Intermediate gas phase precursors during plasma CVD of HMDSO

In plasma enhanced chemical vapor deposition (PECVD) from complex molecules like hexamethyldisiloxan (HMDSO) often not the molecules themselves but intermediate and reactive radicals or molecules are the precursors for film growth. Additionally, such PECVD processes are volume or mass flow limited under many process conditions. In these cases growth rate and film homogeneity is mainly dominated by the precursor content and its spatial distribution in the gas or plasma phase. Therefore the identification of such intermediate precursors is an important task to optimize a PECVD process and also helps us to understand the plasma chemical reactions during PECVD. A combined mass spectrometry and IR absorption study is used to identify intermediate gas phase precursors in HMDSO/O₂ PECVD remote plasmas. For this study a microwave plasma CVD system was used with HMDSO/O₂ ratios between 0.1 and 1 at typical operating pressures between 20 and 70 Pa. Three reactive intermediate species are proposed to act as a precursor for SiO_x film growth from HMDSO/O₂ plasmas. All three having a mass of 148 amu. The related reactive groups are the silanon (Si=O), silanol (Si-OH) and aldehyde (C=O) groups.     

SiOx plasma thin film deposition using a low-temperature cascade arc torch

Plasma thin films were deposited from gas mixtures of hexamethyldisiloxane (HMDSO) and oxygen (O₂) using a low-temperature cascade arc torch (LTCAT). Various properties of the deposited HMDSO plasma coatings, including refractive index (RI), surface contact angle, and hardness were evaluated. The characterization results using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, ellipsometry, and water contact angle measurements indicated that, with increased O₂ addition, the deposited HMDSO plasma thin films were of inorganic SiO_x nature. It was also found that, in the LTCAT plasma system, O₂ addition significantly improves the hardness of the resulting HMDSO plasma coatings. The film hardness of the deposited HMDSO plasma coatings measured by a standard pencil test (ASTM D3363-05) reached 6H with increased O₂ addition in the HMDSO/O₂ gas mixture. Such hard plasma coatings could be potentially used for many important industrial applications, such as anti-scratch coatings on plastic glasses and various plastic lens materials.     

Studies of radiofrequency plasma deposition of hexamethyldisiloxane films and their thermal stability and corrosion resistance behavior

Hexamethyldisiloxane (HMDSO) films (thickness: 282-929 nm) are prepared by the radiofrequency plasma assisted chemical vapour deposition (RF-PACVD) method using an Ar/HMDSO/O₂ gas mixture. The deposition process is carried out in an RF reactor at a working pressure of 1.2 × 10⁻¹ mbar and an RF power range of 20-100 W. From the studies on Ar/O₂ and Ar/HMDSO/O₂ discharge characteristics using a self-compensated emissive probe, it is revealed that electrons play an important role in the plasma polymerization of HMDSO monomers. Optical emission spectroscopy (OES) and Fourier transform infrared (FT-IR) spectroscopy show that the plasma deposited HMDSO films tend to be more inorganic in nature at higher RF powers. A film prepared at an RF power of 100 W exhibits more thermal stability and corrosion resistance behavior in comparison to films deposited at lower powers (20-80 W). A correlation of the results obtained from OES and FT-IR analyses with the thermal stability and corrosion resistance behavior of the films has been attempted.     

HMDSO plasma polymerization and thin film optical properties

Thin films were deposited from hexamethyldisiloxane (HMDSO) in a glow discharge supplied with radiofrequency (rf) power. Actino-metric optical emission spectroscopy was used to follow trends in the plasma concentrations of the species SiH (414.2 nm), CH (431.4 nm), CO (520.0 nm), and H (656.3 nm) as a function of the applied rf power (range 5 to 35 W). Transmission infrared spectroscopy (IRS) was employed to characterize the molecular structure of the polymer, showing the presence of Si-H, Si-O-Si, Si-O-C and C-H groups. The deposition rate, determined by optical interferometry, ranged from 60 to 130 nm/min. Optical properties were determined from transmission ultra violet-visible spectroscopy (UVS) data. The absorption coefficient , the refractive index n, and the optical gap E₀₄ of the polymer films were calculated as a function of the applied power. The refractive index at a photon energy of 1 eV varied from 1.45 to 1.55, depending on the rf power used for the deposition. The absorption coefficient showed an absorption edge similar to other non-crystalline materials, amorphous hydrogenated carbon, and semiconductors. For our samples, we define as an optical gap, the photon energy E₀₄ corresponding to the energy at an absorption of 10⁴ cm⁻¹. The values of E₀₄ decreased from 5.3 to 4.6 as the rf power was increased from 5 to 35 W.     

Measurement of absolute minority species concentration and temperature in a flame by the photothermal deflection spectroscopy technique

It is experimentally demonstrated that absolute concentrations of minority species in flames can be measured by the photothermal deflection spectroscopy (PTDS) technique. In addition, the PTDS signal simultaneously yields the flame temperature the measurement point. Absolute concentration profiles of OH have been measured in a flat-flame burner with methane as fuel. The PTDS measurements agree well with those obtained independently by the absorption technique. The flame temperature measurements by PTDS are also in good agreement with those obtained by the Boltzmann distribution among the rotational levels of OH.     

Effects of surface treatments using PECVD-grown hexamethyldisiloxane on the performance of organic thin-film transistor

Hexamethyldisiloxane (HMDSO) was deposited on a gate dielectric surface by plasma enhanced chemical vapor deposition for surface treatment, and its effects on the microstructure of pentacene and the transistor characteristics were examined. HMDSO films were deposited at room temperature at various RF powers (10 W to 120 W). Atomic force microscopy analysis of the pentacene films showed a significant increase in the grain size of the samples treated under the optimum RF power (10 W), which in turn led to a significant improvement in the electrical mobility. These results show that PECVD-grown HMDSO can be used as an effective surface treatment and warrants further investigation for process optimization.     

An X-ray photoelectron spectroscopic investigation into the chemical structure of deposits formed from hexamethyldisiloxane/ oxygen plasmas

The effect of oxygen addition to microwave-sustained plasmas of hexamethyldisiloxane (HMDSO) has been investigated. Attention was directed to the solid products formed on aluminium substrates (plasma deposits). To enable a quantitative analysis of these, X-ray photoelectron spectroscopy (XPS) of standard silicon-containing materials was carried out. When suitable charge correction is applied to the XP spectra of HMDSO/O₂ plasma deposits, a number of very clear trends emerge. From changes in elemental composition, core line binding energies (Si2p, C 1s, and O 1s) and widths, we show how oxygen addition to the plasma affects the chemical nature of the plasma deposit. The data reported also provide (some limited) information on the reactions taking place in the plasma.     

R.f. plasma deposition from hexamethyldisiloxane-oxygen mixtures

Hexamethyldisiloxane (HMDSO) has been used as a precursor for the deposition of silicon dioxide films at low substrate temperature (25–400°C) by plasma enhanced chemical vapour deposition processing. Effects of the partial pressure of oxygen in the discharge on the deposition rate and the composition of the films are investigated. The deposition rate is found to decrease with increasing oxygen concentration in the HMDSO/O₂ mixture. The chemical composition of the formed films was characterized by X-ray photoelectron spectroscopy and infrared spectroscopy. Over 40% of the oxygen in the gas phase the carbon content of films deposited from HMDSO/O₂ mixtures is less than 5%.     

Plasma characterization of cross-beam pulsed-laser ablation used for carbon thin film deposition

The dynamics of the interaction between two delayed plasmas induced by cross-beam pulsed-laser ablation was analyzed by fast photography using narrow interference filters. In this configuration, two perpendicular rotating carbon targets were ablated by two synchronized laser beams generating two interacting plasma plumes. A Nd: yttrium-aluminum-garnet (1064 nm) laser beam is focused onto a target generating a highly directed plume; subsequently an excimer laser (248 nm) produces a second perpendicular plasma, which expands through the plume region generated by the first laser. In the cross-beam configuration, collision processes cause a reduction in the C II ion kinetic energy from ∼ 110 to 35 eV; moreover, the species of the second plasma which travel on the normal direction to the target surface (toward the substrate) are mainly C II. Interaction between plasmas has been compared with laser-induced plume propagation through a background gas in terms to the drag model. Carbon thin films were deposited by the cross-beam technique for different delays between lasers. Raman spectroscopy was employed to study the changes in the bonding carbon films as a function of the kinetic energy of ablated C ions.     

Plasma diagnostics in plasma processing for nanotechnology and nanolevel chemistry

The author reviews the role of various plasma diagnostics in plasma processing for nanotechnology, and points out some essential methods of spectroscopic methods to diagnose plasmas for nanoprocessing. Two experimental examples are discussed between the characteristics of nanomaterials and plasma parameters. One is measurement of rotation temperature in processing of carbon nanotube. The other is that of vibrational temperature in surface nitriding of titanium by nitrogen plasma processing. We summarize what to measure and how to measure them from the technical viewpoint of plasma diagnostics.     

Plasma diagnostics in plasma processing for nanotechnology and nanolevel chemistry

The author reviews the role of various plasma diagnostics in plasma processing for nanotechnology, and points out some essential methods of spectroscopic methods to diagnose plasmas for nanoprocessing. Two experimental examples are discussed between the characteristics of nanomaterials and plasma parameters. One is measurement of rotation temperature in processing of carbon nanotube. The other is that of vibrational temperature in surface nitriding of titanium by nitrogen plasma processing. We summarize what to measure and how to measure them from the technical viewpoint of plasma diagnostics.     

Physical and tribological properties of diamond films grown in argoncarbon plasmas

Nanocrystalline diamond films have been deposited using a microwave plasma consisting of argon, 2–10% hydrogen and a carbon precursor such as C₆₀ or CH₄. It was found that it is possible to grow the diamond phase with both carbon precursors, although the hydrogen concentration in the plasma was 1–2 orders of magnitude lower than normally required in the absence of the argon. Auger electron spectroscopy, X-ray diffraction measurements and transmission electron microscopy indicate the films are predominantly composed of diamond. Surface roughness, as determined by atomic force microscopy and scanning electron microscopy indicate the nanocrystalline films grown in low hydrogen content plasmas are exceptionally smooth (30–50 nm rms) to thicknesses of 10 m. The smooth nanocrystalline films result in low friction coefficients (μ = 0.04–0.06) and low average wear rates as determined by ball-on-disk measurements.     

Development of a spectrometer using a continuous wave distributed feedback quantum cascade laser operating at room temperature for the simultaneous analysis of N2O and CH4 in the Earth's atmosphere

We report on the development and performance of a gas sensor based on a distributed feedback quantum cascade laser operating in continuous wave at room temperature for simultaneous measurement of nitrous oxide (N(2)O) and methane (CH(4)) concentrations at ground level. The concentrations of the gases are determined by a long path infrared diode laser absorption spectroscopy. The long-term stability of the instrument is evaluated using the Allan variance technique. A preliminary evaluation of the instrument performance is realized by in situ measurements of N(2)O and CH(4) concentrations at ground level during 1 day. The sensor has also been applied to study the time response of N(2)O concentrations to a fertilizer addition in a soil sample and for the comparison between various types of soils.     

Tunable Diode Laser Spectroscopy for Industrial Process Applications: System Characterization in Conventional and New Approaches

Tunable diode laser spectroscopy (TDLS) can only be successfully implemented if a number of system characterization procedures and critical parameter measurements can be made accurately. These include: application of a wavelength/frequency scale to the signals recovered in time; measurement of the frequency dither applied to the laser; measurement of the relative phase between the laser power modulation and frequency modulation; determination of the background amplitude modulation for normalization purposes and measurement of required cross broadening coefficients for the host/target gas mixtures. Easy to implement, accurate and low-cost systems and procedures for achieving these are described and validated below. They were developed for two new approaches to TDLS measurements, viz the residual amplitude modulation (RAM) technique and the phasor decomposition (PD) method, but are equally applicable to all forms of TDLS. Following full system characterization using the new techniques, measurements of the absolute transmission function of the 1650.96 nm absorption line of methane over a wide range of concentration and pressure were made using the RAM technique. The close agreement with theoretical traces derived from HITRAN data validated the entire approach taken, including the system characterization procedures. In addition, measurements of a wide range of gas concentration and pressure were made by curve fitting theoretical traces to the measured transmission functions obtained using a variety of operating conditions. Again, the low errors confirmed the validity of the new methods and the system characterization/measurement procedures described here.     

单体对大气下沉积SiOx薄膜的性能研究

在大气压下,利用工作在16kHz的介质阻挡放电(DBD)等离子枪,以氩气为工作气体,分别用四甲基硅氧烷(TEOS)、六甲基硅氧烷(HMDSO)和八甲基环四硅氧烷(D4)为单体,通过改变载气流量、等离子体放电功率等研究聚合SiOx薄膜的结构性能影响.采用红外光谱(FTIR)分析所沉积SiOx薄膜的结构,通过接触角测试了解其表面亲/疏水性能.     

Differential absorption measurement of methane with two spatially resolved laser lines

Simultaneous and independent lasing on two different atomic lines is achieved with spatial resolution of laser eigenstates in conjunction with intracavity frequency selection. A sensitivity of 0.3 part in 10(6) meter in the differential detection of methane in 1 atm of air is experimentally demonstrated with this novel dual-wavelength laser. Monitoring the output intensities of the two orthogonally polarized eigenstates permits absolute measurement of methane concentration.     

Thermal plasma synthesized nano-powders of (LaCe)B6 starting from oxide-based precursors and its field electron emission performance

High temperature synthesis process of microcrystalline and nanocrystalline (LaCe)B₆ using Self-propagating High temperature Synthesis (SHS) and arc plasma gas phase condensation methods, respectively have been investigated. These methods are rapid and economically viable processes used for the synthesis of technologically important refractory hexaborides. Microcrystalline powders of (LaCe)B₆ were synthesized using the SHS process, starting from oxide precursors of lanthanum, cerium, and boron. The powders obtained using SHS process were used as a precursor to getting nanocrystalline (LaCe)B₆ using the thermal plasma route. The thermal plasma synthesis was carried out using nitrogen and argon plasmas, respectively. In-situ plasma diagnostics were used to identify evaporated species and determine plasma temperature during the formation of nanocrystalline (LaCe)B₆ using optical emission spectroscopy. Further, an effect of plasma input parameters on the structural and optical properties of as synthesized nanocrystalline (LaCe)₆ were investigated using XRD analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. A thorough investigation of morphological and structural properties of synthesized nanocrystalline (LaCe)₆ was carried out using transmission electron microscopy. Finally, field effect electron emission properties of the microcrystalline and nanocrystalline product were investigated and current density, turn on field, stability of emission performance were determined.     

Laser-induced fluorescence ion diagnostics in light of plasma processing

A brief overview of non-perturbing light diagnostics is followed by recent examples of process plasma properties measured via laser-induced fluorescence (LIF), optical emission, and absorption spectroscopy. Examples include radical density measurement via absorption and emission spectroscopy. With LIF, examples show properties of ion beam etching sources and ion velocity angle variations in ICP sheaths near a process surface. Because of the wide range of process plasma parameters, appropriate choice of light diagnostics varies.     

Analysis of the absorption layer of CIGS solar cell by laser-induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) was applied for the elemental analysis of the thin copper indium gallium diselenide (CuIn(1-x)Ga(x)Se(2) [CIGS]) absorption layer deposited on Mo-coated soda-lime glass by the co-evaporation technique. The optimal laser and detection parameters for LIBS measurement of the CIGS absorption layer (1.23 μm) were investigated. The calibration results of Ga/In ratio with respect to the concentration ratios measured by x-ray fluorescence and inductively coupled plasma optical emission spectroscopy showed good linearity.     

Effect of swirl flow on an atmospheric inductively coupled plasma supersonic jet

Recently supersonic jets extracted from atmospheric inductively coupled plasmas (ICP) have attracted a lot of attention. Usually atmospheric ICP generators have employed swirl flow injection in order to stabilize the plasma. However the effect of the swirl flow injection on the performance of atmospheric ICP generators has not been understood enough. This work found that the injection of the swirl flow deteriorates the performance. First we conducted the total enthalpy measurement based on the sonic flow method and evaluated the averaged specific enthalpy. Then laser absorption spectroscopy was employed in order to measure the temperature and the velocity of the extracted supersonic jet. The both measurements observed that the specific enthalpy of the jets decreased with the increase in the swirl flow fraction. This would be because the swirl flow affected the shape and the position of the plasma significantly.