The gas phase ion-molecule reactions in positively and negatively ionized germane/diborane mixtures have been studied by ion trap mass spectrometry. Reaction sequences and rate constants for the most interesting processes have been determined. In positive ionization, formation of Ge-B bonds exclusively occurs through condensation reactions of BnHm+ ions with germane, followed by H2 or BH3 loss. No reactions of ions from germane with B2H6 were observed under the experimental conditions used here. In negative ionization, the GenHm (n = 1, 2) ion families react with diborane to yield the GenBpHq -(p = 1, 2) ions, again via dehydrogenation and BH3 loss, while diborane anions proved to be unreactive. In both positive and negative ionization, Ge-B ions reach appreciable abundances. The present results afford fundamental information about the intrinsic reactivity of gas-phase ions and provide valuable indications about the first nucleation steps ultimately leading to amorphous Ge and B-doped semiconductor materials by chemical vapor deposition methods.
ChopraK.L.PaulsonP.D.DuttaV., “Thin-film solar cells: An overview”, Prog. Photovolt: Res. Appl.12, 69 (2004). doi: 10.1002/pip.541
2.
ZweibelK., “Thin-film PV manufacturing: Material costs and their optimization”, Sol. Energy Mater. Sol. Cells63, 375 (2000). doi: 10.1016/S0927-0248(00)00057-X
3.
ZweibelK., “Issues in thin film PV manufacturing cost reduction”, Sol. Energy Mater. Sol. Cells59, 1 (1999). doi: 10.1016/S0927-0248(99)00019-7
4.
MurotaJ.SakurabaM.TillackB., “Atomically controlled processing for group IV semiconductors by chemical vapor deposition”, Jpn. J. Appl. Phys.45, 6767 (2006). doi: 10.1143/JJAP.45.6767
5.
TanB.L.TanT.L., “A study of Si/Ge selective epitaxial growth by experimental design approach”, Thin Solid Films504, 95 (2006). doi: 10.1016/j.tsf.2005.09.049
BorlandJ.HautalaJ.TabatM.GwinnM.TetreaultT.SkinnerW., “Ge & Ge+B infusion doping and deposition for ultra-shallow junction, blanket and localized SiGe or Ge formation on Cz and SOI wafers”, Proceedings—Electrochemical Society2004–07, 769 (2004).
9.
TalbotA.AvenierG.VincentG.DutartreD., “Growth kinetic and doping of Si and SiGe epi layers on fullsheet substrates”, Mat. Sci. Eng. B114/115, 318 (2004). doi: 10.1016/j.mseb.2004.07.078
10.
ShimH.SakurabaM.TsuchiyaT.MurotaJ., “Work function of impurity-doped polycrystalline Si1-x-yGexCy film deposited by ultraclean low-pressure CVD”, Appl. Surf. Sci.212/213, 209 (2003). doi: 10.1016/S0169-4332(03)00079-5
11.
MurotaJ.MatsuuraT.SakurabaM., “Atomically controlled processing for group IV semiconductors”, Surf. Interface Anal.34, 432 (2002). doi: 10.1002/sia.1332
12.
PesovicN.OzturkM.C., “Effects of Cl2 on in-situ boron doped Si1-xGex alloys”, Proceedings—Electrochemical Society2002–11, 407 (2002).
13.
SimpsonD.L.CroswellR.T.ReismanA.WilliamsC.K.TempleD., “Deposition and characterization of undoped and boron and phosphorus doped (SixGe1-xO2) glass films”, J. Electrochem. Soc.147, 1560 (2000). doi: 10.1149/1.1393394
14.
SimpsonD.L.CroswellR.T.ReismanA.TempleD.WilliamsC.K., “Planarization processes and applications II. B2O3/P2O5 doped GeO2-SiO2 glasses”, J. Electrochem. Soc.146, 3872 (1999). doi: 10.1149/1.1392566
15.
KuhneH.FischerA.MorgensternT.GrützmacherD., “How boron incorporation during Si1–xGex chemical vapor deposition degrades the Ge profile”, J. Solid State Electrochem.2, 273 (1998). doi: 10.1007/s100080050100
16.
KovalevskiiA.A.BorisenkoV.E.BorisevichV.M.DolbikA.V., “Electrical behavior of in situ doped polysilicon films as influenced by the dopants”, Russian Microelectronics34, 140 (2005). doi: 10.1007/s11180-005-0022-7
17.
HerediaJ.A.TorresJ.A.De La HidalgaW.F.J.JaramilloN.A.SanchezM.J.ZunigaI.C.BasurtoP.M.PerezA., “Low resistivity boron doped amorphous silicon–germanium alloy films obtained with a low frequency plasma”, Mat. Res. Soc. Symp. Proc.796, 63 (2004).
18.
SatoH.WakabayashiT., “Semiconductor device having bipolar transistor and method for manufacturing the same”, US Pat. Appl. Publ. (2004). CODEN: USXXCO US 2004056274 A1 20040325
19.
HitchmanM.L.JensenK.F., Chemical vapour deposition: Principles and applications.Academic Press, London, UK (1993).
20.
EkerdtJ.G.SunY.M.SzaboA.SzulkzewskiG.J.WhiteJ.M., “Role of surface chemistry in semiconductor thin film processing”, Chem. Rev.96, 1499 (1996). doi: 10.1021/cr950236z
21.
HessP., Electronic material chemistry.Marcel Dekker, New York, USA (1996).
22.
BenziP.OpertiL.VaglioG.A.VolpeP.SperanzaM.GabrielliR., “Gas phase ion–molecule reactions of monogermane with oxygen and ammonia”, J. Organomet. Chem.354, 39 (1988). doi: 10.1016/0022-328X(88)80637-5
23.
BenziP.OpertiL.VaglioG.A.VolpeP.SperanzaM.GabrielliR., “Gas phase ion-molecule reactions of monogermane with carbon oxides and ethylene: Formation of germanium-carbon bonds”, J. Organomet. Chem.373, 289 (1989). doi: 10.1016/0022-328X(89)85058-2
24.
BenziP.OpertiL.VaglioG.A.VolpeP.SperanzaM.GabrielliR., “Gas phase ion/molecule reactions in monogermane-hydrocarbon mixtures: A comparative Fourier transform mass spectrometry and chemical ionization mass spectrometry study”, Int. J. Mass Spectrom. Ion Processes100, 647 (1990). doi: 10.1016/0168-1176(90)85100-G
25.
OpertiL.SplendoreM.VaglioG.A.VolpeP., “Ion–molecule reactions in germane/silane systems studied by ion trap mass spectrometry”, Spectrochim. Acta49A, 1213 (1993).
26.
OpertiL.SplendoreM.VaglioG.A.VolpeP., “Gas phase ion–molecule reactions in mixtures of silicon and germanium hydrides by ion trap mass spectrometry”, Organometallics12, 4516 (1993). doi: 10.1021/om00035a042
27.
BenziP.OpertiL.RabezzanaR.SplendoreM.VolpeP., “Gas phase ion/molecule reactions in phosphine/germane mixtures studied by ion trapping”, Int. J. Mass Spectrom. Ion Process.152, 61 (1996). doi: 10.1016/0168-1176(95)04326-8
28.
AntoniottiP.OpertiL.RabezzanaR.VaglioG.A., “Gas phase ion chemistry in germane/ammonia, methylgermane/ammonia, and methylgermane/phosphine”, Int. J. Mass Spectrom.182/183, 63 (1999). doi: 10.1016/S1387-3806(98)14236-7
29.
BenziP.OpertiL.RabezzanaR., “Ion chemistry in XH4/allene (X = Ge, Si) gaseous mixtures—formation of X–C bonds”, Eur. J. Inorg. Chem.2000, 505 (2000). doi: 10.1002/1099-0682(200007)2000:7
30.
AntoniottiP.CanepaC.MaranzanaA.OpertiL.RabezzanaR.TonachiniG.VaglioG.A., “Experimental and theoretical study of the formation of germanium-carbon ion species in gaseous germane/ethene mixtures”, Organometallics20, 382 (2001). doi: 10.1021/om0005553
31.
BenziP.OpertiL.RabezzanaR.VaglioG.A., “Gas-phase ion chemistry in germane-propane and germanepropene mixtures”, J. Mass Spectrom.37, 603 (2002). doi: 10.1002/jms.319
32.
OpertiL.RabezzanaR.VaglioG.A., “Gas-phase ion chemistry in GeH4/C2H4/XH3 (X = P, N) systems”, Int. J. Mass Spectrom.228, 403 (2003). doi: 10.1016/S1387-3806(03)00133-7
33.
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
34.
AntoniottiP.OpertiL.RabezzanaR.VaglioG.A.GuariniA., “Negative ion clusters in self-condensation of GeH4”, Rapid Commun. Mass Spectrom.16, 185 (2002). doi: 10.1002/rcm.562
35.
AntoniottiP.OpertiL.RabezzanaR.VaglioG.A., “A theoretical study of structure and stability of various Ge2Hm−(m = 0–5) ions”, J. Mol. Structure (Theochem.)663, 1 (2003). doi: 10.1016/j.theochem.2002.10.001
36.
OpertiL.RabezzanaR.TurcoF.VaglioG.A., “Negative gas-phase ion chemistry of GeH4: A quadrupole ion trap study”, Rapid Commun. Mass Spectrom.19, 1963 (2005). doi: 10.1002/rcm.2011
37.
OpertiL.RabezzanaR.VaglioG.A., “Negative gas-phase ion chemistry of silane: A quadrupole ion trap study”, Rapid Commun. Mass Spectrom.20, 2696 (2006). doi: 10.1002/rcm.2662
38.
OpertiL.RabezzanaR.TurcoF.VaglioG.A., “Gas-phase positive and negative ion/molecule reactions in diborane and silane/diborane mixtures”, Int. J. Mass Spectrom.264, 61 (2007). doi: 10.1016/j.ijms.2007.03.018
39.
NorthropJ.K.LampeF.W.“Ion–molecule reactions in monogermane”, J. Phys. Chem.77, 30 (1973). doi: 10.1021/j100620a006
40.
SenzenS.N.AbernathyR.N.LampeF.W., “GeH5+ and the proton affinity of monogermane”, J. Phys. Chem.84, 3066 (1980). doi: 10.1021/j100460a018
JacksonP.SändigN.DiefenbachM.SchröderD.SchwarzH.SrinivasR., “The importance of dihydrogen complexes HnGe(H2)+ (n = 0,1) to the chemistry of cationic germanium hydrides: Advanced theoretical and mass spectrometric analysis”, Chem. Eur. J.7, 151 (2001).
43.
KudoT.NagaseS., “The germane monopositive (GeH4+) radical cation. An ab initio study of its ground-state structure and kinetic stability”, Chem. Phys. Lett.148, 73 (1988). doi: 10.1016/0009-2614(88)87263-4
44.
DasK.K.BalasubramanianK., “Geometries and energies of GeHn and GeHn+ (n = 1–4)”, J. Chem. Phys.93, 5883 (1990). doi: 10.1063/1.459585
45.
SchreinerP.R.SchaeferH.F.IIISchleyerP.v.R., “The structures, energies, vibrational, and rotational frequencies, and dissociation energy of GeH5+”, J. Chem. Phys.101, 2141 (1994). doi: 10.1063/1.467720
46.
ArchibongE.F.LeszczyńskiJ., “Structures and properties of GeH5+ ions as revealed by post-Hartree–Fock calculations”, J. Phys. Chem.98, 10084 (1994). doi: 10.1021/j100091a023
47.
MinevaJ.RussoN.SiciliaE.ToscanoM., “Spectroscopic constants of SiH2, GeH2, SnH2, and their cations and anions from density functional computations”, Int. J. Quantum Chem.56, 669 (1995). doi: 10.1002/qua.560560604
48.
JemmisE.D.SrinivasG.N.LeszczyńskiJ.KappJ.KorkinA.A.SchleyerP.v.R., “Group 14 analogs of cyclopropenium ion: Do they favor classical aromatic structures?”, J. Am. Chem. Soc.117, 11361 (1995). doi: 10.1021/ja00150a043
49.
ArchibongE.F.SchreinerP.F.LeszczyńskiJ.SchleyerP.v.R.SchaeferH. F.IIISullivanR., “Ab initio prediction of the structure, harmonic vibrational frequencies, and dissociation energy of the H2–GeH3+–H2 cluster ion”, J. Chem. Phys.102, 3667 (1995). doi: 10.1063/1.468596
50.
KappJ.SchreinerP.R.SchleyerP.v.R., “CH3+ is the most trivial carbocation, but are its heavier congeners just lookalikes?”, J. Am. Chem. Soc.118, 12154 (1996). doi: 10.1021/ja962275d
51.
SoS.P., “Ab initio molecular orbital study of the GeH7+ cation”, J. Phys. Chem.100, 8250 (1996). doi: 10.1021/jp953020+
52.
RasulG.PrakashG.K.S.OlahG.A., “Structures of XH32+ (X = C, Si and Ge) and isoelectronic XH3+ (X = B, Al and Ga)”, J. Mol. Struct. (Theochem.)455, 101 (1998). doi: 10.1016/S0166-1280(98)00216-4
53.
SoS.P., “Theoretical study of Ge5H5+ isomers”, Chem. Phys. Lett.291, 523 (1998). doi: 10.1016/S0009-2614(98)00639-3
54.
SoS.P., “Theoretical study of Si3H3+ and Ge3H3+ isomers”, Chem. Phys. Lett.313, 587 (1999). doi: 10.1016/S0009-2614(99)01089-1
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
57.
PaguraC.ValcherS., Institute for Energetics and Interphases of CNR, C.so Stati Uniti 4, 35127 Padova, Italy, GENANSPE—A software tool for spectra intepretation and de-convolution, Internal report 1998-2004. A copy of the program can be asked for by e-mail to c.pagura@ieni.cnr.it
58.
SuT.ChesnavichW. J., “Parametrization of the ion-polar molecule collision rate constants by trajectory calculations”, J. Chem. Phys.76, 5183 (1982). doi: 10.1063/1.442828
59.
LippincotE.R.StutmanJ.M., “Polarizabilities from δ-function potentials”, J. Phys. Chem.68, 2926 (1964). doi: 10.1021/j100792a033
60.
LinstromP.J.MallardW.G. (Eds), Thermochemical data are taken from NIST Chemistry Webbook, NIST Standard Reference Database Number 69. National Institute of Standards and Technology, Gaithersburg, MD, USA, June 2005, http://webbook.nist.gov
61.
DewarM.J.S.McKeeM.L., “Ground states of molecules. 41. MNDO results for molecules containing boron”, J. Am. Chem. Soc.99, 5231 (1977). doi: 10.1021/ja00458a001
62.
FehlnerT.P.KoskiW.S., “The fragmentation of some boron hydrides by electron impact”, J. Am. Chem. Soc.86, 581 (1964). doi: 10.1021/ja01058a010
63.
SakakiS.BiswasB.MusashiY.SugimotoM., “Bonding nature and reaction behavior of inter-element linkages with transition metal complexes. A theoretical study”, J. Organomet. Chem.611, 288 (2000). doi: 10.1016/S0022-328X(00)00456-3
64.
HuS.WangY.WangX.-Y., “Gas phase reactions between SiH4 and B2H6: A theoretical study”, J. Phys. Chem. A107, 1635 (2003). doi: 10.1021/jp027113k
