The positive ion chemistry occurring in SiH4/GeF4 gaseous mixtures was investigated by ion trap mass spectrometry and ab initio theoretical calculations. The GeF3+ cation, the only fragment obtained from ionised GeF4, was unreactive towards SiH4. All the primary ions SiHn+ (n = 0–3) react instead with GeF4 to form SiF+ or SiH2F+. The latter species reacts in turn with SiH4 and GeF4 to form SiH3+ and SiHF2+, respectively. The potential energy profiles conceivably involved in these reactions were investigated by ab initio calculations performed at the MP2 and coupled cluster [CCSD(T)] level of theory.
HitchmanM.L.JensenK.F., Chemical Vapour Deposition: Principles and Applications.Academic Press, London, UK (1993).
2.
HessG.G.LampeF.W., “Ionic reactions in gaseous monosilane”, J. Chem. Phys.44, 2257 (1966). doi: 10.1063/1.1727031
3.
MandichM.L.ReentsW.D.JrJarroldM.F., “Sequential clustering reactions of Si+ with SiD4: Identification of a bottleneck preventing rapid growth of hydrogenated silicon particles”, J. Chem. Phys.88, 1703 (1988). doi: 10.1063/1.454737
4.
MandichM.L.ReentsW.D.Jr, “Sequential clustering reactions of SiD+ with SiD4: Rapid growth to kinetic dead-end structures”, J. Chem. Phys.95, 7360 (1991). doi: 10.1063/1.461362
5.
ReentsW.D.JrMandichM.L., “Sequential reactions of SiD2+ with SiD4”, J. Chem. Phys.96, 4429 (1992). doi: 10.1063/1.462834
6.
MandichM.L.ReentsW.D.JrKolenbranderK.D., “Sequential clustering reactions of SiD3+ with SiD4 and SiH3+ with SiH4: Another case of arrested growth of hydrogenated silicon particles”, J. Chem. Phys.92, 437 (1990). doi: 10.1063/1.458446
7.
ReentsW.D.JrMandichM.L., “Hydrogen/deuterium isotope exchange reaction of SiH3+ with SiD4 and SiD3+ with SiH4: Evidence for hydride stripping reactions”, J. Chem. Phys.93, 3270 (1990). doi: 10.1063/1.458860
8.
MandichM.L.ReentsW.D.Jr, “Sequential reactions of bare silicon clusters with SiD4: Constrained heterogeneous nucleation of deuterated silicon particles”, J. Chem. Phys.90, 3121 (1989). doi: 10.1063/1.456667
9.
RaghavachariK., “Sequential clustering reactions of Si+ with silane: A theoretical study of the reaction mechanisms”, J. Chem. Phys.88, 1688 (1988). doi: 10.1063/1.454147
10.
RaghavachariK., “Sequential clustering reactions of SiH+ with silane: An ab initio molecular orbital study”, J. Chem. Phys.95, 7373 (1991). doi: 10.1063/1.461363
11.
RaghavachariK., “Sequential reactions of SiH2+ with silane: A theoretical study”, J. Chem. Phys.96, 4440 (1992). doi: 10.1063/1.462835
12.
RaghavachariK., “Theoretical studies of clustering reactions. Sequential reactions of SiH3+ with silane”, J. Chem. Phys.92, 452 (1990). doi: 10.1063/1.458448
13.
AllenW.N.ChengT.M.H.LampeF.W., “Ion–molecule reactions in SiH4-D2 mixtures”, J. Chem. Phys.66, 3371 (1977). doi: 10.1063/1.434422
14.
BeggsD.P.LampeF.W., “Ionic reactions in gaseous mixtures of monosilane with methane and benzene”, J. Phys. Chem.73, 4194 (1969). doi: 10.1021/j100846a027
15.
ChengT.M.H.YuT.-Y.LampeF.W., “Ion–molecule reactions in monosilane–methane mixtures”, J. Phys. Chem.77, 2587 (1973). doi: 10.1021/j100640a001
16.
AllenW.N.LampeF.W., “Direct detection of energy-rich collision complexes in the reactions of Si+, SiH+, and SiH3+ ions with benzene”, J. Chem. Phys.65, 3378 (1976). doi: 10.1063/1.433470
17.
MayerM.T.LampeF.W., “Ion–molecule reactions in monosilane–acetylene mixtures”, J. Phys. Chem.78, 2645 (1974). doi: 10.1021/j100619a002
18.
MayerM.T.LampeF.W., “Ion–molecule reactions in monosilane–ethylene mixtures”, J. Phys. Chem.78, 2433 (1974). doi: 10.1021/j100617a004
19.
AllenW.L.LampeF.W., “Persistent collision complexes in the reaction of silyl ions with ethylene”, J. Am. Chem. Soc.99, 6816 (1977). doi: 10.1021/ja00463a005
20.
AbernathyR.N.LampeF.W., “The role of collision complexes in the reaction of silyl ions with ethylene”, J. Am. Chem. Soc.103, 2573 (1981). doi: 10.1021/ja00400a015
21.
AbernathyR.N.LampeF.W., “Collisional moderation by foreign gases in the reaction of silyl ion SiH3+ with C2H4”, Int. J. Mass Spectrom. Ion Phys.51, 3 (1983). doi: 10.1016/0020-7381(83)85022-0
22.
ReuterK.A.JacobsonD.B., “Novel hydrogen/methyl exchange between SiHx(CH3)3–x+ (x = 1–3) and propene in the gas phase”, Organometallics8, 1126 (1989). doi: 10.1021/om00106a046
23.
BareJ.P.LampeF.W., “Free-radical chain formation of siloxanes in the radiolysis of monosilane–nitric oxide mixtures”, J. Phys. Chem.81, 1437 (1977). doi: 10.1021/j100530a001
24.
LimK.P.LampeF.W., “Ion/molecule reactions in silane–carbon monoxide mixtures: Possible synthesis of the SiC radical in the electric discharge chemistry”, Int. J. Mass Spectrom. Ion Processes101, 245 (1990). doi: 10.1016/0168-1176(90)87014-8
25.
ChengT.M.H.LampeF.W., “Positive-ion reactions in monosilane–water mixtures”, J. Phys. Chem.77, 2841 (1973). doi: 10.1021/j100642a004
26.
HallerI., “Ion–molecule reactions in the silane–ammonia system”, J. Phys. Chem.94, 4135 (1990). doi: 10.1021/j100373a047
27.
TachibanaA.KawauchiS.YoshidoN.YamabeT.FukuiK., “Ion–molecule reactions between SiH3+ and NH3”, J. Mol. Struct.300, 501 (1993). doi: 10.1016/0022-2860(93)87042-8
28.
StinespringC.D.WormhoudtJ.C., “Gas phase kinetics analysis and implications for silicon carbide chemical vapor deposition”, J. Cryst. Growth87, 481 (1988). doi: 10.1016/0022-0248(88)90096-6
29.
AllendorfM.D.KeeR.J., “A model of silicon carbide chemical vapor deposition”, J. Electrochem. Soc.138, 841 (1991). doi: 10.1149/1.2085688
30.
WilliamsK.L.MartinI.T.FisherE.R., “On the importance of ions and ion–molecule reactions to plasma surface interface reactions”, J. Am. Soc. Mass Spectrom.13, 518 (2002). doi: 10.1016/S1044-0305(02)00371-9
31.
GalJ.-F.GroverR.MariaP.-C.OpertiL.RabezzanaR.VaglioG.-A.VolpeP., “Gas-phase N-Si ion clusters in ammonia/silane mixtures”, J. Phys. Chem.98, 11978 (1994). doi: 10.1021/j100097a025
32.
AntoniottiP.OpertiL.RabezzanaR.VaglioG.-A.VolpeP.GalJ.-F.GroverR.MariaP.-C., “Gas phase ion–molecule reactions in phosphine/silane mixtures”, J. Phys. Chem.100, 155 (1996). doi: 10.1021/jp951439u
33.
AntoniottiP.CanepaC.OpertiL.RabezzanaR.TonachiniG.VaglioG.-A., “Gas-phase ion chemistry of silane with ethane and ethyne”, J. Organomet. Chem.589, 150 (1999). doi: 10.1016/S0022-328X(99)00397-6
34.
AntoniottiP.CanepaC.OpertiL.RabezzanaR.TonachiniG.VaglioG.-A., “Experimental and theoretical study of the formation of silicon–carbon ion species in gaseous silane/ethene mixtures”, J. Phys. Chem. A103, 10945 (1999). doi: 10.1021/jp992722m
35.
AntoniottiP.OpertiL.RabezzanaR.VaglioG.-A.VolpeP., “Gas phase ion chemistry in silane/propane and silane/propene mixtures”, Int. J. Mass Spetrom.190/191, 243 (1999). doi: 10.1016/S1387-3806(99)00024-X
36.
BenziP.OpertiL.RabezzanaR., “Ion chemistry in XH4/allene (X = Ge, Si) gaseous mixtures – formation of X–C bonds”, Eur. J. Inorg. Chem.505 (2000). doi: 10.1002/(SICI)1099-0682(199903)2000:3
37.
CanepaC.MaranzanaA.OpertiL.RabezzanaR.VaglioG.-A., “Selectivity in gas-phase ion chemistry. Competitive fast reactions in a silane/propene system”, Organometallics20, 4593 (2001). doi: 10.1021/om010339+
38.
OpertiL.RabezzanaR.TurcoF.VaglioG.-A., “Gas-phase ion chemistry in silane/propyne mixtures”, Int. J. Mass Spectrom.227, 235 (2003). doi: 10.1016/S1387-3806(03)00124-6
39.
CalderanS.CarboneP.OpertiL.RabezzanaR.VaglioG.-A., “Gas-phase ion chemistry in the ternary SiH4–C3H6–NH3 system”, J. Mass Spectrom.37, 1205 (2002). doi: 10.1002/jms.379
40.
CalderanS.OpertiL.RabezzanaR.VaglioG.-A., “Gas-phase ion chemistry in the ternary SiH4–C3H6–PH3 system”, J. Mass Spectrom.37, 155 (2002). doi: 10.1002/jms.268
41.
OpertiL.RabezzanaR.TurcoF.VaglioG.-A., “Gas-phase ion chemistry of the allene–phosphine and silane–allene–phosphine systems”, J. Mass Spectrom.39, 665 (2004). doi: 10.1002/jms.639
42.
OpertiL.RabezzanaR.TurcoF.VaglioG.-A., “Gas-phase ion chemistry in the ternary silane–propyne–phosphine system”, J. Mass Spectrom.39, 682 (2004). doi: 10.1002/jms.641
43.
OpertiL.RabezzanaR.TurcoF.VaglioG.-A., “Gas-phase ion chemistry of the propyne/ammonia and silane/propyne/ammonia systems”, Int. J. Mass Spectrom.232, 139 (2004). doi: 10.1016/j.ijms.2003.12.010
44.
OpertiL.RabezzanaR.TurcoF.VaglioG.-A., “Gas-phase ion chemistry in XH4–C3H4–ZH3 (X = Si, Ge; Z = N, P) mixtures”, J. Mass Spectrom.40, 591 (2005). doi: 10.1002/jms.825
45.
LimK.P.LampeF.W., “The reactions of silyl ions with chloromethanes”, Int. J. Mass Spectrom. Ion Processes92, 53 (1989). doi: 10.1016/0168-1176(89)83018-6
46.
KrauseJ.R.LampeF.W., “Extensive redistribution of fluorine and hydrogen in the reaction of CF3+ with SiH4”, J. Am. Chem. Soc.98, 7826 (1976). doi: 10.1021/ja00440a065
47.
KrauseJ.R.LampeF.W., “Ion–molecule reactions in SiH4–CF4 mixtures”, J. Phys. Chem.81, 281 (1977). doi: 10.1021/j100519a001
48.
AntoniottiP.OpertiL.RabezzanaR.TurcoF.VaglioG.A., “Gas-phase ion chemistry of Si+ and NF3: An experimental and theoretical study”, Int. J. Mass Spectrom.255, 225 (2006). doi: 10.1016/j.ijms.2006.01.010
49.
AntoniottiP.OpertiL.RabezzanaR.TurcoF.BorocciS.GrandinettiF., “Positive ion chemistry of SiH4/NF3 gaseous mixtures studied by ion trap mass spectrometry”, Eur. J. Mass Spectrom.15, 220 (2009). doi: 10.1255/ejms.950
50.
AntoniottiP.OpertiL.RabezzanaR.TurcoF.ZanzotteraC.GiordaniM.GrandinettiF., “Gas-phase reactions of XH3+ X = C, Si, Ge) with NF3: A comparative investigation on the detailed mechanistic aspects”, J. Mass Spectrom.44, 1348 (2009). doi: 10.1002/jms.1617
51.
AntoniottiP.BorocciS.BronzolinoN.GiordaniM.GrandinettiF., “Cationic germanium fluorides: A theoretical investigation on the structure, stability, and thermochemistry of GeFn/GeFn+ (n = 1–3)”, J. Phys. Chem. A110, 4900 (2006). doi: 10.1021/jp057064m
52.
AntoniottiP.RabezzanaR.BorocciS.BronzolinoN.GiordaniM.GrandinettiF., “Cationic germanium fluorides. 2. An experimental and theoretical investigation on the reaction between GeF+ and H2O”, Int. J. Mass Spectrom.257, 50 (2006). doi: 10.1016/j.ijms.2006.06.016
53.
AntoniottiP.BorocciS.BronzolinoN.GiordaniM.GrandinettiF., “Fluoromethyl cations and group XIV congeners AHnF3–n+ (A = Si, Ge, Sn, Pb; n = 0–2): From covalent structures to ion–molecule complexes”, Eur. J. Inorg. Chem.3010 (2006). doi: 10.1002/ejic.200600388
54.
AntoniottiP.RabezzanaR.TurcoF.BorocciS.GiordaniM.GrandinettiF., “Ion chemistry in germane/fluorocompounds gaseous mixtures: A mass spectrometric and theoretical study”, J. Mass Spectrom.43, 1320 (2008). doi: 10.1002/jms.1404
55.
AntoniottiP.BottizzoE.OpertiL.RabezzanaR.BorocciS.GrandinettiF., “Gas-phase chemistry of ionized and protonated GeF4: A joint experimental and theoretical study”, J. Mass. Spectrom.46, 465 (2011). doi: 10.1002/jms.1913
56.
SlobodinD.AljishiS.OkadaY.ShenD.S.ChuV.WagnerS., “Hydrogenated fluorinated amorphous silicon–germanium alloys prepared from silane and tetrafluorogermane”, Mat. Res. Soc. Symp. Proc.70, 275 (1986).
57.
AmbrosioR.TorresA.KosarevA.ZunigaC.AbramovA.S., “Silicon–germanium films prepared from SiH4 and GeF4 by low-frequency plasma deposition”, J. Non-Cryst. Solids329, 134 (2003). doi: 10.1016/j.jnon-crysol.2003.08.027
58.
BartmessJ.E.GeorgiadisR.M., “Empirical methods for determination of ionization gauge relative sensitivities for different gases”, Vacuum33, 149 (1983). doi: 10.1016/0042-207X(83)90004-0
59.
OpertiL.SplendoreM.VaglioG.A.FranklinA.M.ToddJ.F.J., “Investigation of the complex reactions of SiH4 and GeH4 in the ion trap using dynamically programmed scanning”, Int. J. Mass Spectrom. Ion Processes136, 25 (1994). doi: 10.1016/0168-1176(94)04026-5
60.
GronertS., “Quadrupole ion trap studies of fundamental organic reactions”, Mass Spectrom. Rev.24, 100 (2005). doi: 10.1002/mas.20008
61.
MarchR.E.ToddJ.F.J., Fundamentals of Ion Trap Mass Spectrometry, Vol. 1. CRC Press, Boca Raton, Florida, USA (1995).
62.
BasicC.EylerJ.R.YostR.A., “Probing trapped ion energies via ion–molecule reaction kinetics: Quadrupole ion trap mass spectrometry”, J. Am. Soc. Mass Spectrom.3, 716 (1992). doi: 10.1016/1044-0305(92)87084-C
63.
LinstromP.J.MallardW.G. (Eds), NIST Chemistry Webbook, NIST Standard Reference Database Number 69. National Institute of Standards and Technology, Gaithersburg, MD, USA, June 2005, http://webbook.nist.gov.
MøllerC.PlessetM.S., “Note on the approximation treatment for many-electrons systems”, Phys. Rev.46, 618 (1934). doi: 10.1103/PhysRev.46.618
66.
GonzalezC.SchlegelH.B., “Reaction path following in mass-weighted internal coordinates”, J. Phys. Chem.94, 5523 (1990). doi: 10.1021/j100377a021
67.
RaghavachariK.TrucksG.W.PopleJ.A.Head-GordonM., “A fifth-order perturbation comparison of electron correlation theories”, Chem. Phys. Lett.157, 479 (1989). doi: 10.1016/S0009-2614(89)87395-6
68.
GlendeningE.D.ReedA.E.CarpenterJ.E.WeinholdF., NBO, Version 3.1 (as implemented in Gaussian 03).
69.
HarlandP. W.CradockS.ThynneJ.C.J., “Positive and negative-ion formation due to the electron bombardment of germanium tetrafluoride”, Int. J. Mass Spectrom. Ion Phys.10, 169 (1972/73). doi: 10.1016/0020-7381(72)83007-9
70.
BasnerR.SchmidtM.TarnovskyV.BeckerK.DeutschH., “Dissociative ionization of silane by electron impact”, Int. J. Mass Spectrom. Ion Processes171, 83 (1997). doi: 10.1016/S0168-1176(97)00063-3
71.
HoP.MeliusC.F., “A theoretical study of the thermochemistry of SiFn and SiHnFm compounds and Si2F6”, J. Phys. Chem.94, 5120 (1990). doi: 10.1021/j100375a047
72.
WangL.ZhangJ., “Quantum chemistry study on cation structures of fluorinated and chlorinated germanes and their radicals”, J. Phys. Chem. A112, 3454 (2008). doi: 10.1021/jp7115752
73.
SuT.ChesnavichW.G., “Parametrization of the ion–polar molecule collision rate constants by trajectory calculations”, J. Chem. Phys.76, 5183 (1982). doi: 10.1063/1.442828
74.
LideR.D. (Ed), CRC Handbook of Chemistry and Physics, 73rd Edn.CRC Press, Boca Raton, Florida, USA (1992).
