Intramolecularly Coordinated Gallium Sulfides: Suitable Single Source Precursors for GaS Thin Films

Abstract

Our studies have been focused on the synthesis of N→Ga coordinated organogallium sulfides [L Ga(μ-S)] (1) and [L Ga(μ-S)] (2) containing either N,C,N- or C,N-chelating ligands L or L (L is {2,6-(Me NCH ) C H } and L is {2-(Et NCH )-4,6-tBu -C H } ). As the result of the different ligands, compounds 1 and 2 differ mutually in their structure. To change the Ga/S ratio, unusually N→Ga coordinated organogallium tetrasulfide L Ga(κ -S ) (3) was prepared and the unprecedented complex [{2-[CH{(CH ) CH }(μ-OH)]-6-CH NMe }C H ]GaS (4) was also isolated as the minor by-product of the reaction. Compounds 1-3 were further studied as potential single-source precursors for amorphous GaS thin film deposition by spin-coating.

Synthesis, Structure and Application of Intramolecularly‐Coordinated Gallium Chalcogenides: Suitable Single‐Source precursors for GaxSey Materials

“…The Ga−Se bond lengths in 1 and 2 (the range of the Ga−Se distance is 2.3624(5)–2.4097(6) Å) are just within the currently known range (2.37–2.54 Å) for organogallium Ga‐Se species . It should be also noted, that an analogous gallium sulfide [L 1 Ga(μ‐S)] 3 was found to be a trimer with six member Ga 3 S 3 , whereas a similar dimeric structure was found for [L 2 Ga(μ‐S)] 2 …”

“…Compound 3 represents the first structurally characterized organogallium complex containing a GaSe 4 fragment, with Se−Se bond lengths ranging from 2.3252(10) to 2.3463(10) Å. It seems that the presence of the ligand L 1 is crucial for the isolation of this fragment since a similar (κ 2 ‐S 4 ) fragment was also isolated in related L 1 Ga(κ 2 ‐S 4 ) …”

“…For 2 , comparison of observed (62 %) mass losses with total expected (65 %) indicate smooth formation of GaSe. Previously, we have reported on the deposition of amorphous GaS material from N→Ga‐coordinated organogallium sulfides by spin‐coating method, where the complex [L 1 Ga(μ‐S)] 3 with different ligand L 1 was the most suitable . Similarly to this process, compound 2 was dissolved in propylamine ( c =0.06 mol l −1 ) and used as SSP for the preparation of GaSe thin films by spin‐coating (for experimental details see Supporting Information).…”

“…Those are the reasons for the single‐source precursors’ application to develop good quality amorphous GaSe thin films presented in this work. Moreover, we have showed the possible preparation of amorphous GaS material by a spin‐coating method using organometallic N→Ga‐coordinated organogallium sulfides as suitable SSPs recently . To expand our studies on the synthesis of remaining amorphous III‐VI materials by the spin‐coating method, here we focus on the synthesis of N→Ga‐coordinated organogallium selenides and tellurides [L 1 Ga(μ‐Se)] 2 ( 1 ), [L 2 Ga(μ‐Se)] 2 ( 2 ) and [L 1 Ga(μ‐Te)] 2 ( 3 ), respectively, containing either N,C,N‐ or C,N‐chelating ligands L 1, 2 (L 1 is {2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 } − and L 2 is {2‐(Et 2 NCH 2 )‐4,6‐ t Bu 2 ‐C 6 H 2 } − ).…”

Synthesis and Application of Monomeric Chalcogenolates of 13 Group Elements

“…Later on, complexes [Me 2 M(SeP i Pr 2 ) 2 n ] (Figure B) and {M(μ‐Te)[N( i Pr 2 PTe) 2 ]} 3 (Figure C) were used for the deposition of cubic M 2 E 3 (E=Se, Te) thin films and the complexes GaCl 3⋅ ( n Bu 2 E) were applied in low pressure CVD (LP‐CVD) of crystalline Ga 2 E 3 . Our previous studies also showed that N→Ga coordinated chalcogenides [LGa(μ‐S)] 3 and [L 1 Ga(μ‐Se)] 2 (L={2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 } − and L 1 ={2‐(Et 2 NCH 2 )‐4,6‐ t Bu 2 ‐C 6 H 2 } − ) (Figure D, E) can be exploited as SSPs for the deposition of III–VI amorphous thin films by spin coating method …”