Chemical-reaction dependence of plasma parameter in reactive silane plasma

Electron temperature in a silane glow-discharge plasma, being an important plasma parameter for determining photo-induced instability in the resulting hydrogenated amorphous silicon (a-Si:H), has been studied under various film-preparation conditions. We have used an optical-emission-intensity ratio of Si¹ to SiH¹ (I_Si¹/I_SiH¹) which corresponds to the high-energy-tail slope of the electron-energy-distribution function in the plasma as a measure of electron temperature in a reactive silane glow-discharge plasma. We have found quite differently from the conventional non-reactive glow-discharge plasma such as hydrogen plasma that the electron temperature in the silane plasma is strongly modified by the substrate temperature (gas temperature) especially under high silane-gas partial-pressure condition. This anomalous behavior of the electron temperature in the silane plasma has been explained by means of gas-phase-polymerization reaction and electron-attachment process to the polymers in the plasma. The electron temperature has been remarkably reduced when a hydrogen-dilution method and a cathode-heating method are used which are considered to control polymer-formation reactions in the silane plasma together with utilization of conventional electron-temperature-controlling methods such as a very high plasma-excitation frequency and an application of magnetic field for electron-confinement. As a consequence of the reduction of electron temperature in the silane plasma, highly stabilized a-Si:H has been successfully obtained even under high growth rate conditions of 1.5 nm s⁻¹.     

Anomalous behavior of electron temperature in silane glow discharge plasmas

The electron temperature measured by an optical emission intensity ratio of Si* to SiH* in a silane (SiH₄) glow-discharge plasma shows an anomalous behavior against film preparation conditions such as gas pressure and substrate temperature. When increasing the gas pressure, the electron temperature decreases first, takes a minimum value at a certain pressure range and then it increases. The electron temperature decreases with increasing substrate temperature, which is quite the opposite trend to a conventional non-reactive hydrogen plasma. These anomalous behaviors of electron temperature in silane plasmas have been explained in terms of feed-back phenomenon in the plasma, starting from an electron-attachment event to higher silane molecules produced in the plasma, causing an increase of electron temperature due to an increase of electron-loss rate, followed by an enhanced production of higher silane molecules. It has also been suggested that the responsible higher silane molecules for the above mentioned feedback phenomenon is penta-silane, Si₅H₁₂.     

Reducing the effects of mismatch between zinc oxide and silicon by silane plasma modification

We investigated the mismatch between zinc oxide (ZnO) and silicon (Si) upon reduction by silane plasma modification in a plasma-enhanced chemical vapor deposition system. This plasma treatment was only carried out for 10?s and the Si–H bonds that were provided by the silane plasma modification as dangling bonds on the Si wafer in addition to functioning as a conjunction layer to reduce the defects. The X-ray diffraction analysis of the ZnO/p-type silicon structure produced by silane plasma modification has a slightly lower full width at the half maximum, which improved the ZnO film’s crystalline properties. After the silane plasma modification ZnO/Si diode is produced, the measured current–voltage characteristics gave favorable rectifying properties and reverse bias had a low leakage current. The ZnO/Si diode under illumination increased the short-circuit current (I_sc) from 7.32 to 19.75?mA/cm², which is an improvement compared with a conventional bare ZnO/Si diode because of the reduced ZnO/Si interface states. Therefore, the silane plasma modification diminishes the effects of the interface and improves the ZnO/Si diode performance.     

Coplanar amorphous silicon thin film transistor fabricated by inductively-coupled plasma CVD

The electrical and optical properties of the a-Si:H films deposited by inductively-coupled plasma chemical vapour deposition (ICP-CVD) have been investigated. The ICP-CVD a-Si:H films deposited at 30 mTorr exhibited the deposition rate of 0.9 Å/s and the hydrogen content of 17 at.%. A novel coplanar self-aligned a-Si:H thin film transistor has been fabricated using Ni-silicide gate and source/drain contacts. The coplanar a-Si:H TFT exhibited a field effect mobility of 0.6 cm²/Vs, a threshold voltage of 2.3 V, a subthreshold slope of 0.5 V/dec.     

Bulk and interface properties of low-temperature silicon nitride films deposited by remote plasma enhanced chemical vapor deposition

Hydrogenated silicon nitride (a-SiN_x:H) films were deposited at temperatures ranging from 50 to 300 °C with remote plasma enhanced chemical vapor deposition (RPECVD) from NH}_{3 and SiH}_{4. The effect of the operating variables, such as deposition temperature and especially the partial pressure ratio of reactant (R=NH₃/SiH₄) on the properties of the Sa-SiN_x:H interface was investigated. The H^* radical was dominantly observed and the deposition rate was proportional to the NH^* radical concentration. The density of highly energetic N ₂ ^* radicals increased in the high plasma power regime in which the film surface was roughened, but they promote surface reactions even at low temperature. The refractive index was more closely related to the film stoichiometry than film density. The interface trap density is related to the amount of silicon intermediate species and Si–NH bonds at the Si/SiN_x:H interface and it can be minimized by reducing the intermediate Si species and Si–NH bonding state. The films showed a midgap interface trap density of 2 × 10¹¹ - 2 × 10¹²cm^-2. © 2001 Kluwer Academic Publishers     

Mass spectrometry of a silane glow discharge during plasma deposition of a-Si: H films

We undertook a mass spectrometric investigation of the ionic and neutral species present during the deposition of a-Si: H using an r.f. glow discharge in silane (mixed with helium or hydrogen). A correlation between the neutral composition of the plasma and the nature of the IR vibrational modes in the deposited film is proposed. The ionic species extracted from the silane discharge are not characteristic of the direct ionization of SiH₄. The predominance of the SiH₃⁺ ion is attributed to the ion-molecule reaction $\text{SiH}{}_2{}^{\mathrm{+}}\text{+ SiH}{}_4\text{→ SiH}{}_3{}^{\mathrm{+}}\text{+ SiH}{}_3$ Secondary ions Si₂H_n⁺ (n = 1?7) are also observed. Mass spectrometry of the ionic species resulting from the interaction of a hydrogen plasma with the a-Si: film suggests that atomic hydrogen plays an active role during the growth of the film.     

Langmuir probe diagnostics of microwave electron cyclotron resonance (ECR) plasma

A Langmuir probe diagnostics is done on the microwave ECR generated plasma in a 2.45 GHz, 1.5 kW facility set up in our laboratory (for thin film deposition) by inserting a probe in the plasma close to substrate location (640 mm away from main ECR zone). A program using Graphical User Interface (GUI) was used for data analysis of I-V probe characteristics to obtain the radial electron energy distribution function (EEDF) in plasma. Plasma parameters such as charged particle density (n_e and n_i), electron temperature (T_e), plasma potential (V_pl) and floating potential (V_float) were estimated at substrate location for two incident microwave power levels at a fixed operating pressure. These parameters were estimated by different methods like orbital motion limited (OML) theory, electron energy distribution function (EEDF) and conventional method. The results obtained by the different methods are compared and observed differences are explained. The results indicate that even though the diffusion of plasma at the substrate location is mainly forced by particle collisions that lead to radial plasma uniformity, it still shows a non-Maxwellian behavior for the electrons with two groups having different energies.     

Structural and optical properties of four-hexagonal polytype nanocrystalline silicon carbide films deposited by plasma enhanced chemical vapor deposition technique

Four-hexagonal polytype films of nanocrystalline silicon carbide (4H-nc-SiC) were deposited by plasma enhanced chemical vapor deposition method with more than 3×10⁴ W m⁻² threshold of power density, high hydrogen dilution ratio, and bias pretreatment. The source gases were silane, methane and hydrogen. Our work showed that under conditions similar to those used for the growth of μc-SiC—except a higher power densities over a threshold, a bigger bias pretreatment on substrates, and a moderate bias deposition—nc-SiC films could indeed be achieved. The Raman spectra and transmission electron microscopy diffraction patterns demonstrated that the as-grown films from the H₂-CH₄-SiH₄ plasma consist of amorphous network and phase-pure crystalline silicon carbide which has the 4H polytype structure. The microcolumnar 4H-SiC nanocrystallites of a mean size of approximately 1.6×10⁻⁸ m in diameter are encapsulated by amorphous SiC networks. The photoluminescence spectra of 4H-SiC at room temperature, peaking at 8.10×10⁻⁷ m using a wavelength of 5.145×10⁻⁷ m of argon ion laser, were obtained at room temperature; the luminescence mechanism is thought to be related to transitions in the energy band gap which could be ascribed to the surface states and defects in the structure of 4H-SiC nanocrystalline in these films due to its small size. The as-grown films showed an optical transmittance of 89% at 6.58×10⁻⁷ m. This higher transmittance is believed to be from the small size and amorphous matrix.     

Cold deposition of large-area amorphous hydrogenated silicon films by dielectric barrier discharge chemical vapor deposition

Amorphous hydrogenated silicon films were deposited on glass substrates at room temperature. This cold deposition process was operated in a dielectric barrier discharge CVD reactor with a fixed strip-shaped plasma matched with a moving substrate holder. The maximum film area was 300 × 600 mm². The film deposition rate as a function of applied peak voltage of DBD power was investigated under different hydrogen-diluted silane concentrations, and the film surface smoothness, continuity, and film/glass adherence were also studied. The maximum deposition rate was 12.2 Å/s, which was performed under the applied peak voltage of 16 kV and a hydrogen-diluted silane concentration of 50%. IR measurements reveal that the silane concentration plays a key role in determining the hydrogen-silicon bonding configurations. With increasing hydrogen-diluted silane concentration, the H-Si bonding configurations shift gradually from Si-H₃ to Si-H. The variation of photo/dark conductivity ratio and optical bandgap versus hydrogen-diluted silane concentration were investigated. The use of DBD-CVD for deposition of a-Si:H films offers certain advantages, such as colder substrate, faster film growth rate, and larger deposition area. However, the consumption of silane for the DBD-PECVD procedure is much greater than for the RF-PECVD process.     

Amorphous hydrogenated silicon-nitride films for applications in solar cells

The application of anti-reflective coatings (ARC) is a good method to improve the solar cell construction. The authors developed the RF plasma enhanced chemical vapour deposition method for preparation of amorphous silicon-nitrogen (a-Si:N:H) films for potential optoelectronic applications. The films have been obtained on borosilicate glass and monocrystalline silicon (1 0 0) (Cz-Si) in a process with optimised technological parameters such as a content of gaseous mixture of silane (SiH₄) and ammonia (NH₃). The properties of samples have been investigated by optical spectroscopy (PERKIN-ELMER Lambda 19) and scanning electron microscopy (SEM). The correlation between film properties and process parameters has been found. The results of optical investigations show that these materials are characterised by a variable optical gap dependent on the nitrogen content. After deposition of a-Si:N:H, a decrease in the total reflectivity, as compared to that of monocrystalline Si, was observed. The simulation of multicrystalline silicon solar cells performance with and without the ARC was done with the use of PC1D programme. The influence of the ARC on solar cell efficiency was observed. The obtained results indicate that a-Si:N:H films are suitable for application as antireflective and protective coatings for solar cells.     

Rapid thermal-plasma annealing of ZnO:Al films for silicon thin-film solar cells

Rapid thermal annealing of sputter-deposited ZnO and Al-doped ZnO (AZO) films with and without an amorphous silicon (a-Si) capping layer was investigated using a radio-frequency (rf) argon thermal plasma jet at atmospheric pressure. The resistivity of bare ZnO films on glass decreased drastically from 10⁶ to 10³ Ω·cm at maximum surface temperatures T_max above 650 °C, whereas the resistivity increased from 10^− 4 to 10^− 3-10^− 2 Ω·cm for bare AZO films. On the other hand, the resistivity of AZO films with a 30-nm-thick a-Si capping layer remained below 10^− 4 Ω·cm, even after TPJ annealing at a T_max of 825 °C. X-ray diffraction and X-ray photoemission electron studies revealed that the film crystallization of both AZO and a-Si layers was promoted without the formation of an intermixing layer. Additionally, the crystallization of phosphorous- and boron-doped a-Si layers at the sample surface was promoted, compared to that of intrinsic a-Si under identical plasma annealing conditions. The role of the a-Si capping layer on sputter-deposited AZO and ZnO films during TPJ annealing is demonstrated. The effects of the mixing of phosphorous and boron impurities in a-Si:H during TPJ annealing of flat and textured AZOs are also discussed.     

Multi-walled carbon nanotubes grow under low pressure hydrogen,air, and argon ambient by arc discharge plasma

Multi-walled carbon nanotubes (MWCNTs) were grown on cathode deposit by arc discharge plasma under H₂, Ar, and air ambient environment. The influence of ambient gas pressure on the structure and physical properties of carbon nanotube were compared. Herein, we highlight the influence of ambient environment and pressure to grow high quality carbon nanotubes. Field emission scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction were used for structural characterization and yield determination. The result revealed that background gas and pressure were crucial factor for growing highly crystalline and highly graphitic with I_D/I_G ratio 0.237 obtained for MWCNTs' synthesized in H₂ environment with extreme low defects.     

Role of argon in hot wire chemical vapor deposition of hydrogenated nanocrystalline silicon thin films

Structural, optical and electrical properties of hydrogenated nanocrystalline silicon (nc-Si:H) films, deposited from silane (SiH₄) and argon (Ar) gas mixture without hydrogen by hot wire chemical vapor deposition (HW-CVD) method were investigated. Film properties are carefully and systematically studied as a function of argon dilution of silane (R_Ar). We observed that the deposition rate is much higher (4-23 Å/s) compared to conventional plasma enhanced chemical vapor deposited nc-Si:H films using Ar dilution of silane (0.5-0.83 Å/s). Characterization of these films with Raman spectroscopy revealed that Ar dilution of silane in HW-CVD endorses the growth of crystallinity and structural order in the nc-Si:H films. The Fourier transform infrared spectroscopic analysis showed that with increasing Ar dilution, the hydrogen bonding in the films shifts from di-hydrogen (Si-H₂) and (Si-H₂)_n complexes to mono-hydrogen (Si-H) bounded species. The hydrogen content in the films increases with increasing Ar dilution and was found to be < 4 at.% over the entire range of Ar dilutions of silane studied. However, the band gap shows decreasing trend with increase in Ar dilution of silane and it has been attributed to the decrease in the percentage of the amorphous phase in the film. The microstructure parameter was found to be > 0.4 for the films deposited at low Ar dilution of silane and ~ 0.1 or even less for the films deposited at higher Ar dilution, suggesting that there is an enhancement of structural order and homogeneity in the film. From the present study it has been concluded that the Ar dilution of silane is a key process parameter to induce the crystallinity and to improve the structural ordering in the nc-Si:H films deposited by the HW-CVD method.     

The control of the high-density microwave plasma for large-area electronics

A uniform, low-temperature, and high-density microwave plasma (2.45 GHz) is produced without magnetic field, utilizing a spokewise antenna. The plasma maintains a uniform state in Ar low pressure of several 10 mTorr with high electron density, >10¹¹ cm⁻³, and a temperature less than 2.5 eV within ±6% over 16 cm in diameter. Highly crystallized and photoconductive, hydrogenated microcrystalline silicon (μc-Si:H) film is produced from dichlorosilane (SiH₂Cl₂), H₂ and Ar mixture at high deposition rate of more than 5 Å/s. This low-temperature and high-density microwave plasma source has a high potential not only for etching but for future large-area film deposition processes.     

High rate growth highly crystallized microcrystalline silicon films using SiH4/H2 high-density microwave plasma

The plasma parameter for fast deposition of highly crystallized microcrystalline silicon (μc-Si) films with low defect density is presented using the high-density and low-temperature microwave plasma (MWP) of a SiH₄-H₂ mixture. A very high deposition rate of ∼ 65 Å/s has been achieved at SiH₄ concentration of 67% diluted in H₂ with high Raman crystallinity I_c / I_α > 3 and low defect density of 1-2 × 10¹⁶ cm^− 3 by adjusting the plasma condition. Contrary to the conventional rf plasma, the defect density of the μc-Si films strongly depend on substrate temperature T_s and it increased with increasing T_s despite T_s below 300 °C, suggesting that the real surface temperature at the growing surface was higher than the monitored value. The sufficient supply of deposition precursors such as SiH₃ at the growth surface under an appropriate ion bombardment was effective for the fast deposition of highly crystallized μc-Si films as well as the suppression of the incubation and transition layers at the initial growth stage.     

Spectroscopic ellipsometry studies on hydrogenated amorphous silicon thin films deposited using DC saddle field plasma enhanced chemical vapor deposition system

Hydrogenated amorphous silicon (a-Si H) films deposited on crystalline silicon substrates using the DC saddle field (DCSF) plasma enhanced chemical vapor deposition (PECVD) system have been investigated. We have determined the complex dielectric function, ε(E) = ε₁(E) + iε₂(E) for hydrogenated amorphous silicon (a-Si:H) thin films by spectroscopic ellipsometry (SE) in the 1.5-4.5 eV energy range at room temperature. The results indicate that there is a change in the structure of the a-Si:H films as the thickness is increased above 4 nm. This is attributed to either an increase in the bonded hydrogen content and, or a decrease of voids during the growth of a-Si:H films. The film thickness and deposition temperature are two important parameters that lead to both hydrogen content variation and silicon bonding change as well as significant variations in the optical band gap. The influence of substrate temperature during deposition on film and interface properties is also included.     

Time and space resolved Langmuir probe measurements of a pulsed vacuum arc plasma

The time and space evolution of pulsed vacuum arc plasma parameters have been measured using a single cylindrical Langmuir probe in a free expansion cup. Electron density n_e, effective electron temperature T_eff and electron energy distribution function (EEDF) are derived from the I-V curves using Druyvesteyn method. Results show that during the discharge time, the electron density n_e is between 0.27 and 1.82 × 10¹⁸ m⁻³ and the effective electron temperature T_eff is between 6.14 and 14.72 eV, both of which decrease as a function of the discharge time. The electron energy distribution function (EEDF) is no-Maxwellian since the high-energy electrons depart from the Maxwellian distribution. Due to the plasma expansion, the electron density n_e decreases as increase of the expansion distance, but the effective electron temperature T_eff is weakly dependent on the distance in the free expansion cup.     

Dependence of the a-Si:H defect density of states on the magnetic field profile of an electron cyclotron resonance microwave plasma

The magnetic field profile of an electron cyclotron resonance microwave plasma was systematically altered to determine subsequent effects on a-Si:H film quality. The mobility gap deep density N_D deposition rate and light-to-dark conductivity were determined for the a-Si:H films. By variation of the magnetic field profile N_D could be altered by more than an order of magnitude, from 1 × 10¹⁶ to 1 × 10¹⁷ cm⁻³ at 0.7 mTorr and 1 × 10¹⁶ to 5 × 10¹⁷ cm⁻³ at 5 mTorr as determined by junction capacitance techniques. Two deposition regimes were found to occur for the conditions of this study. Highly divergent magnetic fields resulted in poor quality a-Si:H, while for magnetic field profiles defining a more highly confined plasma, the a-Si:H was of device quality and relatively independent of the magnetic field configuration. The data is interpreted as a consequence of silane depletion for highly divergent magnetic field profiles.     

Optical and structural characterization of inhomogeneities in a-Si:H TO μc-Si transition

The a-Si:H films with different thickness and microstructure have been deposited with rf-PECVD using a plasma of silane diluted with hydrogen. The structure and optical analysis were carried out by X-ray diffraction, UV-VIS and Raman spectroscopy. Spectral refractive indices, optical energy band gaps, extinction coefficients, phases ratio and grain size were determined as a function of the hydrogen dilution (R = H₂/SiH₄). Hydrogen dilution of silane results in an inhomogeneous growth during which the material evolves from amorphous hydrogenated silicon (a-Si:H) to micro-crystalline hydrogenated silicon (μc-Si:H). XRD analysis indicated that films with R = 0 and R = 20 were amorphous and homogeneous, while films with R = 40 and higher were micro-crystalline consisting medium range ordered silicon hydride (Si₄H) and μc-Si phases with different size of crystallites, which was confirmed also by Raman spectroscopy.     

Emission spectroscopy of a dipolar plasma source in hydrogen under low pressures

Low-temperature hydrogen plasma has been investigated under the conditions of electron cyclotron resonance by emission spectroscopy. The molecular distribution functions over the low rotational and vibrational levels of the hydrogen molecule in the d³Π_u^- triplet state have been measured. The translational, rotational, and vibrational temperatures of the ground and excited triplet states of the hydrogen molecule are determined. The obtained translational and vibrational temperatures indicate that low-temperature hydrogen plasma under the conditions of electron cyclotron resonance is a more efficient source of vibrationally excited hydrogen molecules in comparison with the other gas discharges.