Ligand influence on the formation of P/Se semiconductor materials from metal–organic complexes

Abstract

The complexes [Ni{(SeP(i)Pr(2))(2)N}(2)] (2), [Ni(Se(2)P(i)Pr(2))(2)] (), and [Co(Se(2)P(i)Pr(2))(2)] (4) were synthesised and the X-ray single crystal structures of (1) and (2) were determined. Thin films of nickel selenide, cobalt selenide and cobalt phosphide have been deposited by the chemical vapour deposition method using imidodiselenophosphinato-nickel(ii) (1), -cobalt(ii) [Co{(SeP(i)Pr(2))(2)N}(2)] (3), diselenophosphinato-nickel(ii) (2), -cobalt(ii) (4) and diselenocarbamato-nickel(ii) [Ni(Se(2)CNEt(2))(2)] (5), and -cobalt(iii) [Co(Se(2)CNEt(2))(3)] (6) precursors.

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr2)2N}2] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

“…In the work presented herein, the structural, spectroscopic, and electrochemical investigation of [Fe{(EP i Pr 2 ) 2 N} 2 ] [E = S ( 1 ), Se ( 2 )] is described to extend the dataset of Fe II complexes bearing [R 2 P(E)NP(E)R 2 ] – ligands. The ligands employed in this study afford the structurally characterized first‐row transition‐metal complexes [M II L 2 ] (E = S, M = Mn, Co, Ni, Zn;, E = Se, M = Co, Ni,, Zn) . The [(SeP i Pr 2 ) 2 N] – ligand exhibits a remarkable flexibility, as it affords both tetrahedral and square‐planar [Ni{(SeP i Pr 2 ) 2 N} 2 ] isomers , , .…”

“…The ligands employed in this study afford the structurally characterized first‐row transition‐metal complexes [M II L 2 ] (E = S, M = Mn, Co, Ni, Zn;, E = Se, M = Co, Ni,, Zn) . The [(SeP i Pr 2 ) 2 N] – ligand exhibits a remarkable flexibility, as it affords both tetrahedral and square‐planar [Ni{(SeP i Pr 2 ) 2 N} 2 ] isomers , , . It is of interest that the synthesis of the [Cu{(EP i Pr 2 ) 2 N} 2 ] complexes has not yet been achieved, most likely because of the propensity of Cu I ions to afford stable trinuclear [Cu I 3 {(EP i Pr 2 ) 2 N} 3 ] compounds (E = S, Se) …”

“…The application of such methods to various precursors to afford first‐row transition‐metal chalcogenides has been reviewed recently by O'Brien and co‐workers . For instance, [M{(EP i Pr 2 ) 2 N} 2 ] (M = Ni, E = S, Se;, , M = Zn, E = Se) have been used for the deposition of ME (E = S, Se) and MP (M = Ni, Zn). For [Bi{(EP i Pr 2 ) 2 N} 3 ] (E = S, Se), the formation of Bi 2 E 3 has been observed .…”

Experimental and Theoretical Investigations of the Contact Ion Pairs Formed by Reactions of the Anions [(EPR2)2N]− (R = iPr, tBu; E = S, Se) with the Cations [(TePR2)2N]+ (R = iPr, tBu)

“…The primary focus has been the coordination chemistry of these bidentate ligands, and several reviews that provide details of the complexes of 1 with a diverse array of main group, lanthanide and transition metals have been published. [3][4][5] A significant recent application of these complexes, particularly in the case of the selenium derivative (1, E = Se, R = i Pr), has been as single-source precursors for the generation of metal selenides in the form of semiconducting thin films [6][7][8][9][10][11][12][13][14][15][16][17] or quantum dots 18 via CVD or solvothermal processes.…”

Facile Synthesis of Bis(dichalcogenophosphinate)s and a Remarkable [Li8(OH)6]2+ Polyhedron

“…Despite this potential drawback, diselenophosph(in)ates have been studied in some depth both for their diverse coordination chemistry, in particularly with soft metal centers such as copper(I), 8 and for their potential applications such as precursors to metal selenide semi-conducting materials. [9][10][11][12][13] In contrast, the heavier ditellurophosp(in)ate homologs are virtually unreported -the only structurally characterized example being the solvent separate ion pair complex [Ph 2 PTe 2 ][Li(THF) 3.5 (TMEDA) 0.25 ] (TMEDA = tetramethyl-ethylenediamine). 14 We have recently reported upon a clean and high-yielding route to dichalcogenophosphinates based upon the treatment of metallated secondary phosphines with two equivalents of elemental chalcogen (Scheme 1).…”