Influence of SiNx:H film properties according to gas mixture ratios for crystalline silicon solar cells

The Hydrogenated silicon nitride (SiN_x:H) using plasma enhanced chemical vapor deposition is widely used in photovoltaic industry as an antireflection coating and passivation layer. In the high temperature firing process, the SiN_x:H film should not change the properties for its use as high quality surface layer in crystalline silicon solar cells. For optimizing surface layer in crystalline silicon solar cells, by varying gas mixture ratios (SiH₄ + NH₃ + N₂, SiH₄ + NH₃, SiH₄ + N₂), the hydrogenated silicon nitride films were analyzed for its antireflection and surface passivation (electrical and chemical) properties. The film deposited with the gas mixture of SiH₄ + NH₃ + N₂ showed the best properties in before and after firing process conditions.The single crystalline silicon solar cells fabricated according to optimized gas mixture condition (SiH₄ + NH₃ + N₂) on large area substrate of size 156 mm × 156 mm (Pseudo square) was found to have the conversion efficiency as high as 17.2%. The reason for the high efficiency using SiH₄ + NH₃ + N₂ is because of the good optical transmittance and passivation properties. Optimized hydrogenated silicon nitride surface layer and high efficiency crystalline silicon solar cells fabrication sequence has also been explained in this study.     

Temperature effect on deposition rate of silicon nitride films

Temperature effects on deposition rate of silicon nitride films were characterized by building a neural network prediction model. The silicon nitride films were deposited by using a plasma enhanced chemical vapor deposition system and process parameter effects were systematically characterized by 2⁶⁻¹ fractional factorial experiment. The process parameters involved include a radio frequency power, pressure, temperature, SiH₄, N₂, and NH₃ flow rates. The prediction performance of generalized regression neural network was drastically improved by optimizing multi-valued training factors using a genetic algorithm. Several 3D plots were generated to investigate parameter effects at various temperatures. Predicted variations were experimentally validated. The temperature effect on the deposition rate was a complex function of parameters but N₂ flow rate. Larger decreases in the deposition rate with the temperature were only noticed at lower SiH₄ (or higher NH₃) flow rates. Typical effects of SiH₄ or NH₃ flow rate were only observed at higher or lower temperatures. A comparison with the refractive index model facilitated a selective choice of either SiH₄ or NH₃ for process optimization.     

Optical and Structural Properties of Ammonia-Free Amorphous Silicon Nitride Thin Films for Photovoltaic Applications

Hydrogenated amorphous silicon nitride (a-SiN_x:H) thin films have been deposited through the green chemistry route using silane (SiH₄) and nitrogen (N₂) as process gases with SiH₄ flow being variable and N₂ flow being constant without the use of pollutant and corrosive ammonia (NH₃) by the plasma-enhanced chemical vapor deposition technique at 13.56 MHz. Fourier transform infrared spectroscopy analysis shows various possible vibrational modes of Si-H, Si-N, and N-H bonds present in the film. Raman spectroscopy is performed on these samples to calculate volume fractions corresponding to amorphous phases present in the a-SiN_x:H films. The refractive index (η) values are calculated using Swanepoel's method, which are in the range of 2.89 to 3.17. The thickness of the deposited films has been evaluated using transmission spectra. Absorption coefficient and band gap (E _g) values are obtained from optical absorption studies. An increase in the E _g and a decrease in the η value have been observed for the samples grown with decreasing SiH₄ flow.     

Chemical control of physical properties in silicon nitride films

Amorphous hydrogenated silicon nitride (a-SiN _x H _y ) films were prepared by plasma-enhanced chemical vapor deposition (PECVD). The physical properties and chemical structures of the resulting materials were systematically investigated. Results reveal that the a-SiN _x H _y films similarly consist of four kinds of Si–N groups, including Si₃N₄, H–Si–N₃, H₂–Si–N₂, and Si₃–Si–N. Deposition at 13.56 MHz and 300 ^°C with flow ratio of SiH₄/NH₃=30/30 sccm leads to the yield of Si_0.39N_0.38H_0.23 films that exhibit excellent properties of high uniformity, high elastic modulus, moderate refractive index and optical band gap, low UV absorption, and ultralow residual stress (?0.17 MPa). Such Si_0.39N_0.38H_0.23 films hold considerable promise for applications in solar cells and infrared sensors. In contrast, an increase of Si or N content in a-SiN _x H _y films will cause the degradation of the properties, so that the films are unsuitable for solar cells. Moreover, a new conception of network degree was proposed to evaluate and explain the properties of a-SiN _x H _y films. Particularly, this work discloses the relationships between the chemical structures and physical properties, and suggests a basic approach to the yield of a-SiN _x H _y films with controlled physical properties.     

激发频率对高氢稀释下纳米晶硅薄膜生长特性的影响

利用等离子体增强化学气相沉积技术,在高氢稀释条件下,研究不同激发频率对纳米晶硅薄膜生长特性的影响.剖面透射电子显微镜(TEM)分析结果显示,不同激发频率下制备的纳米晶硅薄膜晶化区均呈锥状结构生长,但13.56 MHz激发频率下制备的纳米晶硅薄膜最初生长阶段存在非晶态孵化层,即纳米晶硅薄膜的形成经历了由非晶态孵化层到晶态结构层的转变.而高激发频率(40.68 MHz)下硅纳米晶则能直接在非晶态衬底上生长形成.Raman谱和红外吸收谱测量结果表明高激发频率(40.68 MHz)下制备的纳米晶硅薄膜不但具有较高     

Low-temperature formation of silicon nitride films using pulsed-plasma CVD under near atmospheric pressure

Silicon nitride (SiN_X) film fabrication on polyethylene terephthalate (PET) substrates has been achieved at a low temperature (∼100 °C) by plasma enhanced chemical vapor deposition operated at near atmospheric pressures. A short-pulse based power system was employed to maintain a stable discharge of SiH₄, H₂ and N₂ in near atmospheric pressures without the use of any inert gases such as He. The deposited films were characterized by X-ray photoelectron spectroscopy. Cross sections of the films were observed by scanning electron microscope (SEM). Despite the use of N₂ in place of NH₃, a high deposition rate (290 nm/min) was obtained by this near-atmospheric-pressure plasma.     

Properties of a-Si:N:H films beneficial for silicon solar cells applications

Amorphous silicon-nitride thin films a-Si:N:H were obtained by plasma enhanced chemical vapour deposition (PECVD) method from SiH₄+NH₃ at 13.56 MHz. The process parameters were chosen to obtain the films of properties suitable for optoelectronic and mechanical applications. FTIR analysis of a-Si:N:H films indicated the presence of numerous hydrogen bonds (Si-H and N-H) which passivate structural defects in multicrystalline silicon and react with impurities. The morpho-logical investigations show that the films are homogeneous. The deposition of a-Si:N:H layers leads to the decrease in friction coefficient of used substrates. Optical properties were optimised to obtain the films of low effective reflectivity, large energy gap E_g from 2.4 to 2.9 eV and refractive index in the range of 1.9 to 2.2. Reduction of friction coefficient for monocrystalline silicon after covering with a-Si:N:H films was observed: from 0.25 to 0.18 for 500 cycles.     

射频激发热丝化学气相沉积制备硅薄膜过程中光发射谱的研究

采用射频(rf)激发,在热丝化学气相沉积(HWCVD)制备微晶硅薄膜的过程中产生发光基元,测量了rf激发HWCVD (rf-HWCVD)的光发射谱,比较了相同工艺条件下rf-HWCVD和等离子体增强CVD(PECVD)的光发射谱,分析了rf功率、热丝温度和沉积气压对rf-HWCVD光发射谱的影响.结果表明,在射频功率<0.1W/cm²时,rf-HWCVD发射光谱反映了HWCVD高的气体分解效率和高浓度原子氢的特点,能够解释气压变化与微晶硅薄膜微结构的关系,是研究HWCVD气相过程的有 关键词： HWCVD OES 微晶硅     

Growth characteristics of amorphous-layer-free nanocrystalline silicon films fabricated by very high frequency PECVD at 250 ℃

Amorphous-layer-free nanocrystalline silicon films were prepared by a very high frequency plasma enhanced chemical vapor deposition(PECVD) technique using hydrogen-diluted SiH4 at 250 C.The dependence of the crystallinity of the film on the hydrogen dilution ratio and the film thickness was investigated.Raman spectra show that the thickness of the initial amorphous incubation layer on silicon oxide gradually decreases with increasing hydrogen dilution ratio.High-resolution transmission electron microscopy reveals that the initial amorphous incubation layer can be completely eliminated at a hydrogen dilution ratio of 98%,which is lower than that needed for the growth of amorphous-layer-free nanocrystalline silicon using an excitation frequency of 13.56 MHz.More studies on the microstructure evolution of the initial amorphous incubation layer with hydrogen dilution ratios were performed using Fourier-transform infrared spectroscopy.It is suggested that the high hydrogen dilution,as well as the higher plasma excitation frequency,plays an important role in the formation of amorphous-layer-free nanocrystalline silicon films.     

氢稀释对纳米晶硅薄膜晶化特性的影响及薄膜生长机理

以SiH₄与H₂作为前驱气体,采用射频等离子增强化学气相沉积技术制备了纳米晶硅薄膜.利用Raman散射和红外吸收光谱等技术,对不同氢稀释比条件下薄膜的微观结构和键合特性进行了研究.结果表明,随着氢稀释比增加,薄膜的晶化率明显提高,而氢稀释比过高时,薄膜晶化率呈现减少趋势.红外吸收光谱分析表明,纳米晶硅薄膜中氢的键合模式与薄膜的晶化特性密切相关.随着氢稀释比增加,薄膜中整体氢含量和SiH₂键合密度明显减少,而在高氢稀释比条件下,氢稀释比增加导致薄膜中SiH₂键合密度和整体氢含量增加.     

The microstructure and optical properties of crystallized hydrogenated silicon films prepared by very high frequency glow discharge

A series of nc-Si:H films with different crystalline volume fractions have been deposited by very high frequency glow discharge in a plasma with a silane concentration [SiH₄]/([SiH₄] + [H₂]) varying from 2% to 10%. The nc-Si:H films have been characterized by Raman spectroscopy, XRD diffraction, and UV-vis-near infrared spectrophotometer. The deposition rate increases nearly linear with increasing the silane concentration while the crystalline volume fraction decrease from 58% to 12%. The refractive index and the absorption of the samples were obtained through a modified four-layer-medium transmission model based on the envelope method. It was found that the refractive indices and absorption coefficient increase with increasing silane concentration. Compared to the films deposited using conventional RF-PECVD with excitation frequency of 13.56 MHz, the samples prepared by very high frequency glow discharge have higher absorption coefficients, which is due to its better compactness and lower defect density.     

Resonant CO2 laser-induced breakdown in polyatomic molecules

Summary The onset of CO₂ laser-induced breakdown has been observed by irradiating several polyatomic species (SiH₄, NH₃, hydrocarbons, fluorohydrocarbons) at a wavelength resonant with an IR active vibration. Primary fragmentation and subsequent ion and radical secondary reactions have been monitored detecting the spontaneous luminescence with a gateable optical multichannel analyser. The resonant laser-induced processes can be of importance in etching reactors where hydrocarbons and fluoro-hydrocarbons are commonly used, as well as in laser chemical vapour deposition reactors for the production of sinterable Si₃N₄ and SiC powders.     

Spectroscopic Measurements of Plasma Temperatures in a Radio Frequency Discharge

Argon and mixtures of argon with CH₄, C₂H₂ and N₂ have been excited in a 27.2 MHz radio frequency discharge at pressures of 10 and 5 Torr. Plasma spectra have been recorded and analyzed. The excitation temperatures of Ar I and H, the C₂ and CN vibrational temperatures and the N₂ and CN rotational temperatures have been determined and discussed.     

Stable silicon‐centered localized singlet 1,3‐diradicals XSi(GeY2)2SiX: theoretical predictions

Some localized singlet 1,3‐σ‐diradicals, XSi(GeY₂)₂SiX, (X = H, CH₃, SiH₃, C(CH₃)₃, NH₂ for X = F; Y = H, CH₃, OH, NH₂, SiH₃ for X = H) are theoretically designed by the orbital phase theory, the density functional theory (DFT) calculations , the second order Møller–Plesset perturbation theory (MP2), and the complete active space self‐consistent field (CASSCF) methods. The silicon‐centered singlet diradicals are more stable than the lowest triplets and than the bicylic σ‐bonded isomers if the isomers exist. The most stable singlet diradicals are not the π‐type diradicals, but the σ‐type diradicals where the radicals interact with each other through the Si? Ge bonds in the four‐membered rings. Copyright © 2007 John Wiley & Sons, Ltd.     

Numerical study of the effect of gas flow in low pressure inductively coupled Ar/N<Subscript>2</Subscript> plasmas

The effect of gas flow in low pressure inductively coupled Ar/N₂ plasmas operating at the rf frequency of 13.56 MHz and the total gas pressure of 20 mTorr is studied at the gas flows of 5–700 sccm by coupling the plasma simulation with the calculation of flow dynamics. The gas temperature is 300 K and input power is 300 W. The Ar fractions are varied from 0% to 95%. The species taken into account include electrons, Ar atoms and their excited levels, N₂ molecules and their seven different excited levels, N atoms, and Ar⁺, N⁺, N₂ ⁺, N₄ ⁺ ions. 51 chemical reactions are considered. It is found that the electron densities increase and electron temperatures decrease with a rise in gas flow rate for the different Ar fractions. The densities of all the plasma species for the different Ar fractions and gas flow rates are obtained. The collisional power losses in plasma discharges are presented and the effect of gas flow is investigated.     

UV-CVD deposited SiNH films on InP: Optimization of the physico-chemical and interface properties

High quality silicon nitride films are deposited at low temperature on InP substrates by direct photolysis at 185 nm of a NH₃-SiH₄ gas mixture. The composition of the films is measured by nuclear analysis. The thickness and refractive index are obtained by ellipsometry at 632.8 nm. As-deposited and post annealed samples are electrically characterized: quasi-static I(V) at 5×10^–4 Hz and C(V) characteristics at 1 MHz are performed on InP MIS diodes structures in order to optimize bulk and interface properties. At 250° C and 4 Torr, it is found that the highest critical field (measured for a leakage current density of 10^–9 A/cm²) is obtained for the injected ratio [SiH₄]/[NH₃]=2%. For these conditions, the film is stoichiometric, the critical field is 4 MV/cm and the resistivity is 6×10¹⁵ cm. The interface state density (N _ss) on InP is deduced from Terman analysis. The annealing conditions and the surface cleaning of InP have been optimized in order to reduce the N _ss which is, for our best conditions, as low as 2×10¹¹ eV^–1 cm^–2.     

Experimental equipment for studies of interaction of IR-radiation with liquid hydrides of groups IV–VI elements

The complex of special experimental apparatus for studies of interaction between IR-radiation and the thermally-stable volatile inorganic hydrides of groups IV–VI elements of the 2nd, 3rd and 4th periods in the liquid state and in the liquefied gas solutions is described. The main methods of solute concentration and integral absorption coefficients measurement are considered. The results of studies of IR-radiation absorption by volatile inorganic hydrides such as SiH₄, NH₃, PH₃, AsH₃, H₂S, and H₂Se in the liquid state and in the cryogenic solutions are presented. Using intensity, frequency and IR-absorption band contour data, the main mechanisms of intermolecular interactions in these liquids are discussed.     

Ion bombardment of amorphous silicon films during plasma-enhanced chemical vapor deposition in an rf discharge

The characteristics of ion and electron fluxes to the surface of a growing silicon film are investigated in various rf discharge regimes in silane at frequencies of 13.56 MHz and 58 MHz in plasma-enhanced chemical vapor-deposition (PECVD) apparatus. The energy spectra of the ions and electrons bombarding the growing film are measured. The electronic properties of films grown under various degrees of ion bombardment are studied. The correlation of these properties with the ion parameters in the rf discharge plasma during film growth is discussed. Zh. Tekh. Fiz. 68, 52–59 (February 1998)     

CHF3 Dual-Frequency Capacitively Coupled Plasma by Optical Emission Spectroscopy

We investigate the intermediate gas phase in the CHFs 13.56 MHz/2 MHz dual-frequency capacitively couple plasma （CCP） for the SiCOH low dielectric constant （low-k） film etching, and the effect of 2MHz power on radicals concentration. The major dissociation reactions of CHF3 in 13.56MHz CCP are the low dissociation bond energy reactions, which lead to the low F and high CF2 concentrations. The addition of 2MHz power can raise the probability of high dissociation bond energy reactions and lead to the increase of F concentration while keeping the CF2 concentration almost a constant, which is of advantage to the SiCOH low-k films etching. The radical spatial uniformity is dependent on the power coupling of two sources. The increase of 2 MHz power leads to a poor uniformity, however, the uniformity can be improved by increasing 13.56 MHz power.     

Rotational and Vibrational Temperature Measurements in a High‐Pressure Cylindrical Dielectric Barrier Discharge (C‐DBD)

The rotational (T_R) and vibrational (T_v) temperatures of N₂ molecules were measured in a high‐pressure cylindrical dielectric barrier discharge (C‐DBD) source in Ne with trace amounts (0.02 %) of N₂ and dry air excited by radio‐frequency (rf) power. Both T_R and T_v of the N₂ molecules in the C ³Π_u state were determined from an emission spectroscopic analysis the 2^nd positive system (C ³Π_u → B³Π_g). Gas temperatures were inferred from the measured rotational temperatures. As a function of pressure, the rotational temperature is essentially constant at about 360 K in the range from 200 Torr to 600 Torr (at 30W rf power) and increases slightly with increasing rf power at constant pressure. As one would expect, vibrational temperature measurements revealed significantly higher temperatures. The vibrational temperature decreases with pressure from 3030 K at 200 Torr to 2270 K at 600 Torr (at 30 W rf power). As a function of rf power, the vibrational temperature increases from 2520 K at 20 W to 2940 K at 60 W (at 400 Torr). Both T_R and T_v also show a dependence on the excitation frequency at the two frequencies that we studied, 400 kHz and 13.56 MHz. Adding trace amounts of air instead of N₂ to the Ne in the discharge resulted in higher T_R and T_v values and in a different pressure dependence of the rotational and vibrational temperatures. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)