Synthesis · 2D Semiconducting Metal–Organic Framework Thin Films for Organic Spin Valves

4 structured synthesis routes

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

Complete recipeSource: SI

Route 1: Other

S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films

Metal precursors0.1 mM Cu(OAc)2 solution in ethanol

Linker precursors0.01 mM HHTP solution in ethanol

SolventsChloroform, isopropanol, octanol, ethanol, water

AdditivesH2O2:NH4OH:H2O (1:1:5) cleaning bath; 3-APTMS self-assembled monolayer

AtmosphereN2 stream drying; growth atmosphere not otherwise specified

TemperatureLSMO cleaning bath 85 C; 3-APTMS/octanol reflux; oven drying 70 C

TimeLSMO chloroform sonication 10 min; cleaning bath 30 min; isopropanol sonication 10 min; 3-APTMS reflux 20 min; oven dry 15 min; each growth cycle 20 min Cu and 40 min HHTP

Substrate orientationPatterned LSMO electrodes on (001)-oriented STO

Oxidant / reductantH2O2-containing substrate cleaning bath

Work-upRinsed with alcohol and water after silanisation; washed with pure ethanol after each MOF growth cycle.

ActivationDried in N2 stream and at 70 C before growth; no post-growth activation stated.

Scalability contextIn situ layer-by-layer growth on LSMO; thickness controlled by cycle number.

Show 4 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	0.1 mM in ethanol	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Linker	HHTP	0.01 mM in ethanol	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Additive	(3-aminopropyl)trimethoxysilane (3-APTMS)	1:100 (v/v) solution in octanol	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Solvent	ethanol	Not specified	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films

Complete recipeSource: SI

Route 2: Other

S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films

Metal precursors0.1 mM Cu(OAc)2 solution in ethanol

Linker precursors0.01 mM HHTP solution in ethanol

SolventsEthanol; deionized water, ethanol, acetone, isopropyl alcohol for cleaning

AdditivesPiranha solution for quartz; H2O2:NH4OH:H2O (1:1:5) for ITO; N2 drying

AtmosphereN2 stream drying; growth atmosphere not otherwise specified

TemperatureSubstrate pretreatment: quartz piranha 100 C; ITO H2O2/NH4OH/H2O 85 C

TimeEach growth cycle: Cu(OAc)2 soak 20 min; HHTP soak 40 min

Substrate orientationquartz glass or ITO glass

Oxidant / reductantH2O2-containing substrate cleaning baths

Work-upWashed with pure ethanol after each repeating growth cycle.

ActivationFunctionalised substrates dried in N2 stream before growth; no post-growth activation stated.

Scalability contextFilm thickness controlled by number of growth cycles; reported growth rate about 5 nm per cycle.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	Cu(OAc)2	0.1 mM in ethanol	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Linker	HHTP	0.01 mM in ethanol	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Solvent	ethanol	Not specified	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Additive	H2SO4/H2O2 piranha solution	H2SO4 (95%-98%)/H2O2 (30%) = 7:3	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films
Additive	H2O2:NH4OH:H2O bath	1:1:5	S4 · Fabrication Procedure of Cu3(HHTP)2 2D c-MOF Thin Films

Complete recipeSource: SI

Route 3: Solvothermal

S4 · Synthesis of Cu3(HHTP)2 Powder

Metal precursorsCopper acetate (16 mg)

Linker precursorsHHTP (13 mg)

Solvents2 mL water/N,N-dimethylformamide (DMF), v/v = 1:1

Atmospheresealed vial; atmosphere not specified

Temperature85

Time24

Work-upNatural cooling to room temperature; centrifuged; washed with water and acetone.

ActivationDried in vacuum for 12 h.

Show 3 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	copper acetate	16 mg	S4 · Synthesis of Cu3(HHTP)2 Powder
Linker	HHTP	13 mg	S4 · Synthesis of Cu3(HHTP)2 Powder
Solvent	water/N,N-dimethylformamide (DMF)	2 mL; v/v = 1:1	S4 · Synthesis of Cu3(HHTP)2 Powder

Complete recipeSource: SI

Route 4: Other

S4 · Fabrication of the Cu3(HHTP)2 2D c-MOF-Based Spin Valves

Metal precursorsLSMO target; Cu(OAc)2; Co (99.95%); Au (99.999%) granules

Linker precursorsHHTP

SolventsEthanol for Cu3(HHTP)2 layer-by-layer growth

Additives3-APTMS-modified LSMO/STO bottom electrode

AtmosphereLSMO RF sputtering in 0.5 Pa Ar/O2 mixed atmosphere (Ar 10 sccm, O2 6 sccm); annealing in 260 Pa pure O2; Co and Au by thermal evaporation

TemperatureLSMO growth 770 C; in-situ annealing 770 C; room-temperature cooling at 5 K/min

TimeLSMO in-situ annealing 1 h; MOF cycles 20 min Cu and 40 min HHTP; Co/Au evaporation times not reported

Substrate orientation(001)-oriented SrTiO3

Work-upCo deposited at less than 16.7 Angstrom/s through a shadow mask; Au cap deposited by thermal evaporation.

Scalability contextDevice junction area 200 x 200 um2; 30-100 nm MOF spacers reported.

Show 5 structured reagent records

Role	Reagent	Amount / concentration	Source
Metal Source	La0.67Sr0.33MnO3 (LSMO) target	Not specified	S4 · Fabrication of the Cu3(HHTP)2 2D c-MOF-Based Spin Valves
Metal Source	Co	99.95%; around 50 nm-thick electrode	S4 · Fabrication of the Cu3(HHTP)2 2D c-MOF-Based Spin Valves
Metal Source	Au granules	99.999%; more than 50 nm layer	S4 · Fabrication of the Cu3(HHTP)2 2D c-MOF-Based Spin Valves
Metal Source	Cu(OAc)2	0.1 mM in ethanol	S4 · Fabrication of the Cu3(HHTP)2 2D c-MOF-Based Spin Valves
Linker	HHTP	0.01 mM in ethanol	S4 · Fabrication of the Cu3(HHTP)2 2D c-MOF-Based Spin Valves