Multi-phase structured silicon carbon nitride thin films prepared by hot-wire chemical vapour deposition

In this work, Silicon Carbon Nitride (Si-C-N) thin films were deposited by Hot Wire Chemical Vapour Deposition (HWCVD) technique from a gas mixture of silane (SiH₄), methane (CH₄) and nitrogen (N₂). Six sets of Si-C-N thin films were produced and studied. The component gas flow rate ratio (SiH₄:CH₄:N₂) was kept constant for all film samples. The total gas flow-rate (SiH₄ + CH₄ + N₂) was changed for each set of films resulting in different total gas pressure which represented the deposition pressure for each of these films ranging from 40 to 100 Pa. The effects of deposition pressure on the chemical bonding, elemental composition and optical properties of the Si-C-N were studied using Fourier transform infrared (FTIR) spectroscopy, Auger Electron Spectroscopy (AES) and optical transmission spectroscopy respectively. This work shows that the films are silicon rich and multi-phase in structure showing significant presence of hydrogenated amorphous silicon (a-Si:H) phase, amorphous silicon carbide (a-SiC), and amorphous silicon nitride (a-SiN) phases with Si-C being the most dominant. Below 85 Pa, carbon content is low, and the films are more a-Si:H like. At 85 Pa and above, the films become more Si-C like as carbon content is much higher and carbon incorporation influences the optical properties of the films. The properties clearly indicated that the films underwent a transition between two dominant phases and were dependent on pressure.     

Patterning of porous silicon nanostructures and eliminating microcracks on silicon nitride mask using metal assisted chemical etching

A method for selective formation of reproducible, high fidelity and controllable nano and micrometer size porous Si areas over n-type Si wafers is provided. A 400 nm thick Silicon Nitride layer was used as the mask layer while Platinum and Palladium nanoparticles were deposited over the unprotected areas to obtain porous areas through metal assisted chemical etching process. Nanoparticles were deposited by electroless plating solutions containing H₂PtCl₆ and PdCl₂. Good controls over pore size and depth were obtained with well defined and sharp edges of the patterned areas. The results were compared to porous structures obtained via electrochemical etching process, indicating the superiority of metal assisted etching in terms of its simplicity as well as the ability of Silicon Nitride layer acting as the mask layer.     

Visible electroluminescence from silicon nanoclusters embedded in chlorinated silicon nitride thin films

Visible electroluminescence (EL) has been obtained from devices with active layers of silicon nanocrystals embedded in chlorinated silicon nitride (Si-nc/SiN_x:Cl) thin films, deposited by remote plasma enhanced chemical vapour deposition, using SiCl₄/NH₃/H₂/Ar. The active nc-Si/SiN_x:Cl film was sandwiched between Al contacts and a transparent conductive contact of ZnO_x:Al deposited by the pyrosol process. White EL centred at around 600 nm was observed, with a turn-on voltage of 5 V, and the intensity increasing as a function of voltage. Recombination between electron-hole pairs generated in the Si-nc by electron impact ionization is proposed as the EL mechanism.     

氮化硼薄膜在退火相变中的应力研究

利用射频溅射系统在P型Si（100）衬底上制备氮化硼薄膜。对其进行600～1000℃的常压下N2保护退火。通过傅立叶变换红外谱（FTIR）分析，发现hBN-cBN-hBN的可逆相变。通过不同温度退火后立方相横光学振动模式峰位的移动，计算了氮化硼薄膜中残余应力的变化。发现沉积后退火很好地解决了高立方相氮化硼薄膜应力释放的问题，可提高立方氮化硼薄膜在硅衬底上的粘附性。并且探索性地讨论在退火过程中c-BN成核、生长与薄膜中应力变化的关系。     

Effect of high-frequency on etching of SiCOH films in CHF3 dual-frequency capacitively coupled plasmas

The effect of high-frequency (HF) frequency on etching characteristics of SiCOH films in a CHF₃ dual-frequency capacitively couple plasma driven by 13.56 MHz/2 MHz, 27.12 MHz/2 MHz or 60 MHz/2 MHz sources was investigated in this work. The surface structure of the films after etching and the CHF₃ discharge plasma were characterized. The increase of HF frequency reduced the critical HF power for the etching, suppressed the C:F deposition at the surface of etched films, and improved the etching of SiCOH films. The improvement of etching was attributed to the increase of ions energy and F concentration at high HF frequency.     

Properties of plasma enhanced chemical vapor deposited silicon nitride for the application in multicrystalline silicon solar cells

Hydrogenated films of silicon nitride (SiNx:H) were investigated by varying the deposition condition in plasma enhanced chemical vapor deposition (PECVD) reactor and annealing condition in infrared (IR) heated belt furnace to find the optimized condition for the application in multicrystalline silicon solar cells. By varying the gas ratio (ammonia to silane), the silicon nitride films of refractive indices 1.85-2.45 were obtained. Despite the poor deposition rate, silicon wafer with the film deposited at 450 °C showed the best minority carrier lifetime. The film deposited with the gases ratio of 0.57 showed the best peak of carrier lifetime at the annealing temperature of 800 °C. The performance parameters of cells fabricated by varying co-firing peak temperature also showed the best values at 800 °C. The multicrystalline silicon (mc-Si) solar cells fabricated in conventional industrial production line applying the optimized film deposition and annealing conditions on large area substrate (125 mm × 125 mm) was found to have the conversion efficiency of 15%.     

ECR-PECVD制备氮化硅薄膜的键态结构

用红外光谱和拉曼光谱分析了用低温电子回旋共振等离子体CVD技术制备的Si3N4薄膜的键态结构。结果表明Si3N4薄膜主要由Si-N键结构组成，还含有Si-H和Si-O-Si键结构。随着沉积温度的提高，Si3N4薄膜中的Si-H键减少，氢含量降低。可利用提高沉积温度来减少Si3N4薄膜中的氢含量。在沉积温度为420℃时Si3N4薄膜的Raman光谱在短波方向出现一新的展宽的拉曼散射峰。     

Effect of silane flow rate on structural,electrical and optical properties of silicon thin films grown by VHF PECVD technique

Hydrogenated silicon thin films deposited by VHF PECVD process for various silane flow rates have been investigated. The silane flow rate was varied from 5 sccm to 30 sccm, maintaining all other parameters constant. The electrical, structural and optical properties of these films were systematically studied as a function of silane flow rate. These films were characterized by Raman spectroscopy, Scanning Electron Microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy and UV–visible (UV–Vis) spectroscopy. Different crystalline volume fraction (22%–60%) and band gap (∼1.58 eV–∼1.96 eV) were achieved for silicon thin films by varying the silane concentration. A transition from amorphous to nanocrystalline silicon has been confirmed by Raman and FTIR analysis. The film grown at this transition region shows the high conductivity in the order of 10⁻⁴ Ω⁻¹ cm⁻¹.     

Enhanced deposition of cubic boron nitride films on roughened silicon and tungsten carbide-cobalt surfaces

We report the influence of substrate surface roughness on cubic boron nitride (cBN) film deposition under low-energy ion bombardment in an inductively coupled plasma. Silicon and cemented tungsten carbide-cobalt (WC-Co) surfaces are roughened by low-energy ion-assisted etching in a hydrogen plasma, followed by deposition in a fluorine-containing plasma. Infrared absorption coefficients are measured to be 22,000 cm⁻¹ and 17,000 cm⁻¹ for sp²-bonded BN and cBN phases, respectively, for our films. For the silicon substrates, the film growth rate and the cBN content in the film increase with increasing the surface roughness, while the amount of sp²BN phase in the film shows only a small increase. A larger surface roughness of the substrate results in a smaller contact angle of water, indicating that a higher surface free energy of the substrate contributes to enhancing growth of the cBN film. For the WC-Co substrates, the film growth rate and the cBN content in the film increase similarly by roughening the surface.     

Characterization of surface profiles of LPCVD silicon nitride films by RBS profile

Abstract

A Rutherford backscattering spectrometry (RBS)‐profile was applied to the characterization of the surface profile of silicon nitride films prepared by low pressure chemical vapor deposition (LPCVD). This method detected inhomogeneity in the silicon nitride films and demonstrated Si‐richness near the interface. This method was also used to study the silicon nitride profiles associated with bird's beak formation in VLSI devices. This paper presents a scheme for an auto‐search routine for an RBS‐profile program. The potential of the RBS‐profile method for the characterization of LPCVD silicon nitride films are demonstrated.     

PECVD法生长氮化硅工艺的研究

采用了等离子体增强化学气相沉积法(plasma-enhanced chemical vapor deposition,PECVD)在聚酰亚胺(polyimide,PI)牺牲层上生长氮化硅薄膜,讨论沉积温度、射频功率、反应气体流量比等工艺参数对氮化硅薄膜的生长速率、氮硅比、残余应力等性能的影响,得到适合制作接触式射频MEMS开关中悬梁的氮化硅薄膜的最佳工艺条件.     

Oxygen plasma etching of silver-incorporated diamond-like carbon films

Diamond-like carbon (DLC) film as a solid lubricant coating represents an important area of investigation related to space devices. The environment for such devices involves high vacuum and high concentration of atomic oxygen. The purpose of this paper is to study the behavior of silver-incorporated DLC thin films against oxygen plasma etching. Silver nanoparticles were produced through an electrochemical process and incorporated into DLC bulk during the deposition process using plasma enhanced chemical vapor deposition technique. The presence of silver does not affect significantly DLC quality and reduces by more than 50% the oxygen plasma etching. Our results demonstrated that silver nanoparticles protect DLC films against etching process, which may increase their lifetime in low earth orbit environment.     

纳米多孔硅的电化学制备及性能研究

纳米多孔硅是一种潜在的化学和生物传感材料,本文采用电化学腐蚀法制备纳米多孔硅。采用SEM技术分析多孔硅的表面形貌,研究了腐蚀条件对多孔硅的孔隙率、厚度、I-V特性的影响。结果表明,多孔硅的孔隙率随着腐蚀电流密度和腐蚀时间的增加而呈线性增大趋势;其厚度随着腐蚀电流密度的增加而近似呈线性增大趋势,随腐蚀时间的成倍增加而显著增大;其I-V特性表现出非整流的欧姆接触。     

Chemical stability of hydrogen-containing boron nitride films obtained by plasma enhanced chemical vapour deposition

The purpose of this paper is the investigation of the dehydrogenation kinetics of boron nitride films during thermal annealing. BN_x:H films on silicon substrates were prepared by remote plasma enhanced chemical vapour deposition at 473 K using a mixture of borazine and helium. IR spectroscopy and ellipsometry were used to characterize the film properties and composition. The films contain a certain amount of hydrogen in B---H and N---H bonds. The breakage kinetics of these bonds is different. The breakage of N---H bonds determines the hydrogen annealing kinetics at 973–1073 K. The low-temperature annealing (673–873 K) of B---H bonds is sensitive to the generation of hydrogen from N---H bonds. Heat treatment leads to ordering of the films.     

Formation of gas barrier films by Cat-CVD method using organic silicon compounds

Silicon nitride (SiN_x) and silicon oxynitride (SiO_xN_y) films have been formed by catalytic chemical vapor deposition (Cat-CVD) method using hexamethyldisilazane (HMDS). Addition of NH₃ gas and increase in gas pressure can prevent carbonization of tungsten (W) catalyzer. These SiO_xN_y films have high gas barrier ability compare to the case of SiO_xN_y films using SiH₄ and thus are expected for novel sealing films.     

p-Si TFT栅绝缘层用SiN薄膜的制备与研究

以NH3和SiH4为反应源气体，采用射频等离子体增强化学气相沉积（RF-PECVD）法在多晶硅（P-Si）衬底上沉积了一系列SiN薄膜并进行了相关性能测试。系统地分析讨论了反应源气体流量比和反应压强对siN薄膜介电常数、电学性能及界面特性的影响，在制备高质量的P-Si TFT栅绝缘层用SiN薄膜方面具有重要的参考价值。     

Dielectric functions of PECVD-grown silicon nanoscale inclusions within rapid thermal annealed silicon-rich silicon nitride films

Spectroscopic ellipsometry (SE) measurements were carried out in order to characterize the optical properties of silicon nanoscale inclusions (Si-ni) contained in silicon-rich silicon nitride (SRSN) films. These films were deposited using the plasma enhanced chemical vapor deposition (PECVD) technique followed by rapid thermal annealing (RTA) during 1 min. We focus our study on the influence of the deposition and annealing conditions - such as the ammonia to silane flow ratio R, the annealing atmosphere and temperature - on the optical responses of the SRSN layers and the behavior of the Si-ni dielectric functions. Our results suggest that the variation of R affects in a more significant way the structure and optical properties of the SRSN films than the change of the annealing gas or temperature.     

等离子体刻蚀提纯冶金硅研究

通过自行设计的冷等离子体粉粒纯化系统,将硅粉撒进辉光放电区,以Ar气为反应气体,利用鞘层区域辉光放电的冷等离子体对硅粉料的作用,进行一系列的处理后,硅粉表面形貌平整度明显提高,纯度从98.75 9,6提高到99.56%.在此基础上,设计射频感应放电等离子体的振动倾斜反应室,经实验,将硅粉纯度提高到99.96 9,6,接近太阳级硅的要求,也为该研究未来的发展提供了新的思路和理论参考.     

化学刻蚀法制备多孔硅的表面形貌研究

应用各种表面形貌分析方法如SEM、TEM、AFM等,通过对用化学刻蚀法形成的多孔硅进行表面形貌分析,发现由于横向腐蚀比较严重而使多孔硅层在达到一定深度后就会自动脱落。腐蚀中由于大量H2的析出,对硅晶体产生巨大的应力,这些应力使硅在比较脆弱的晶粒边界或缺陷处产生微裂纹,多孔硅就从这些地方开始和生长。