Phosphite copper(i) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

Abstract

Metal-organics [((RO)(3)P)(m)CuO(2)CCF(3)] (R = CH(3): 11a, m = 1; 11b, m = 2; 11c, m = 3. R = CH(2)CH(3): 12a, m = 1; 12b, m = 2; 12c, m = 3. R = CH(2)CF(3): 13a, m = 1; 13b, m = 2; 13c, m = 3) are either accessible by the reaction of [((RO)(3)P)(m)CuCl] (R = CH(3): 5a, m = 1; 5b, m = 2; 5c, m = 3. R = CH(2)CH(3): 6a, m = 1; 6b, m = 2; 6c, m = 3) with [KO(2)CCF(3)] (7), or treatment of [Cu(2)O] (8) with HO(2)CCF(3) (9) and P(OR)(3) (2, R = CH(3); 3, R = CH(2)CH(3); 4, R = CH(2)CF(3)). (31)P{(1)H} NMR spectra [((CH(3)O)(3)P)(m)CuO(2)CCF(3)] (m = 1, 1.5, 2, 2.5, 3, 3.5, and 4) have been studied at 25 and -80 °C showing phosphite ligand exchange in solution. The molecular structures of 11a and 13a-13c in the solid state are reported. Complexes 11a and 13a are tetramers featuring μ-η(2)(1κO:2κO')- and μ(3)-η(2)(1κO:2κO':3κO')-(11a) or μ(3)-η(2)(1κO:2κO':3κO')-bonded O(2)CCF(3) ligands (13a) with the Cu(I) ions being part of CuPO(2) and CuPO(3) units (11a), while in 13a solely a CuPO(3) moiety is present. Skeletal isomerism of 11a vs. 13a is discussed. Compound 13b is dimeric ({CuP(2)O(2)}(2)) with pseudo-tetrahedral Cu environments and μ-η(2)(1κO:2κO')O(2)CCF(3) functionalities. In monomeric 13c the O(2)CCF(3) ligand is η(1)(κO)-bonded to a tetra-coordinated Cu(i) ion. The thermal solid state properties of 11, 12 and 13 were studied by Thermo Gravimetry (TG). These complexes decompose by phosphite elimination, decarboxylation and dealkylation. Hot-wall Chemical Vapour Deposition (CVD) experiments were carried out at 380 °C using 11c as precursor for the deposition of copper onto pieces of TiN-coated oxidized silicon substrates. Copper layers of high purity were obtained with grain sizes between 200-1200 nm.

Organophosphine/phosphite stabilized disilver(i) methanedisulphonates: synthesis, solid state structures and their potential use as MOCVD precursors

“…The carbon resonances of -CH 2 -on -O 3 SCH 2 SO 3 -are observed in the lower field (68.1-68.9 ppm) comparing to that of [P(OEt) 3 ] (60.1-61.3 ppm).At room temperature, the phosphorus resonance signals for all coordination complexes 2a-2e and 2f-2h appear between 5.0-11.5 ppm and 126.8-130.3 ppm as single signals, respectively. A trend can be seen in the chemical shift of the 31 P{ 1 H} NMR signals for 2f-2h as a previous report 42. Complexes with only one equivalent phosphite ligand per silver(I) centre show a signal at higher field, while addition of a second and a third equivalent of P(OEt)3 subsequently shifts the signals to lower field, i.e.…”

Dithiocarbamate copper(I) and silver(I) complexes: Synthesis, structure and thermal behavior

“…As expected, the analogous copper complexes show no coupling pattern under similar conditions. The additional signal broadening for the phosphine copper(I) species (up to 9000 Hz) results from the quadrupole effect of the copper isotopes 63 Cu and 65 Cu (I = 3/2), respectively, which makes the appropriate studies in comparison to silver more complicated [15]. The temperature dependent 31 P{ 1 H} NMR spectra of representative [Ag(PBu 3 ) 2 (S 2 CNMe(C 2 H 4 OH))] (8a) are shown in Fig.…”

Synthesis of β‐Ketoiminato Copper(II) Complexes and Their Use in Copper Deposition

“…For the formation of copper and copper oxides several methods have been applied including electrochemical deposition,, thermal oxidation of copper, magnetron sputtering, spin‐coating, chemical beam epitaxy (CBE), atomic layer deposition (ALD), and chemical vapor deposition (CVD) , , …”

“…[20][21][22] For the formation of copper and copper oxides several methods have been applied including electrochemical deposition, [23,24] thermal oxidation of copper, [25] magnetron sputtering, [26] spin-coating, [27][28][29][30][31] chemical beam epitaxy (CBE), [32] atomic layer deposition (ALD) [6,[33][34][35][36][37] and chemical vapor deposition (CVD). [8,10,[38][39][40] For the vacuum-based deposition of copper or copper oxide films the precursors can be classified in two groups: Copper(I) and copper(II) compounds, respectively. [41][42][43] Beneficial for copper(I) complexes is their ability to deposit pure copper films at low temperature (Ͻ200°C) usually without addition of any reducing agents.…”

“…[41][42][43] Beneficial for copper(I) complexes is their ability to deposit pure copper films at low temperature (Ͻ200°C) usually without addition of any reducing agents. [41] Representatives are copper(I) β-diketonates (for example, [Cu(η 2 -H 2 C=CHSiMe 3 )(hfac)], [44] hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; [(R 3 P) 2 Cu(acac)], R = nBu, [6,34,37] OMe, [45] Et, [45] acac = acetylacetonate), alkoxides (i.e., [Cu(OtBu)] 4 [38] ), and carboxylates ([((RO) 3 P) m CuO 2 CCF 3 ], [39] R = Me, Et, CH 2 CF 3 ; m = 1, 2, 3; [(nBu 3 P) m CuO 2 CR], [46] R = Me, CF 3 , Ph, CH=CHPh; m = 1, 2, 3). Commonly, copper(II) complexes are solids and need the addition of reducing agents for the deposition of pure copper films at higher temperature (Ͼ250°C).…”