Novel method for chemical vapor deposition and atomic layer epitaxy using radical chemistry

Hukka, Terttu I.; Rawles, Robin E.; D'Evelyn, Mark P.

doi:10.1016/0040-6090(93)90157-k

Cited by 26 publications

(10 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1 , 2 Surface hydrogen also plays a crucial role in the growth of silicon by atomic layer epitaxy (ALE), 3 -6 and almost certainly is critically important in diamond ALE processes cumrently being developed. 7 Water is produced in diamond growth reactors 8 . 9 upon addition of 0210.11 or oxygen-containing precursors 12 -17 and is present at impurity levels in all reactors, yet waterdiamond reactions are neglected in all existing diamond growth models and single-crystal surface studies of the interaction of H 2 0 with diamond have not yet been performed.…”

Section: Introductionmentioning

confidence: 99%

Interaction of hydrogen and water with diamond (100): Infrared spectroscopy

Struck¹,

D'Evelyn²

1993

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

View full text Add to dashboard Cite

Reproduction, in whole or in part, is permitted for any purpose of the United States Government.This document has been approved for public release and sale; its distribution is unlimited. 12 28 048 SREPORT DOCUMENTATION PAGEForm Approved II OMB No. 0704-0188 P•Joc' recr•t'-i uroen for this collection of information s •estimated to average I hour Oer response. including the time for reviewing instructliort . searching existing data sOurces gathe-ra and maintainrng the data needed, and completing and reviening the collection of information. Approved for public release; distribution is unlimited. ABSTRACT (Maximum 200 words)We report the first investigation of the adsorption of deuterium and water on diamond (100) by infrared multiple-internal-reflection spectroscopy using a natural type iHa diamond internal reflection element. Infrared evidence was seen for the monohydride surface structure, with one hydrogen atom per surface carbon atom (Sc1D mode at 901 cm-l), while the dihydride (CD2) structure was not observed. Following exposure to water at elevated temperature, infrared absorption features were detected at 1280, 1200, 1125, 1080, and 720 cm-1 , and are assigned to ether (C-O-C), hydroxyl (C-OH), and carbonyl (>C=O) modes. The substantial observed reactivity of diamond with water indicates a potentially important role for surface hydroxyl and oxide species in the surface chemistry and morphological development of CVD diamond films.14. AbstractWe report the first investigation of the adsorption of water on diamond (100) by infrared multiple-internal-reflection spectroscopy, using a natural type Ha diamond internal reflection element. Infrared spectroscopic results on the adsorption of atomic deuterium are also presented.

show abstract

Section: Introductionmentioning

confidence: 99%

Interaction of hydrogen and water with diamond (100): Infrared spectroscopy

Struck¹,

D'Evelyn²

1993

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

View full text Add to dashboard Cite

show abstract

“…1 [2][3][4][5][6][7][8][9][10][11][12][13][14][15] We attribute the near-firstorder kinetics to preferential pairing of adsorbed atoms on surface dimers due to the existence of weak n bonds on clean surface dimers. 14 , 16 We have proposed a doubly-occupied dimer model that quantitatively accounts for the desorption kinetics on both Si(100) 13 -15 and Ge(100) 11 and have suggested that preferential pairing is a general phenomenon on group IV (100)2x 1 surfaces.…”

Section: Discussionmentioning

confidence: 99%

Competitive Pairing and the Chemistry of Coadsorbed Hydrogen and Halogens on Ge(100)

1992

Self Cite

View full text Add to dashboard Cite

Puolic re•o•oing Curden for this collectiOn of information is estimated to average I hour per response. including the time for reviewing instructions. searching exrstng data sources.gatheno and rmaintaining the data needed, and completinsg and reviewing the collection of information. Send comments reearding this burden estimate or anV other aspect of this coae-Uol• of information. ncluding suggestions for reducing this Ouroen. Approved for public release; distribution is unlimited. ABSTRACT (Maximum 200 words)The chemistry of coadsorbed H and X (X--C, Br) on semiconductor surfaces is important in epitaxial growth of silicon from chlorosilanes and of SixGel-x alloys, in hydrogenating/ halogenating cycles in atomic layer epitaxy, and also provides an intmsting model system, yet has received little attention to date. We have investigated the interaction of Ha and HBr with Ge(100) by temperature-programmed desorption, and find that H2, HCI and HBr each desorb with near-first-order kinetics near 570-590 K and that GeCl2 and GeBr2 desorb with nearsecond-order kinetics near 675 K and 710 K, respectively. Analysis of the desorption kinetics of H2 and HX leads to the conclusion that adsorbed H and X atoms pair preferentially in a qualitatively similar way as H atoms adsorbed alone on Ge(100)2xl or Si(100)2xl and that pairing of H+X occurs in competition with pairing of H+H. SUBJECT TERMS ABSTRACTThe chemistry of coadsorbed H and X (X--Cl, Br) on semiconductor surfaces is important in epitaxial growth of silicon from chlorosilanes and of SixGel.x alloys, in hydrogenating/ halogenating cycles in atomic layer epitaxy, and also provides an interesting model system, yet has received little attention to date. We have investigated the interaction of HCI and HBr with Ge(100) by temperature-programmed desorption, and find that H2, HC1 and HBr each desorb with nearfirst-order kinetics near 570-590 K and that GeC12 and GeBr 2 desorb with near-second-order kinetics near 675 K and 710 K, respectively. Analysis of the desorption kinetics of H2 and LIX leads to the conclusion that adsorbed H and X atoms pair preferentially in a qualitatively sinila way as H atoms adsorbed alone on Ge(100)2xl or Si(100)2xl and that pairing of H+X occurs in competition with pairing of H+H.

show abstract

“…Further interest in hydrogen-halogen surface chemistry stems from recent observations that atomic hydrogen can readily abstract halogen atoms from Si(lOO), 2 5 -2 7 which is directly relevant to ALE. 5 ,9, 1 1 Much more attention has been devoted to the adsorption of hydrogen or halogen atoms individually. The structures of adsorbed hydrogen on Ge(100) 2 8 " 3 0 are directly analogous to those on Si(lOO), 30 -3 3 the most stable species being the monohydride, with one hydrogen atom on each dimerized surface atom.…”

Section: Introductionmentioning

confidence: 99%

“…Several techniques involving alternating cycles of a halogenated precursor and hydrogen have been proposed for ALE of silicon 7 -12 and diamond. 5 Besides being important for growth, hydrogen-chlorine chemistry is also important in the etching of silicon. 13 In addition to being technologically important, coadsorbed hydrogen and halogen atoms on semiconductor surfaces constitute an interesting model system from a fundamental point of view.…”

Section: Introductionmentioning

confidence: 99%

Adsorption, desorption, and decomposition of HCl and HBr on Ge(100): Competitive pairing and near-first-order desorption kinetics

D'Evelyn

Yang

Cohen

1994

The Journal of Chemical Physics

View full text Add to dashboard Cite

We have investigated the surface chemistry of coadsorbed hydrogen and halogen atoms on Ge(100), produced by dissociative chemisorption of HCl and HBr, by temperature-programmed desorption. The initial sticking probability S0 for HCl decreases from 0.6 at a substrate temperature of 270 K to 0.05 at 400 K, indicative of a precursor state to adsorption. For HBr S0 is constant at 0.7 over the same temperature range. A fraction f of adsorbed hydrogen atoms desorb associatively as H2 near 570 K, while the remaining (1−f) H atoms recombine with adsorbed halogen atoms and desorb as the hydrogen halide (HX) near 580–590 K. The activation energies for desorption of H2, HCl, and HBr are all approximately 40 kcal/mol. For both HCl and HBr f is 0.7 at low initial coverage and decreases slightly to 0.6 at saturation. The fraction f of adsorbed halogen atoms left on the surface following the competitive desorption of H2 and HX desorb as the dihalides GeCl2 and GeBr2 near 675 and 710 K, respectively. Desorption of H2, HCl, and HBr occurs with near-first-order kinetics, similar to the behavior of hydrogen adsorbed alone, which we attribute to preferential pairing induced by the π bond on unoccupied Ge dimers. We introduce and solve a generalized doubly occupied dimer model incorporating competitive pairing of H+H, H+X, and X+X on Ge dimers to explain the near-first-order kinetics. The model quantitatively accounts for both the desorption kinetics and the relative yields of H2 and HX with pairing energies of ≊3 kcal/mol. Implications of the present results for surface thermochemistry, chemical vapor deposition, and atomic layer epitaxy of Ge and Si(100)2×1 surfaces are discussed.

show abstract

Novel method for chemical vapor deposition and atomic layer epitaxy using radical chemistry

Cited by 26 publications

References 42 publications

Interaction of hydrogen and water with diamond (100): Infrared spectroscopy

Interaction of hydrogen and water with diamond (100): Infrared spectroscopy

Competitive Pairing and the Chemistry of Coadsorbed Hydrogen and Halogens on Ge(100)

Adsorption, desorption, and decomposition of HCl and HBr on Ge(100): Competitive pairing and near-first-order desorption kinetics

Contact Info

Product

Resources

About