Comparison of Trichlorosilane and Trichlorogermane Decomposition on Silicon Surfaces Using FTIR Spectroscopy

1992 ◽  
Vol 282 ◽  
Author(s):  
A. C. Dillon ◽  
M. B. Robinson ◽  
S. M. George
Keyword(s):  
Porous Silicon ◽  
High Surface ◽  
High Vacuum ◽  
Atomic Layer ◽  
Layer Growth ◽  
Ultra High Vacuum ◽  
Silicon Surfaces ◽  
Absorption Feature ◽  
Surface Species ◽  
Thermal Stabilities

ABSTRACTFourier transform infrared (FTIR) transmission spectroscopy was used to compare the decomposition of trichlorosilane (SiHCl3) and trichlorogermane (GeHCl3) on silicon surfaces. Chlorosilanes, such as SiHCl3 are employed in silicon chemical vapor deposition (CVD). Chlorosilanes and chlorogermanes are also possible molecular precursors for the controlled atomic layer growth of silicon and germanium. GeHCl3 may be useful for the deposition of germanium on silicon surfaces and the growth of Si1−xGex heterostructures. The FTIR studies were performed in-situ in an ultra-high vacuum chamber on high surface area, porous silicon samples. The FTIR spectra revealed that SiHCl3 dissociatively adsorbs at 200 K to form SiH, SiClx, ClSiH and Cl2SiH surface species. The presence of ClxSiH species is revealed by ClxSiH stretching (2196 cm−1) and bending (775, 744 cm−1) vibrations. The presence of these modes indicates that there is incomplete decomposition of SiHCl3 upon adsorption at 200 K. GeHCl3 also dissociatively adsorbs at 200 K to form SiH and SiClx species. An infrared absorption feature in the Ge-H stretching region (1970–1995 cm−1) was not detected in the FTIR spectrum. The absence of a Ge-H absorption feature argues that there is a complete transfer of hydrogen from germanium to surface silicon atoms at 200 K. The thermal stabilities of the surface species were studied with annealing experiments. The Clx SiH formed upon initial SiHCl3 exposures at 200 K were observed to decompose between 200–590 K and form additional surface SiH and SiCl species. For both GeHCl3 and SiHCl3 dissociative adsorption on porous silicon, the SiCL. (x = 2 or 3) surface species were converted to silicon monochloride surface species between 200–600 K. In addition, SiH surface species were lost upon annealing between 680–780 K as H2 desorbed from the surface. The adsorption kinetics of SiHCl3 and GeHCl3 were also monitored on porous silicon at various isothermal temperatures. These experiments provide insight into the surface chemistry of chlorosilanes and chlorogermanes during CVD and atomic layer controlled growth.

Ftir Studies of Water and Ammonia Decomposition on Silicon Surfaces

1990 ◽  
Vol 204 ◽  
Author(s):  
A.C. Dillon ◽  
P. Gupta ◽  
M.B. Robinson ◽  
A.S. Bracker ◽  
S.M. George
Keyword(s):  
Silicon Surface ◽  
Silicon Oxide ◽  
High Surface ◽  
High Vacuum ◽  
High Surface Area ◽  
Ftir Spectra ◽  
Ultra High Vacuum ◽  
Silicon Surfaces ◽  
Surface Species ◽  
Surface Hydrogen

ABSTRACTFourier transform infrared (FTIR) transmission spectroscopy. was used to monitor the decomposition of H2O (D2O) and NH3(ND3) on silicon surfaces. Experiments were performed in-situ in an ultra-high vacuum (UHV) chamber using high surface area poroussilicon samples. The FTIR spectra revealed that H2O dissociates upon adsorption at 300K to form SiH and SiNH2 surface species. NH3 also issociates upon adsorption at 300 K to form SiH and SiOH2 species. Silicon samples with saturation exposures of H2O and NH3 were progressively annealed from 300 K to 860 K. The FTIR spectra of an H2O-saturated silicon surface revealed that the SiOH species decomposed to form a silicon oxide species and additional surface hydrogen between 460 K and 580 K. Likewise, the SiNH2 species decomposed between 540 K and 660 K to produce silicon nitride and additional surface hydrogen. In both cases, the Sill surface species decreased as H2 desorption from the silicon surface was observed above 700 K.

Decomposition of Alkylsilanes on Silicon Surfaces Using Transmission Ftir Spectroscopy

1991 ◽  
Vol 222 ◽  
Author(s):  
A. C. Dillon ◽  
M. B. Robinson ◽  
M. Y. Han ◽  
S. M. George
Keyword(s):  
Porous Silicon ◽  
Silicon Surface ◽  
High Surface ◽  
High Surface Area ◽  
Atomic Layer ◽  
Silicon Surfaces ◽  
Surface Species ◽  
Reaction Products ◽  
Molecular Precursors ◽  
Hydride Elimination

ABSTRACTFourier transform infrared (FTIR) transmission spectroscopy was used to monitor the decomposition of alkylsilanes such as diethylsilane (DES) [(CH3 CH2)2SiH2], di-t-butylsilane (DTBS) [((CH3)3C)2SiH2] and ethylsilane (ES) [CH3CH2SiH3 on high-surface-area porous silicon samples. The FTIR spectra revealed that tKe akylsilanes dissociatively adsorb on porous silicon at 300 K to form SiH and Si-alkyl species. As the silicon surface was progressively annealed, the Si-alkyl species decomposed and produced gas phase ethylene (DES,ES) or isobutylene (DTBS). The decomposition of the alkyl group was accompanied by the growth of additional SiH surface species. These reaction products were consistent with a [β-hydride elimination reaction. Above 700 K, the SiH surface species decreased concurrently with the desorption of H2 from the porous silicon surface. The uptake of surface species was also monitored at various adsorption temperatures to determine the optimal exposure temperatures for carbon-free silicon deposition. Carbon contamination was not detected at adsorption temperatures below 640 K prior to H2 desorption. Because the alkylsilane adsorption process is self-limiting at temperatures below 640 K, alkylsilanes may be useful molecular precursors for the atomic layer epitaxy (ALE) of silicon.

In-Situ Transmission Electron Microscopy of the Formation of Metal-Semiconductor Contacts

1990 ◽  
Vol 181 ◽  
Author(s):  
J. M. Gibson ◽  
D. Loretto ◽  
D. Cherns
Keyword(s):  
High Surface ◽  
High Vacuum ◽  
Volume Ratio ◽  
Ultra High Vacuum ◽  
Silicon Surfaces ◽  
Transmission Electron ◽  
Metal Silicides ◽  
Phase Sequence ◽  
Semiconductor Contacts

ABSTRACTWe have studied the formation of metal silicides in-situ in an ultra-high vacuum transmission electron microscope. Metals were deposited on in-situ cleaned, reconstructed silicon surfaces and annealed. For the metals Ni and Co, we find that the phase sequence in ultra-thin films is different from that seen in ≈1000 Å thick films, and attribute this to the high surface-to-volume ratio. In general reactions occur at room temperature, to form an epitaxial phase if possible. We report preliminary new results on the formation of Pd2Si.

Germanium Deposition on Silicon: Surface Chemistry of (CH3CH2)2GeH2 and GeC14

1992 ◽  
Vol 282 ◽  
Author(s):  
P. A. Coon ◽  
M. L. Wise ◽  
A. C. Dillon ◽  
S. M. George
Keyword(s):  
Porous Silicon ◽  
Surface Chemistry ◽  
Silicon Surface ◽  
Atomic Layer ◽  
Silicon Surfaces ◽  
Desorption Kinetics ◽  
Surface Species ◽  
Adsorption And Desorption ◽  
Controlled Deposition ◽  
Sticking Coefficients

ABSTRACTDiethylgermane, (CH3CH2)2GeH2, and germanium tetrachloride, GeCl4 may be useful precursors for chemical vapor deposition (CVD) or atomic layer controlled deposition of germanium. To explore the surface chemistry of these alternative precursors, the adsorption and desorption kinetics of (CH3CH2)2GeH2 (DEG) and GeCl4 on Si(111) 7×7 have been examined using laser-induced thermal desorption (LITD), and temperature programmed desorption (TPD) techniques. Fourier transform infrared (FTIR) spectroscopy has also been employed to monitor the decomposition of DEG on porous silicon surfaces. The FTIR spectra revealed that DEG dissociatively adsorbs on porous silicon surfaces at 200 K to form SiH, GeH, and SiCH2CH3 surface species. No spectral features were observed for GeCH2CH3 surface species. The TPD studies following DEG exposures on Si(111) 7×7 observed CH2=CH2 and H2 desorption products at 700 and 800 K, respectively. The production of CH2=CH2 (ethylene) was consistent with a βhydride elimination mechanism from surface ethyl species, i.e. SiCH2CH3(ad) → SiH(ad) + CH2=CH2 (g). Similar TPD experiments following GeCl4 exposures monitored the desorption of only SiCl2 at approximately 920 K. Desorption of SiCl2 indicates that the chlorine on GeCl4 has transferred to the silicon surface. Atomic Ge was also observed to desorb at 1200 K following both DEG and GeCl4 adsorption. LITD experiments measured initial reactive sticking coefficients of So ∼0.05 for DEG and So ∼1.0 for GeCl4 at 200 K. As expected from a precursor-mediated adsorption model, the sticking coefficients decreased versus increasing surface temperature. The sticking coefficients for these germanium containing precursors were higher than the corresponding sticking coefficients for (CH3CH2)2SiH2 and SiCl4. Possible recipes for the CVD or atomic layer controlled deposition of germanium on silicon can be proposed based on the surface chemistry and adsorption and desorption kinetics for DEG and GeCl4.

Effects of Hydrogen Coverage on Silicon Surface Reactivity

1992 ◽  
Vol 259 ◽  
Author(s):  
A.C. Dillon ◽  
M.B. Robinson ◽  
S.M. George ◽  
P. Gupta
Keyword(s):  
Porous Silicon ◽  
Silicon Surface ◽  
High Surface ◽  
Surface Cleaning ◽  
Surface Reactivity ◽  
Silicon Surfaces ◽  
Initial Surface ◽  
Hydrogen Passivation ◽  
Surface Species ◽  
Oxidation Rates

ABSTRACTHydrogen passivation of silicon surfaces plays an important role in silicon surface cleaning and preparation. To measure the effect of hydrogen passivation on silicon surface reactivity, Fourier transform infrared (FTIR) transmission spectroscopy was used to monitor the oxidation of silicon surfaces versus hydrogen coverage. Experiments were performed insitu in an ultrahigh vacuum (UHV) chamber using high surface area poroussilicon samples. Si-H stretching and bending vibrations and Si-O-Si stretching vibrations were employed to monitor the silicon surface species. Oxidation studies with O2 conducted versus various initial hydrogen coverages revealed that oxidation rates and apparent oxygen saturation levels on porous silicon decreased as a function of initial surface hydrogen coverage. Exceptional surface stability was observed when the porous silicon surface was passivated by both monohydride and dihydride surface species. In addition, new blue-shifted Si-H stretching and bending features were observed following the oxidation of partially hydrogen-passivated porous silicon which indicated the presence of Ox SiH species. Thermal annealing studies revealed that the thermal stability of these OxSiH species increased with increasing oxidation of the silicon surface. These results have important implications for silicon growth and surface cleaning because they indicate that hydrogen removal is more difficult when the silicon surface is contaminated with oxygen. These FTIR results have also been compared with earlier results of oxidation versus hydrogen coverage on Si(111) 7×7.

Coverage and Stability of NHx Terminated Cobalt and Ruthenium Surfaces: a First Principles Investigation

2019 ◽  
Author(s):  
Ji Liu ◽  
Michael Nolan
Keyword(s):  
Metal Surfaces ◽  
High Vacuum ◽  
Atomic Layer ◽  
Nitrogen Plasma ◽  
Operating Conditions ◽  
Ultra High Vacuum ◽  
Bridge Site ◽  
Stable Surface ◽  
Saturation Coverage ◽  
The Stability

<div>In the atomic layer deposition (ALD) of Cobalt (Co) and Ruthenium (Ru) metal using nitrogen plasma, the structure and composition of the post N-plasma NHx terminated (x = 1 or 2) metal surfaces are not well known but are important in the subsequent metal containing pulse. In this paper, we use the low-index (001) and (100) surfaces of Co and Ru as models of the metal polycrystalline thin films. The (001) surface with a hexagonal surface structure is the most stable surface and the (100) surface with a zigzag structure is the least stable surface but has high reactivity. We investigate the stability of NH and NH2 terminations on these surfaces to determine the saturation coverage of NHx on Co and Ru. NH is most stable in the hollow hcp site on (001) surface and the bridge site on the (100) surface, while NH2 prefers the bridge site on both (001) and (100) surfaces. The differential energy is calculated to find the saturation coverage of NH and NH2. We also present results on mixed NH/NH2-terminations. The results are analyzed by thermodynamics using Gibbs free energies (ΔG) to reveal temperature effects on the stability of NH and NH2 terminations. Ultra-high vacuum (UHV) and standard ALD</div><div>operating conditions are considered. Under typical ALD operating conditions we find that the most stable NHx terminated metal surfaces are 1 ML NH on Ru (001) surface (350K-550K), 5/9 ML NH on Co (001) surface (400K-650K) and a mixture of NH and NH2 on both Ru (100) and Co (100) surfaces.</div>

Ultra High Vacuum Scanning Tunneling Microscopy Observation of Multilayer Step Structure on GaAs and AlAs Vicinal Surface Grown by Metalorganic Vapor Phase Epitaxy

1996 ◽  
Vol 448 ◽  
Author(s):  
Jun-Ya Ishizaki ◽  
Yasuhiko Ishizaki ◽  
Takashi Fukui
Keyword(s):  
Scanning Tunneling Microscopy ◽  
High Vacuum ◽  
Gaas Layer ◽  
Layer Growth ◽  
Ultra High Vacuum ◽  
Scanning Tunneling ◽  
Vicinal Surface ◽  
Microscopy Observation ◽  
Tunneling Microscopy ◽  
Atomic Structures

AbstractWe observe the atomic structures at the multilayer step region on MOVPE-grown GaAs (001) vicinal surface using ultra high vacuum scanning tunneling microscopy (UHV-STM), and clarify that (4×2) or (4×3) like reconstruction units are dominant. Oxide free AlAs surfaces grown on GaAs vicinal surface are also successfully observed by UHV-STM. The reconstruction units at the multilayer step region on AlAs surface have the same units on GaAs vicinal surface. GaAs surface has the lack of dimmer rows on the terrace region just below the multilayer step region, while AlAs surface has dimmer rows even on the terrace just below the multilayer step region. GaAs layer growth leads tothe step bunching phenomenon and AlAs surface leads to the step debunching phenomenon.

scholarly journals Selective Growth of Al2O3 on Size-Selected Platinum Clusters by Atomic Layer Deposition

2019 ◽  
Author(s):  
Timothy J. Gorey ◽  
Yang Dai ◽  
Scott Anderson ◽  
Sungsik Lee ◽  
Sungwon Lee ◽  
...  
Keyword(s):  
Atomic Layer Deposition ◽  
Photoelectron Spectroscopy ◽  
High Vacuum ◽  
Atomic Layer ◽  
Ultra High Vacuum ◽  
Ex Situ ◽  
Dimensional Structure ◽  
Alumina Layer ◽  
X Ray ◽  
Layer Deposition

In heterogeneous catalysis, atomic layer deposition (ALD) has been developed as a tool to stabilize and reduce carbon deposition on supported nanoparticles. Here, we discuss use of high vacuum ALD to deposit alumina films on size-selected, sub-nanometer Pt/SiO2 model catalysts. Mass-selected Pt24 clusters were deposited on oxidized Si(100), to form model Pt24/SiO2 catalysts with particles shown to be just under 1 nm, with multilayer three dimensional structure. Alternating exposures to trimethylaluminum and water vapor in an ultra-high vacuum chamber were used to grow alumina on the samples without exposing them to air. The samples were probed in situ using X-ray photoelectron spectroscopy (XPS), low-energy ion scattering spectroscopy (ISS), and CO temperature-programmed desorption (TPD). Additional samples were prepared for ex situ experiments using grazing incidence small angle x-ray scattering spectroscopy (GISAXS). Alumina growth is found to initiate at least 60 times more efficiently at the Pt24 cluster sites, compared to bare SiO2/Si, with a single ALD cycle depositing a full alumina layer on top of the clusters, with substantial additional alumina growth initiating on SiO2 sites surrounding the clusters. As a result, the clusters were completely passivated, with no exposed Pt binding sites.

Molecular beam epitaxy, atomic layer deposition, and multiple functions connected via ultra-high vacuum

2019 ◽  
Vol 512 ◽  
pp. 223-229 ◽  
Author(s):  
K.Y. Lin ◽  
H.W. Wan ◽  
K.H.M. Chen ◽  
Y.T. Fanchiang ◽  
W.S. Chen ◽  
...  
Keyword(s):  
Molecular Beam Epitaxy ◽  
Atomic Layer Deposition ◽  
Molecular Beam ◽  
High Vacuum ◽  
Atomic Layer ◽  
Ultra High Vacuum ◽  
Multiple Functions ◽  
Layer Deposition
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