Growth of Nanocrystalline Silicon Films by Helicon Wave Plasma Chemical Vapour Deposition

Nanocrystalline silicon (nc-Si) thin films have been prepared by a helicon-wave plasma chemical vapour deposition technique on glass-Si substrates. The structural properties and the surface morphology are characterized by Raman spectroscopy, x-ray diffraction and atomic force microscopy. It is proven that the deposited films have the features of high crystalline fraction and large grain size compared with that in the normal plasma-enhanced chemical vapour deposition regime. The crystalline fraction of the deposited films varying from 0%to 72% can be obtained by adjusting the substrate temperature.     

Effects of Flow Rate Variation on SiCln （n 〈 3） Densities in SICl4 Plasmas

Radicals produced by the plasma enhanced chemistry vapour deposition technique in SiCl4 plasma are identified by mass spectrometry using our newly proposed straight-line fit method. Since flow rate is one of the most important parameters in depositing thin films, we present the effects of SiCl4 flow rate variation on SiCln （n 〈 3） densities. The experimental results demonstrate that Si and SiCln （n = 1, 2） densities decrease with increasing SiCl4 flow rate. After reaching the minimum values at a flow rate of 17 and 13sccm, respectively, Si and SiCln （n = 1, 2） densities slightly increase with further increase of flow rate to 20.5sccm. These results could be interpreted to which the depletion fraction of SiCl4 decreases and the residence time of SiCl4 molecule becomes shorter, with the increasing SICl4 flow rate. In order to obtain high-quality poly-Si films with high growth rate, it is better to use smaller flow rate of SICl4 source gas for depositing films.     

Influence of total gas flow rate on microcrystalline silicon films prepared by VHF-PECVD

Hydrogenated microcrystalline silicon (\mu c-Si:H) films are fabricated by very high frequency plasma enhanced chemical vapour deposition (VHF-PECVD) at a silane concentration of 7% and a varying total gas flow rate (Hk₂+SiHk₄). Relations between the total gas flow rate and the electrical and structural properties as well as deposition rate of the films are studied. The results indicate that with the total gas flow rate increasing the photosensitivity and deposition rate increase, but the crystalline volume fraction (Xk_c) and dark conductivity decrease. And the intensity of (220) peak first increases then decreases with the increase of the total gas flow rate. The cause for the changes in the structure and deposition rate of the films with the total gas flow rate is investigated using optical emission spectroscopy (OES).     

Low-Temperature Growth of Polycrystalline silicon Films by SiCl4／H2 rf Plasma Enhanced Chemical Vapour Deposition

Polycrystalline silicon film was directly fabricated at 200℃ by the conventional plasma enhanced chemical vapour deposition method from SiCl4 with H2 dilution. The crystallization depends strongly on the deposition power.The maximum crystMlinity and the crystalline grain size are over 80% and 200—50Onm, respectively. The results of energy dispersive spectroscopy and infrared spectroscopy measurements demonstrate that the film is mostly composed of silicon, without impurities such as Cl, N, C and bonded H. It is suggested that the crystallization at such a low temperature originates from the effects of chlorine, i.e., in-situ chemical, etching, in-situ chemical cleaning, and the detachment of bonded H.     

Optical emission spectroscopy study on depositionprocess of microcrystalline silicon

This paper reports that the optical emission spectroscopy (OES) is used to monitor the plasma during the deposition process of hydrogenated microcrystalline silicon films in a very high frequency plasma enhanced chemical vapour deposition system. The OES intensities (SiH\sj{*}, H微晶硅 VHF-PECVD 发射光谱学 薄膜物理学microcrystalline silicon, VHF-PECVD, optical emission spectroscopy2005-11-092005-11-092005-12-12This paper reports that the optical emission spectroscopy （OES） is used to monitor the plasma during the deposition process of hydrogenated microcrystalline silicon films in a very high frequency plasma enhanced chemical vapour deposition system. The OES intensities （Sill^＊, H^＊ and H^＊β） are investigated by varying the deposition parameters. The result shows that the discharge power, silane concentrations and substrate temperature affect the OES intensities. When the discharge power at silane concentration of 4% increases, the OES intensities increase first and then are constant, the intensities increase with the discharge power monotonously at silane concentration of 6%. The SiH^＊ intensity increases with silane concentration, while the intensities of H^＊α and H^＊β increase first and then decrease. When the substrate temperature increases, the SiH^＊ intensity decreases and the intensities of H^＊α and H^＊β are constant. The correlation between the intensity ratio of IH^＊α/ISiH^＊ and the crystalline volume fraction （Xc） of films is confirmed.     

OES study of the gas phase during diamond films deposition in high power DC arc plasma jet CVD system

This paper used optical emission spectroscopy (OES) to study the gas phase in high power DC arc plasma jet chemical vapour deposition (CVD) during diamond films growth processes. The results show that all the deposition parameters (methane concentration, substrate temperature, gas flow rate and ratio of H₂/Ar) could strongly influence the gas phase. C₂ is found to be the most sensitive radical to deposition parameters among the radicals in gas phase. Spatially resolved OES implies that a relative high concentration of atomic H exists near the substrate surface, which is beneficial for diamond film growth. The relatively high concentrations of C₂ and CH are correlated with high deposition rate of diamond. In our high deposition rate system, C₂ is presumed to be the main growth radical, and CH is also believed to contribute the diamond deposition.     

Effect of CO2 Addition on Preparation of Diamond Films by Direct-Current Hot-Cathode Plasma Chemical Vapor Deposition Method

Diamond films are deposited on Mo substrates by dc hot-cathode plasma chemical vapor deposition method using a CH4-H2-CO2 gas mixture. Adjusting the flow of CO2, we study the relevant influence on surface morphology, grain orientation and crystalline quality of films with scanning electron microscopy, x-ray diffraction, Raman spectroscopy, respectively. The results show that grain orientation of the films has a transition with the increasing CO2 addition, from （100） orientation to （110） orientation and then （111） orientation. The crystalline quality is improved but the growth rate is decreased by raising the flow of CO2. The experimental results are also discussed briefly.     

Influence of reaction gas flows on the properties of SiGe:H thin film prepared by plasma assisted reactive thermal chemical vapour deposition

A new preparing technology, very high frequency plasma assisted reactive thermal chemical vapour deposition （VHFPA-RTCVD）, is introduced to prepare SiGe：H thin films on substrate kept at a lower temperature. In the previous work, reactive thermal chemical vapour deposition （I~TCVD） technology was successfully used to prepare SiGe：H thin films, but the temperature of the substrate needed to exceed 400℃. In this work, very high frequency plasma method is used to assist RTCVD technology in reducing the temperature of substrate by largely enhancing the temperature of reacting gases on the surface of the substrate. The growth rate, structural properties, surface morphology, photo- conductivity and dark-conductivity of SiGe：H thin films prepared by this new technology are investigated for films with different germanium concentrations, and the experimental results are discussed.     

Fabrication of high growth rate solar-cell-quality μc-Si:H thin films by VHF-PECVD

Several series of Si:H films were fabricated by the very high frequency plasma enhanced chemical vapour deposition (VHF-PECVD) at different substrate temperatures (T_s) and silane concentration (SC=[SiH_4]/[SiH_4+H_2]%). The results of Raman spectroscopy showed structural evolution of the Si:H films with the variation of T_s and SC. The results of x-ray diffraction (XRD) measurements indicated that T_s also influences the crystal orientation of the Si:H films. The modulation effect of T_s on crystalline volume fraction (X_c) is more evident for the high SC, which shows different trend compared to low SC. In addition, the growth rate of the films also showed a regular change with the variation of SC and T_s. Different samples in the series showed a similar increase in dark conductivity and a decrease in photosensitivity with increasing T_s and decreasing SC. Device-quality microcrystalline silicon materials were deposited at a high growth rate, characterized by relatively low dark conductivity and relatively high photosensitivity in a certain crystalline range. The microcrystalline silicon solar cell with a conversion efficiency of 4.55% has been prepared by VHF-PECVD.     

Deposition of Hydrogen-Free Silicon Nitride Thin Films by Microwave ECR plasma Enhanced Magnetron Sputtering at Room Temperature

Hydrogen-free silicon nitride （SiNx） films were deposited at room temperature by microwave electron cyclotron resonance （MW-ECR） plasma enhanced unbalance magnetron sputtering system. Both Fourier-transform infrared spectroscopy and x-ray photoelectron spectroscopy are used to study the bonding type and the change of bonding structures of the silicon nitride films. The results indicate that the chemical structure and composition of SiNx films deposited by this technique depend strongly on the N2 flow rates, the stoichiometric SiNx film, which has the highest hardness of 22.9 GPa, could be obtained at lower N2 flow rate of 4 sccm.     

Analysis of heating effect on the process of high deposition rate microcrystalline silicon

A possible heating effect on the process of high deposition rate microcrystalline silicon has been studied.It includes the discharge time-accumulating heating effect,discharge power,inter-electrode distance,and total gas flow rate induced heating effect.It is found that the heating effects mentioned above are in some ways quite similar to and in other ways very different from each other.However,all of them will directly or indirectly cause the increase of the substrate surface temperature during the process of depositing microcrystalline silicon thin films,which will affect the properties of the materials with increasing time.This phenomenon is very serious for the high deposition rate of microcrystalline silicon thin films because of the high input power and the relatively small inter-electrode distance needed.Through analysis of the heating effects occurring in the process of depositing microcrystalline silicon,it is proposed that the discharge power and the heating temperature should be as low as possible,and the total gas flow rate and the inter-electrode distance should be suitable so that device-grade high quality deposition rate microcrystalline silicon thin films can be fabricated.     

Luminescent-wavelength tailoring silicon-rich silicon nitride LED

Wavelength tunable photoluminescence （PL） of Si-rich silicon nitride （SRSN） film with buried Si nanocrystals （Si-ncs） grown by plasma enhanced chemical vapor deposition （PECVD） under Sill4 and NH3 environment is investigated. Intense broadband visible emissions tunable from blue to red can be obtained from the as-deposited SiNs thin films with increasing NH3 flow rate from 150 to 250 sccm and detuning the SiH4/NH3 flow ratio during deposition. To date, the normalized PL wavelength of SiNx films after anneal- ing could be detuned over the range of 385-675 nm by decreasing the NH3 flow rate, corresponding to an enlargement on Si-nc size from 1.5-2 to 4-5 nm. The PL linewidth is decreased with increasing ammonia flow rate due to the improved uniformity of Si-ncs under high NH3 flow rate condition. In addition, the PL intensity is monotonically increasing with the blue shift of PL wavelength due to the increasing density of small-size Si-ncs. The ITO/SiNx/p-Si/Al diode reveals highly resistive property with the turn-on voltage and power-voltage slope of only 20 V and 0.18 nW/V, respectively. The turn-on voltage can further reduce from 20 to 3.8 V by improving the carrier injection efficiency with p-type Si nano-rods.     

Structural Characterization and Photoluminescent Properties of Zn1—xMgxO Films on Silicon

Zn1-xMgxO films have been grown on silicon at various substrate temperatures by pulsed laser deposition.The structural and photoluminescent properties of films as a function of substrate temperature have been studied.The optimized substrate temperature is 650℃.The x-ray diffraction spectra indicate that the films are highly C-axis oriented,and no phase separation is observed.The crystal grain size of the films is about 100nm as examined by atomic force microscopy.The cross-sectional transmission electron microscopy verified the C-axis orientation of the Zn1-xMgxO.Thesr films showed ultraviolet photoluminescence at room temperature.The near-band-edge emission peak of the Zn1-xMgxO film deposited at 600℃ has a blueshift (0.40eV) larger than that of the film deposited at 500℃ (0.33eV).The ratio of the near-band-edge to defect level peak intensity is as large as 159.     

Field Emission Characteristics of BN Films Treated with H2 and O2 Plasma

BN films were synthesized on the (100)-oriented surface of n-Si (0.008-0.02Ωm) by rf magnetron sputtering physical vapor deposition (PVD). A BN film was first treated with H2 plasma for 60 rain and then the H2 treated sample was treated with O2 plasma for 15rain. The films were characterizes by using Fourier transform infrared spectra (FTIR) and atomic force microscopy (AFM). The field emission characteristics of BN films were measured in an ultrahigh vacuum system. A turn-on electric field of 8 V/μm and a current of 400μA/cm^2 were obtained for the BN film treated with H2 plasma. The results show that the surface plasma treatment makes no apparent influence on the surface morphology of the BN films. The transformations of the sample emission characteristics have to do with the surface negative electron affinity (NEA) of the films possibly. The turn-on electric field of the BN film treated with H2 plasma is lower than that without treatment, which possibly attributes to the surface NEA effect. The surface NEA of the H2 treated BN film is lost after O2 plasma treatment.     

Excellent Passivation of p-Type Si Surface by Sol-Gel Al2O3 Films

Al2O3 films with a thickness of about lOOnm synthesized by spin coating and thermally treated are applied for field-induced surface passivation of p-type crystalline silicon. The level of surface passivation is determined by techniques based on photoconductance. An effective surface recombination velocity below lOOcm/s is obtained on 10Ωcm p-type c-Si wafers （Cz Si）. A high density of negative fixed charges in the order of 10^12 cm^-2 is detected in the Al2O3 films and its impact on the level of surface passivation is demonstrated experimentally. Furthermore, a comparison between the surface passivation achieved for thermal SiO2 and plasma enhanced chemical vapor deposition SiNx ：H films on the same c-Si is presented. The high negative fixed charge density explains the excellent passivation of p-type c-S/by Al2O3.     

Effects of deposition pressure and plasma power on the growth and properties of boron-doped microcrystalline silicon films

Using diborane as doping gas, p-doped μc-Si：H layers are deposited by using the plasma enhanced chemical vapour deposition （PECVD） technology. The effects of deposition pressure and plasma power on the growth and the properties of μc-Si：H layers are investigated. The results show that the deposition rate, the electrical and the structural properties are all strongly dependent on deposition pressure and plasma power. Boron-doped μc-Si：H films with a dark conductivity as high as 1.42 Ω^-1·cm^-1 and a crystallinity of above 50% are obtained. With this p-layer, μc-Si：H solar cells are fabricated. In addition, the mechanism for the effects of deposition pressure and plasma power on the growth and the properties of boron-doped μc-Si：H layers is discussed.     

Dependence of Structure and Haemocompatibility of Amorphous Carbon Films on Substrate Bias Voltage

Tetrahedral amorphous hydrogenated carbon (ta-C:H) films on Si(lO0) substrates were prepared by using a magnetic-field-filter plasma stream deposition system. Samples with different ratios of sp^3-bond to sp^2-bond were obtained by changing the bias voltage applied to the substrates. The ellipsometric spectra of various carbon films in the photon energy range of 1.9-5.4eV were measured. The refractive index n and the relative sp^3 C ratio of these films were obtained by simulating their ellipsometric spectra using the Forouhi-Bloomer model and by using the Bruggeman effective medium approximation, respectively. The haemocompatibility of these ta-C:H films was analysed by observation of platelet adhesion and measurement of kinetic clotting time. The results show that the sp^3 C fraction is dependent on the substrate bias voltage, and the haemocompatibility is dependent on the ratio of sp^3-bond to sp^2-bond. A good haemocompatibility material of ta-C:H films with a suitable sp^3 C fraction can be prepared by changing the substrate bias voltage.     

The role of hydrogen in hydrogenated microcrystalline silicon film and in deposition process with VHF-PECVD technique

The role of hydrogen in hydrogenated microcrystalline silicon ($\mu $c-Si:H) thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition (VHF-PECVD) technique have been investigated in this paper. With \textit{in situ} optical emission spectroscopy (OES) diagnosis during the fabrication of $\mu $c-Si:H thin films under different plasma excitation frequency $\nu _{\rm e }$ (60MHz--90MHz), the characteristic peak intensities ($I_{{\rm SiH}^*}$, $I_{{\rm H}\alpha^*}$ and $I_{{\rm H}\beta ^*}$) in SiHVHF-PECVD技术 氢化微晶硅 光发射光谱 薄膜学VHF-PECVD technique, hydrogenated microcrystalline silicon, role of hydrogen, optical emission spectroscopyProject supported by the Natural Science Foundation of Guangdong Province, China (Grant No 05300378), the State Key Development Program for Basic Research of China (Grant Nos G2000028202 and G2000028203) and the Program on Natural Science of Jinan University, Guangzhou, China (Grant No 51204056).2005-11-252005-11-252006-01-05The role of hydrogen in hydrogenated microcrystalline silicon （μc-Si：H） thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition （VHF-PECVD） technique have been investigated in this paper. With in situ optical emission spectroscopy （OES） diagnosis during the fabrication of μc-Si：H thin films under different plasma excitation frequency Ve （60MHz-90MHz）, the characteristic peak intensities （IsiH＊, IHα＊ and IHβ＊ ） in SiH4＋H2 plasma and the ratio of （IHα＊ ＋ IHβ＊ ） to IsiH＊ were measured; all the characteristic peak intensities and the ratio （IHα＊ ＋ IHβ＊ ）/IsiH＊ are increased with plasma excitation frequency. It is identified that high plasma excitation frequency is favourable to promote the decomposition of SiH4＋H2 to produce atomic hydrogen and SiHx radicals. The influences of atomic hydrogen on structural properties and that of SiHx radicals on deposition rate of μc-Si：H thin films have been studied through Raman spectra and thickness measurements, respectively. It can be concluded that both the crystalline volume fraction and deposition rate are enhanced with the increase of plasma excitation frequency, which is in good accord with the OES results. By means of FTIR measurements, hydrogen contents of μc-Si：H thin films deposited at different plasma excitation frequency have been evaluated from the integrated intensity of wagging mode near 640 cm^-1. The hydrogen contents vary from 4% to 5%, which are much lower than those of μc-Si：H films deposited with RF-PECVD technique. This implies that μc-Si：H thin films deposited with VHF-PECVD technique usually have good stability under light-soaking.     

Deposition of SiOx barrier films by O2/TMDSO RF-PECVD

This paper reports that the SiOx barrier films are deposited on polyethylene terephthalate substrate by plasmaenhanced chemical vapour deposition （PECVD） for the application of transparent barrier packaging. The variations of 02/Tetramethyldisiloxane （TMDSO） ratio and input power in radio frequency （RF） plasma are carried out to optimize barrier properties of the SiOx coated film. The properties of the coatings are characterized by Fourier transform infrared, water vapour transmission rate （WVTR）, oxygen transmission rate （OTR）, and atomic force microscopy analysers. It is found that the 02/TMDSO ratio exceeding 2：1 and the input power over 200 W yield SiOx films with low carbon contents which can be good to the barrier （WVTR and OTR） properties of the SiOx coatings. Also, the film properties not only depend on oxygen concentration of the inlet gas mixtures and input power, but also relate to the surface morphology of the coating.     

Mechanical strains in pecvd SiN_x:H films for nanophotonic application

Hydrogenated amorphous silicon nitride films(Si N x:H) are deposited at low temperature by high-frequency plasmaenhanced chemical vapor deposition(HF PECVD). The main effort is to investigate the roles of plasma frequency and plasma power density in determining the film properties particularly in stress. Information about chemical bonds in the films is obtained by Fourier transform infrared spectroscopy(FTIR). The stresses in the Si N x:H film are determined from substrate curvature measurements. It is shown that plasma frequency plays an important role in controlling the stresses in Si N x:H films. For silicon nitride layers grown at plasma frequency 40.68 MHz initial tensile stresses are observed to be in a range of 400 MPa–700 MPa. Measurements of the intrinsic stresses of silicon nitride films show that the stress quantity is sufficient for film applications in strained silicon photonics.