HYDROGENATED AMORPHOUS SILICON THIN-FILM DEPOSITION BY DIRECT PHOTO-ENHANCED DECOMPOSITION OF SILANE USING AN INTERNAL HYDROGEN DISCHARGE LAMP.

Hydrogenated amorphous silicon (a-Si:H) thin films have been deposited from silane using a novel photo-enhanced decomposition technique. The system comprises a hydrogen discharge lamp contained within the reaction vessel; this unified approach allows high energy photon excitation of the silane molecules without absorption by window materials or the need for mercury sensitisation. The film growth rates (exceeding 4 Angstrom/s) and material properties obtained are comparable to those of films produced by plasma-enhanced CVD techniques. The reduction of energetic charged particles in the film growth region should enable the fabrication of cleaner semiconductor/insulator interfaces in thin-film transistors.

Defect and disorder reduction by annealing in hydrogenated tetrahedral amorphous carbon

Hydrogenated tetrahedral amorphous carbon (ta-C:H) is a form of diamond-like carbon with a high sp3 content (>60%), grown here using a plasma beam source. Information on the behaviour of hydrogen upon annealing is obtained from effusion measurements, which show that hydrogen does not effuse significantly at temperatures less than 500 °C in films grown using methane and 700 °C in films grown using acetylene. Raman measurements show no significant structural changes at temperatures up to 300 °C. At higher temperatures, corresponding to the onset of effusion, the Raman spectra show a clustering of the sp2 phase. The density of states of ta-C:H is directly measured using scanning tunnelling spectroscopy. The measured gradients of the conduction and valence band tails increase up to 300 °C, confirming the occurrence of band tail sharpening. Examination of the photoluminescence background in the Raman spectra shows an increase in photoluminescence intensity with decreasing defect density, providing evidence that paramagnetic defects are the dominant non-radiative recombination centres in ta-C:H.

Hydrogenated amorphous silicon and silicon nitride deposited at less than 100° C by ECR-PECVD for thin film transistors

A systematic study has been made of the growth of both hydrogenated amorphous silicon (a-Si:H) and silicon nitride (a-SiN) by electron cyclotron resonance plasma enhanced chemical vapour deposition (ECR-PECVD). In the case of a-SiN, helium and nitrogen gas is injected into the system such that it passes through the resonance zone. These highly ionised gases provide sufficient energy to ionise the silane gas, which is injected further downstream. It is demonstrated that a gas phase reaction occurs between the silane and nitrogen species. It is control of the ratio of silane to nitrogen in the plasma which is critical for the production of stoichiometric a-SiN. Material has been produced at 80°C with a Si:N ratio of 1:1.3 a breakdown strength of ∼6 MV cm-1 and resistivity of > 1014 Ω cm. In the case of a-Si:H, helium and hydrogen gas is injected into the ECR zone and silane is injected downstream. It is shown that control of the gas phase reactions is critical in this process also. a-Si:H has been deposited at 80 °C with a dark conductivity of 10-11 Ω-1 cm-1 and a photosensitivity of justbelowl 4×104. Such materials are suitable for use in thin film transistors on plastic substrates.

PHOTOENHANCED DEPOSITION OF HYDROGENATED AMORPHOUS SILICON THIN FILMS.

This paper will review the different U. V. lamp photo-CVD (Chemical Vapor Deposition) techniques which have been utilized for the production of highly photoconductive hydrogenated amorphous silicon (a-Si:H) thin films. Most of these require the transmission of U. V. light through a window into the reaction vessel; leading to unwanted U. V. light absorption by the window and the a-Si:H film which tends to form on its inner surface. A deposition system developed in our laboratory will also be described, which circumvents these problems by incorporating a windowless discharge lamp into the reaction vessel.

Characterization of defect removal in hydrogenated and deuterated amorphous silicon thin film transistors

Thin film transistors (TFTs) utilizing an hydrogenated amorphous silicon (a-Si:H) channel layer exhibit a shift in the threshold voltage with time under the application of a gate bias voltage due to the creation of metastable defects. These defects are removed by annealing the device with zero gate bias applied. The defect removal process can be characterized by a thermalization energy which is, in turn, dependent upon an attempt-to-escape frequency for defect removal. The threshold voltage of both hydrogenated and deuterated amorphous silicon (a-Si:D) TFTs has been measured as a function of annealing time and temperature. Using a molecular dynamics simulation of hydrogen and deuterium in a silicon network in the H2 * configuration, it is shown that the experimental results are consistent with an attempt-to-escape frequency of (4.4 ± 0.3) × 1013 Hz and (5.7 ± 0.3) × 1013 Hz for a-Si:H and a-Si:D respectively which is attributed to the oscillation of the Si-H and Si-D bonds. Using this approach, it becomes possible to describe defect removal in hydrogenated and deuterated material by the thermalization energies of (1.552 ± 0.003) eV and (1.559 ± 0.003) eV respectively. This correlates with the energy per atom of the Si-H and Si-D bonds. © 2006 Elsevier B.V. All rights reserved.

Effect of hydrogen dilution on the deposition of carbon-rich a-SiC:H films by the electron cyclotron resonance method

The deposition of hydrogenated amorphous silicon carbide (a-SiC:H) films from a mixture of silane, acetylene and hydrogen gas using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) process is reported. The variation in the deposition and film characteristics such as the deposition rate, optical band gap and IR absorption as a function of the hydrogen dilution is investigated. The deposition rate increases to a maximum value of about 250 Å min-1 at a hydrogen dilution ratio of about 20 (hydrogen flow (sccm)/acetylene + silane flow (sccm)) and decreases in response to a further increase in the hydrogen dilution. There is no strong dependence of the optical band gap on the hydrogen dilution within the dilution range investigated (10-60) and the optical band gap calculated from the E04 method varied marginally from about 2.85 to 3.17 eV. The room temperature photoluminescence (PL) peak energy and intensity showed a prominent shift to a maximum value of about 2.17 eV corresponding to maximum PL intensity at a moderate hydrogen dilution of about 30. The PL intensity showed a strong dependence on the hydrogen dilution variation.

Doping mechanism in tetrahedral amorphous carbon

Doping in hydrogenated amorphous silicon occurs by a process of an ionised donor atom partially compensated by a charged dangling bond. The total energies of various dopant and dopant/bonding combinations are calculated for tetrahedral amorphous carbon. It is found that charged dangling bonds are less favoured because of the stronger Coulombic repulsion in ta-C. Instead the dopants can be compensated by weak bond states in the lower gap associated with odd-membered π-rings or odd-numbered π-chains. The effect is that the doping efficiency is low but there are not charged midgap recombination centres, to reduce photoconductivity or photoluminescence with doping, as occurs in a-Si:H.

Doping mechanism in tetrahedral amorphous carbon

Doping in hydrogenated amorphous silicon occurs by a process of an ionized donor atom partially compensated by a charged dangling bond. The total energies of various dopant and dopant/bonding combinations are calculated for tetrahedral amorphous carbon. It is found that charged dangling bonds are less favored because of the stronger Coulombic repulsion in ta-C. Instead the dopants can be compensated by weak bond states in the lower gap associated with odd-membered π-rings or odd-numbered π-chains. The effect is that the doping efficiency is low but there are not charged midgap recombination centres, to reduce photoconductivity or photoluminescence with doping, as occurs in a-Si:H.

Local hydrogen reactions of H*2 in a-Si:H

Hydrogen rearrangements at the H*2 complex are used as a model of low energy, local transitions in the two-hydrogen density of states of hydrogenated amorphous silicon (a-Si:H). These are used to account for the low activation energy motion of H observed by nuclear magnetic resonance, the low energy defect annealing of defects formed by bias stress in thin film transistors, and the elimination of hydrogen from the growth zone during the low temperature plasma deposition of a-Si:H. © 1998 Elsevier Science B.V. All rights reserved.

Surface atomic properties of tetrahedral amorphous carbon

The surface energy and surface atomic structure of tetrahedral amorphous carbon has been calculated by an ab-initio method. The surface atoms are found to reconstruct into sp2 sites often bonded in graphitic rings. Placing the dangling bonds on adjacent surface atoms lower their energy by π-bonding and this is the source of the low surface energy. The even lower surface energy of hydrogenated amorphous carbon (a-C:H) is due to the hydrogenation of all broken surface bonds. © 2005 Elsevier B.V. All rights reserved.

High rate deposition of ta-C:H using an electron cyclotron wave resonance plasma source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 1.5 nm/s over a 4-inch diameter and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized as having an sp3 content of up to 77%, plasmon energy of 27 eV, refractive index of 2.45, hydrogen content of about 30%, optical gap of up to 2.1 eV and RMS surface roughness of 0.04 nm. © 1999 Elsevier Science S.A. All rights reserved.