrode width and 5 um gap · 15 nm for resistivity measurements | p003 / article p.10251 · Experimental Section |
| Reduced Cu-DMD 2H/8Cu DFT modelresearch_0610__mat__mat_cu_dmd_model | Model · Model System · Model | One H2 equivalent per eight Cu sites: 2H+/2e- per 8 Cu | p005 / article p.10253 · Figure caption · Figure 3b |
| Reduced Cu-DMD 4H/8Cu DFT modelresearch_0610__mat__mat_cu_dmd_model | Model · Model System · Model | Two H2 equivalents per eight Cu sites: 4H+/4e- per 8 Cu | p005 / article p.10253 · Figure caption · Figure 3c |
| Pristine Cu-DMD 3D DFT modelresearch_0610__mat__mat_cu_dmd_model | Model · Model System · Model | Pristine calculated Cu-DMD_4units_3D model | p015 / SI p.14 · Structure models |
| O2-treated Cu-DMD after H2 reductionresearch_0610__mat__mat_cu_dmd | Electrode · Target Sample · Doped | H2-treated film subsequently annealed in flowing O2 up to 130 deg CInterdigitated Au electrode arrays | p005 / article p.10253 · Results and Discussion · Figure S9b |
| Cu-DMD film on Pt-coated Siresearch_0610__mat__mat_cu_dmd | Thin Film · Target Sample · Pristine Framework | As-deposited substrate-orientation comparisonPt-coated Si substrate | p004 / SI p.3 · Supporting Information · Figure S4e,f |
| Cu-DMD film on quartz for UV-vis-NIRresearch_0610__mat__mat_cu_dmd | Thin Film · Target Sample · Pristine Framework | As-deposited and H2/He-annealed optical comparisonQuartz · 15 nm | p003 / article p.10251 · Experimental Section |
| Cu-DMD film on TiN-coated Siresearch_0610__mat__mat_cu_dmd | Thin Film · Target Sample · Pristine Framework | As-deposited substrate-orientation comparisonTiN-coated Si substrate | p005 / SI p.4 · Supporting Information · Figure S6a |