Hydrogen dependent surface morphology study of plasma deposited SiN(x):H films for two gas systems SiH4/NH3 and SiH4/N2

Partially amorphous silicon nitride thin films were deposited using plasma enhanced chemical vapor deposition technique using the two gas systems: SiH4/NH3 and SiH4/N2. Fourier Transform infrared spectroscopy was employed to derive the relative changes in the bonded hydrogen content with increasing flow rates of NH3 and N2. Surface morphology was monitored using atomic force microscopy. Root mean square surface roughness was found to be dependent on the NH3 and N2 flow rates, unlike silicon nitride films deposited by rf magnetron sputtering with variation in (N2/Ar) (Li et al. Thin Solid Films 334 (1998) 140). The discrepancy has been explained in the light of bonded hydrogen content in these films. The X-ray diffraction technique has also been used to observe the phases of the nitride films which showed the presence of silicon nitride grains oriented in (200), (400) and (221) directions in the predominantly amorphous as-deposited SiN(x):H films.     

Hydrogen-related mechanical stress in amorphous silicon and plasma-deposited silicon nitride

Hydrogen concentrations in amorphous silicon (a-Si) prepared by electron beam evaporation or plasma deposition as well as in plasma-deposited silicon nitride were measured as a function of annealing conditions using the photon-proton scattering method. Comparison with IR evaluations of SiH bonds shows the existence of “quasi-free” (IR inactive) hydrogen in a-Si. The amount of this component can be altered by annealing. The dependence of the mechanical stress on the annealing conditions was determined interferometrically, and the intrinsic contribution was separated in the case of plasma-deposited silicon nitride. As the hydrogen content decreases monotonically with increasing annealing temperature, the initial compressive stress of plasma-deposited a-Si or silicon nitride films changes to a tensile stress. For these films a linear correlation between the amount of mechanical stress and the number of SiH or NH bonds is shown. Evaporated a-Si films show a totally different stress behaviour from that of plasma-deposited a-Si. No correlation of stress with the hydrogen concentration was found for the evaporated a-Si films.     

Luminescence tuning of amorphous Si quantum dots prepared by plasma-enhanced chemical vapor deposition

Amorphous Si (a-Si) quantum dots (QDs) embedded in a silicon nitride film were prepared by a plasma-enhanced chemical vapor deposition (PECVD) technique using gaseous mixtures of silane, hydrogen and nitrogen. We observed that the Si QDs had an amorphous structure from the Raman spectroscopy measurement. The Fourier transform infrared (FTIR) spectra showed that the relative transmittance of the SiH bands decreased, but that of the NH bands increased, with increasing nitrogen flow rate. During the deposition of SiNx, the number of dangling bonds of silicon acting as nucleation sites increased. As the hydrogen flow rate increased the growth rate decreased, due to the reduction in the hydrogen partial pressure. The hydrogen and nitrogen gas flow rates were found to be important parameters for determining the size of the a-Si QDs. In addition, we observed that the PL peak shifted toward a higher energy with increasing hydrogen and nitrogen gas flow rates, which was attributed to the increase in the quantum confinement effect in the a-Si QDs.     

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

Silicon nitride films prepared by reactive plasma sputtering

Silicon nitride films were prepared by reactive plasma sputtering in nitrogen at a pressure of 2×10^-4 Torr. The residual gas in the reactor during film sputtering was analysed. The chemical composition of the films was determined from infrared absorption spectra in the wavelength region 2.0–15.0 μm and by the elastic scattering of ³He particles.The best quality silicon nitride films were obtained in pure nitrogen at the minimum residual gas pressures. An absorption minimum at 11.0 μm in the infrared spectra, corresponding to the Si-N chemical bond in the Si₃N₄ molecule, was observed in our films, indicating that their composition was close to stoichiometric.With a residual hydrogen pressure above 10% or a residual oxygen pressure above 2% the generation of new chemical bonds Si-H, N-H and Si-O respectively was observed in the silicon nitride films.     

Structure and electronic states in a-Si:H thin films

The hydrogenated amorphous silicon (a-Si:H) thin films were prepared by plasma enhanced chemical vapor deposition at various substrate temperatures. This paper examined the relationship between structural evolution and electronic states of the tested thin films. Raman spectroscopy was used to evaluate the structural evolution in amorphous network. Meanwhile, Fourier transform infrared spectroscopy was applied to explore the change of hydrogen in thin films. Results show that the order of network on short and intermediate scales, the content and bonding mode of bonded hydrogen, as well as the intrinsic stress and silicon coordination defects, and closed rings in the thin films, vary with the deposition temperature. The dielectric spectra of samples were measured using SE850 spectra ellipsometer. The density of electronic band states (DOS) in both valence band and conduction band for a-Si:H thin films was obtained by fitting the measured dielectric spectra. The results, verified by optical measurement, reveal that the effect of hydrogenation on band edge DOS is predominant in comparison with that of network relaxation.     

氮化硅介质薄膜内应力的实验研究

研究了等离子体增强化学气相沉积氮化硅介质薄膜的内应力。采用钠光平面干涉测量了氮化硅薄膜内应力,通过改变薄膜沉积时的工艺参数,考察了反应气体流量比、沉积温度、射频功率密度等因素对氮化硅薄膜内应力的影响。在此基础上,对氮化硅介质薄膜本征应力的形成机制进行了分析讨论。     

氮对纳米硅氮薄膜晶化的影响

在电容式耦合等离子体化学气相沉积系统中，用高氢稀释硅烷和氮气为反应气氛制备纳米硅氮（ｎｃ－ＳｉＮｘ２Ｈ）薄膜，结果表明，当Ｎ２／ＳｉＨ４气体流量比（Ｘｎ）从Ｉ增加为４时，薄膜的晶态率从５８％降至１４％，晶粒尺寸从１０ｎｍ降至５ｎｍ，Ｎ／Ｓｉ含量比从０．０３增至０．１２，当Ｘｎ≥５，则生成非晶硅氮（ａ－ＳｉｕＮｘ２Ｈ）薄膜，当Ｘｎ从１增加为１０时，薄膜暗电导率从１０＾－５（Ωｃｍ）＾－１降至１０＾－     

Optical and structural properties of silicon oxynitride deposited by plasma enhanced chemical vapor deposition

We present an overview of the properties of silicon oxynitride material (SiON) deposited by plasma enhanced chemical vapor deposition (PECVD) for photovoltaic applications. SiON films were deposited using silane (SiH₄), ammonia (NH₃) and nitrogen protoxide (N₂O) as precursor gases in a low frequency PECVD. Varying the gas flow mixture leads to a whole range of SiON layers starting from the silicon oxide to the silicon nitride with unique stoichiometries and properties. Thanks to spectroscopic ellipsometry measurements we have confirmed the suitability of SiON for antireflection coating layers due to the range of the refractive indexes attainable. SiON structure was analyzed by X-ray photo-electron spectroscopy. We have thus highlighted the critical role of oxygen behavior on the SiON network and the progressive replacement of nitrogen by oxygen atoms when the oxygen precursor increases. The type of chemical bonds present in SiON layers was also investigated by infrared spectroscopy. The SiON layers also contain a non-negligible amount of hydrogen which might be useful for passivation applications. The behavior of hydrogen content was thus analyzed by elastic recoil decay analysis and desorption characterization. A typical rapid thermal annealing was performed on the SiON samples in order to simulate the solar cells contact annealing and to investigate its impact on the dielectric film properties. It was found that hydrogen becomes weakly bonded to the films and strongly decreases in quantity with the annealing. The surface passivation effect is presented in the last part of this paper. The trend before and after a rapid thermal annealing showed opposite results which could be explained by the high porosity of the layers and the formation of Si-O bonds.     

A low‐cost dehydrogenation system of amorphous silicon thin films used for fabricating low‐temperature polycrystalline silicon

Low‐temperature polycrystalline silicon thin‐film transistors were widely employed in active‐matrix flat‐panel displays and giant microelectronics. In general, a‐Si thin films prepared by plasma‐enhanced chemical vapor deposition contain hydrogen. To prevent the ablation caused by sudden hydrogen eruption during excimer laser crystallization (ELC), two dehydrogenation systems are developed in this study to reduce hydrogen content before excimer laser crystallization. One is a ceramic heater‐based dehydrogenation system and the other is a quartz tube radiant heater‐based dehydrogenation system. The hydrogenated amorphous silicon (a‐Si : H) thin films prepared by plasma‐enhanced chemical vapor deposition are dehydrogenated by both systems. Fourier‐transform infrared absorption spectra revealed that the hydrogen content reduces after dehydrogenation processing. Raman measurements confirmed that the a‐Si : H thin films are still amorphous phase. The major potential advantages of quartz tube radiant heater‐based dehydrogenation system include rapid heating speed, good dehydrogenation quality, small footprint and low cost. Two‐steps temperature rise method is a good candidate for dehydrogenation processing because it provides sample with low thermal distortion.     

Microstructures of microcrystalline silicon thin films prepared by hot wire chemical vapor deposition

Undoped hydrogenated microcrystalline silicon (μc-Si:H) thin films were prepared at low temperature by hot wire chemical vapor deposition (HWCVD). Microstructures of the μc-Si:H films with different H₂/SiH₄ ratios and deposition pressures have been characterized by infrared spectroscopy X-ray diffraction (XRD), Raman scattering, Fourier transform (FTIR), cross-sectional transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The crystallization of silicon thin film was enhanced by hydrogen dilution and deposition pressure. The TEM result shows the columnar growth of μc-Si:H thin films. An initial microcrystalline Si layer on the glass substrate, instead of the amorphous layer commonly observed in plasma enhanced chemical vapor deposition (PECVD), was observed from TEM and backside incident Raman spectra. The SAXS data indicate an enhancement of the mass density of μc-Si:H films by hydrogen dilution. Finally, combining the FTIR data with the SAXS experiment suggests that the Si---H bonds in μc-Si:H and in polycrystalline Si thin films are located at the grain boundaries.     

用ECRCVD方法制备优质氮化硅钝化膜

利用电子回旋共振等离子体化学气相沉积(ECR—CVD)技术，以SiH4和N2为反应气体进行了氮化硅钝化薄膜的低温沉积技术的研究。采用原子力显微镜、傅立叶变换红外光谱和椭圆偏振光检测等技术对薄膜的表面形貌、结构、厚度和折射率等性质进行了测量。结果表明，采用ECR—CVD技术能够在较低的衬底温度条件下以较高的沉积速率制备厚度均匀的氮化硅薄膜，薄膜中H含量很低。薄膜沉积速率随微波功率和混合气体中硅烷比例的增加而增大。折射率随微波功率的增大而减小，随混合气体中硅炕比例的增大而增大。在相同气体混合比和微波功率条件下，较高衬底温度条件下制备的薄膜折射率较大。     

Structural and optical properties of amorphous oxygenated iron boron nitride thin films produced by reactive co-sputtering

Amorphous oxygenated iron boron nitride (a-FeBN:O) thin films were prepared by reactive radio-frequency (RF) sputtering, from hexagonal boron nitride chips placed on iron target, under a total pressure of a gas mixture of argon and oxygen maintained at 1 Pa. The films were deposited onto silicon and glass substrates, at room temperature. The power of the generator RF was varied from 150 to 350 W. The chemical and structural analyses were investigated using X-ray photoelectron spectroscopy (XPS), energy dispersive of X-ray and X-ray reflectometry (XRR). The optical properties of the films were obtained from the optical transmittance and reflectance measurements in the ultraviolet-visible-near infrared wavelengths range. XPS reveals the presence of boron, nitrogen, iron and oxygen atoms and also the formation of different chemical bonds such as Fe-O, B-N, B-O and the ternary BNO phase. This latter phase is predominant in the deposited films as observed in the B 1s and N 1s core level spectra. As the RF power increases, the contribution of N-B bonds in the as-deposited films decreases. The XRR results show that the mass density of a-FeBN:O thin films increases from 2.6 to 4.12 g/cm³ with increasing the RF power from 150 to 350 W. This behavior is more important for films deposited at RF power higher than 150 W, and has been associated with the enhancement of iron atoms in the film structure. The optical band gap decreases from 3.74 to 3.12 eV with increasing the RF power from 150 to 350 W.     

HWP-CVD氮化硅薄膜的结构和光学特性

采用傅立叶红外吸收谱和紫外-可见透射谱研究了螺旋波等离子体增强化学气相沉积法制备的氢化非晶氮化硅薄膜的原子间键合结构和光学特性。结果表明,在不同硅、氮活性气体配比R下,薄膜表现出不同的Si/N比和H原子键合方式,富氮样品中H原子主要和N原子结合,而富硅样品中主要和Si原子结合。随着R的增加,薄膜的光学带隙E_g和E₀₄逐渐减小,此结果关联于薄膜结构无序性程度的增加,而薄膜的(E₀₄-E_g)和Tauc斜率B值之间存在着相互制约关系。     

The influence of CH4 addition on composition, structure and optical characteristics of SiCN thin films deposited in a CH4/N2/Ar/hexamethyldisilazane microwave plasma

Amorphous silicon carbonitride (a-SiCN) thin films were synthesized in a microwave plasma assisted chemical vapor deposition system using N₂, Ar, CH₄ and hexamethyldisilazane vapor (HMDSN). Composition, morphology and optical constants of the layers have been studied as a function of CH₄ rate in the range 0 to 9%. It was found that films are mainly composed of silicon nitride like compound whatever the CH₄ rate. However, CH₄ addition leads to less hydrogenated and denser films. In addition, a refractive index augmentation from 1.7 to 2.0 and a Tauc gap decrease from 5.2 eV to 4.8 eV is measured with CH₄ rate increase. It is believed that the refractive index augmentation is due to higher thin film density whereas hydrogen bonds decrease is assumed to contribute to the band gap narrowing. Besides, CH₄ addition to the gaseous mixture increases thin film oxidation resistance. These results show the ability of varying composition, structure and optical constants of a-SiCN films by modifying CH₄ rate in a N₂/Ar/HMDSN plasma.     

氢稀释对纳米晶硅薄膜微结构的影响

采用电感耦合等离子体化学气相沉积技术制备了氮化纳米硅薄膜,利用Raman散射、x射线衍射、红外吸收等技术对不同氮稀释条件下薄膜的微观结构和键合特性变化进行了研究.结果表明,较高的氢稀释比导致薄膜从非晶硅到纳米晶硅的结构转化,随着氮稀释比的增加,所沉积薄膜的晶化度及纳米晶硅的晶粒尺寸单调增加,纳米硅颗粒呈现在(110)方...     

Hydrogen and nitrogen effects on optical and structural properties of amorphous carbon

Two series of amorphous carbon alloys were deposited by reactive sputtering using a graphite target and argon as a sputtering gas. The effect of hydrogen or nitrogen on the structure of amorphous carbon was investigated using photothermal deflection spectroscopy (PDS), UV–Vis–near infrared spectroscopy, Fourier Transform Infrared (FT-IR), Raman and Photoluminescence (PL) techniques. The change in the structure of hydrogenated amorphous carbon (a-C:H) is due to the fact that H incorporation favours the formation of sp³ sites. In fact, the hydrogen incorporation relaxes the structure enough to improve electronic properties by increasing the number of terminal bonds. In the amorphous carbon nitride (a-CN) films, the lone pairs belonging to the nitrogen atoms are important in determining the optical properties of the films. The nitrogen alters the structure of carbon and creates cavities to be responsible for hydroxyl (OH) inclusions.     

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.     

Evolution of structural and optical properties of nanostructured silicon carbon films deposited by plasma enhanced chemical vapour deposition

Nanostructured silicon carbon films composed of silicon nanocrystallites embedded in hydrogenated amorphous silicon carbon matrix have been deposited by plasma enhanced chemical vapour deposition technique using silane and methane gas mixture highly diluted in hydrogen. The structural and optical properties of the films have been investigated by X-ray diffraction, Raman, Fourier transform infrared, ultra violet-visible-near infrared and photoluminescence spectroscopies while the composition of the films has been obtained from nuclear techniques. The study has demonstrated that the structure of the films evolves from microcrystalline to nanocrystalline phase with the increase in radio frequency (rf) power. Further, it is shown that with increasing the rf power the size of silicon nanocrystallites decreases while the optical gap increases and a blueshift of visible room temperature photoluminescence peak can be observed.     

Effect of film thickness on hydrogen content in a-Si : H

The hydrogen content, its depth distribution, and its bonding configuration have been studied in hydrogenated amorphous silicon prepared by plasma-enhanced chemical vapor deposition with hydrogen-diluted silane. Nuclear reaction analysis and infrared spectroscopy were used to determine the total amount of hydrogen and its bonded component, respectively. It has been established that the total concentration of hydrogen does not depend on the film thickness, and has a uniform depth profile. The concentration of bonded hydrogen changes with the film thickness within the measurement accuracy. The data obtained suggest the presence of molecular (non-bonded) hydrogen, uniformly distributed in concentration across the film thickness.