Effects of hydrogen plasma annealing on the luminescence from a-Si:H/SiO2 and nc-Si/SiO2 multilayers

Effects of post-hydrogen plasma annealing (HPA) on a-Si:H/SiO₂ and nc-Si/SiO₂ multilayers have been investigated and compared. It is found that photoluminescence (PL) from hydrogen-passivated samples was improved due to the reduction of non-radiative recombination defects. Some interesting difference is that during HPA, atomic hydrogen can directly passivate defects of a-Si:H/SiO₂, which results in the reappearance of luminescence band at 760 nm, while for nc-Si/SiO₂, hydrogen passivation requires additional thermal annealing after nc-Si/SiO₂ multilayer was treated by HPA. It is indicated that higher atomic mobility is needed to passivate defects at nc-Si/SiO₂ interface compared with a-Si:H/SiO₂ interface.     

Photoluminescence properties of SiNx/Si amorphous multilayer structures grown by plasma-enhanced chemical vapor deposition

Very thin (nanometric) silicon layers were grown in between silicon nitride barriers by SiH₂Cl₂/H₂/NH₃ plasma-enhanced chemical vapor deposition (PECVD). The multilayer structures were deposited onto fused silica and silicon substrates. Deposition conditions were selected to favor Si cluster formation of different sizes in between the barriers of silicon nitride. The samples were thermally treated in an inert atmosphere for 1 h at 500 °C for dehydrogenation. Room-temperature photoluminescence (RT-PL) and optical transmission in different ranges were used to evaluate the optical properties of the structures. UV-VIS absorption spectra present two band edges. These band edges are well fitted by the Tauc model typically used for amorphous materials. RT-PL spectra are characterized by strong broad bands, which have a blue shift as a function of the deposition time of the silicon layer, even for as-grown samples. The broad luminescence could be associated with the confinement effect in the silicon clusters. After annealing of the samples, the PL bands red shift. This is probably due to the thermal decomposition of N-H bonds with further effusion of hydrogen and better nitrogen passivation of the nc-Si/SiN_x interfaces.     

尺寸可控的纳米硅的生长模型和实验验证

基于经典热力学理论，对a-SiN_x/a-Si:H/a-SiN_x三明治结构或a-Si:H/a-SiN_x多层膜结构中纳米硅成核，以及从球形到鼓形的生长过程进行了研究. 建立了限制性晶化理论模型：在纳米硅生长过程中，由于界面能增大将导致生长停止，给出限制性晶化条件——a-Si:H子层厚度小于34 nm. 在激光晶化和常规热退火两种方法形成的a-SiN_x/nc-Si/a-SiN_x三明治结构和nc-Si/a-SiN_x多层膜结构中验证了该理论模型. 关键词： 非晶硅 纳米硅 激光辐照 结晶     

氢化非晶硅薄膜退火形成的纳米硅及其光致发光

本文报道对氢化非晶硅(a-Si:H)薄膜在600～620℃温度下快速退火10s可以形成纳米晶硅(nc-Si),其Raman散射表明,在所形成的nc-Si在薄膜中的分布是随机的,直径在1.6～15nm范围内,并且在强激光辐照下观察了nc-Si在薄膜中的结晶和生长情况.经退火所形成的nc-Si可见光辐射较弱,不能检测到它们的光致发光(PL),但用氢氟酸腐蚀钝化后则可检测到较强的红PL,并且钝化后的nc-Si在空气中暴露一定的时间后,其辐射光波长产生了蓝移.文中就表面钝化和量子限制对可见光辐射的重要性作了讨论.     

激光限制结晶技术制备nc-Si/SiO2多层膜

在等离子体增强化学气相淀积系统中，采用aSi:H层淀积和原位等离子体氧化相结合的逐层生长技术制备了aSi:H/SiO_2多层膜.在激光诱导限制结晶原理基础上，使用KrF准分子脉冲激光为辐照源，对aSi:H/SiO_2多层膜进行辐照，使纳米级厚度的aSi:H子层晶化.Raman散射谱和电子衍射谱的结果表明，经过激光辐照后纳米Si颗粒在原始的aSi:H子层内形成，晶粒尺寸可以根据aSi:H层的厚度精确控制.还研究了样品的光致发光（PL）特性以及激光辐照能量密度对PL性质的影响. 关键词： 脉冲激光 多层膜 限制结晶     

Ultra fast melting process in femtosecond laser crystallization of thin a-Si layer

In this paper, we investigated the mechanism of crystallization induced by femtosecond laser irradiation for an amorphous Si (a-Si) thin layer on a crystalline Si (c-Si) substrate. The fundamental, SHG, THG wavelength of a Ti:Sapphire laser was used for the crystallization process. To investigate the processed areas we performed Laser Scanning Microscopy (LSM), Transmission Electron Microscopy (TEM) and Imaging Pump-Probe measurements. Except for 267 nm femtosecond laser irradiation, the crystallization occurred well. The threshold fluences for the crystallization using 800 nm and 400 nm femtosecond laser irradiations were 100 mJ/cm² and 30 mJ/cm², respectively. TEM observation revealed that the crystallization occurred by epitaxial growth from the boundary surface between the a-Si layer and c-Si substrate. The melting depths estimated by Imaging Pump-Probe measurements became shallower when the shorter wavelength was used.     

Optimization of laser patterning of textured gallium-doped zinc oxide for amorphous silicon photovoltaics

Laser scribing process of in-house textured gallium-doped zinc oxide (GZO) is optimized, aiming to improve the performance of amorphous silicon (a-Si:H) photovoltaic (PV) modules. The reasons for different scribing quality of textured GZO and SnO₂:F scribed at 1064 nm with pulse duration of 40 ns were analyzed. Apart from separation resistance, quality of the scribed lines was evaluated by laser scan microscopy from three-dimensional images. Other types of lasers, such as laser with shorter pulse duration, laser at 355 nm and laser with Gaussian-to-tophat converter, were used to smooth the edges and flatten the bottoms of the scribed lines. The proper laser scribing realizes the advantages of textured GZO films used as front contacts in PV modules. A short-circuit current density of 14.3 mA/cm² and an initial aperture area efficiency of 8.8% were obtained on 16 cm × 16 cm textured GZO coated glass scribed at 355 nm with pulse duration of 40 ns.     

a-Si∶O∶H薄膜微结构及其高温退火行为研究

以微区Raman散射、X射线光电子能谱和红外吸收对等离子体增强化学气相沉积(PECVD)法制备的氢化非晶硅氧(a-Si∶O∶H)薄膜微结构及其退火行为进行了细致研究.结果表明a-Si∶O∶H薄膜具有明显的相分离结构,富Si相镶嵌于富O相之中,其中富Si相为非氢化四面体结构形式的非晶硅(a-Si),富O相为Si,O,H三种原子随机键合形成的SiO_x∶H(x≈1.35).经1150℃高温退火,薄膜中的H全部释出;SiO_x∶H(x≈1.35)介质在析出部分Si原子的同     

Morphology, optical and electrical properties of Cu-Ni nanoparticles in a-C:H prepared by co-deposition of RF-sputtering and RF-PECVD

We report optical and electrical properties of Cu-Ni nanoparticles in hydrogenated amorphous carbon (Cu-Ni NPs @ a-C:H) with different surface morphology. Ni NPs with layer thicknesses of 5, 10 and 15 nm over Cu NPs @ a-C:H were prepared by co-deposition of RF-sputtering and RF-Plasma Enhanced Chemical Vapor Deposition (RF-PECVD) from acetylene gas and Cu and Ni targets. A nonmetal-metal transition was observed as the thickness of Ni over layer increases. The surface morphology of the sample was described by a two dimensional (2D) Gaussian self-affine fractal, except the sample with 10 nm thickness of Ni over layer, which is in the nonmetal-metal transition region. X-ray diffraction profile indicates that Cu NPs and Ni NPs with fcc crystalline structure are formed in these films. Localized Surface Plasmon Resonance (LSPR) peak of Cu NPs is observed around 600 nm in visible spectra, which is widen and shifted to lower wavelengths as the thickness of Ni over layer increases. The variation of LSPR peak width correlates with conductivity variation of these bilayers. We assign both effects to surface electron delocalization of Cu NPs.     

Aluminium-induced crystallization of amorphous silicon films deposited by DC magnetron sputtering on glasses

Amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) films were deposited by DC magnetron sputtering technique with argon and hydrogen plasma mixture on Al deposited by thermal evaporation on glass substrates. The a-Si/Al and a-Si:H/Al thin films were annealed at different temperatures ranging from 250 to 550 °C during 4 h in vacuum-sealed bulb. The effects of annealing temperature on optical, structural and morphological properties of as-grown as well as the vacuum-annealed a-Si/Al and a-Si:H/Al thin films are presented in this contribution. The averaged transmittance of a-Si:H/Al film increases upon increasing the annealing temperature. XRD measurements clearly evidence that crystallization is initiated at 450 °C. The number and intensity of diffraction peaks appearing in the diffraction patterns are more important in a-Si:H/Al than that in a-Si/Al layers. Results show that a-Si:H films deposited on Al/glass crystallize above 450 °C and present better crystallization than the a-Si layers. The presence of hydrogen induces an improvement of structural properties of poly-Si prepared by aluminium-induced crystallization (AIC).     

Crystallization kinetics of amorphous SiC films: Influence of substrate

The crystallization kinetics of amorphous silicon carbide films was studied by means of X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films were deposited by radio frequency (r.f.) magnetron sputtering on glassy carbon and single crystalline silicon substrates, respectively. TEM micrographs and XRD patterns show the formation of nano-crystalline β-SiC with crystallite sizes in the order of 50 nm during annealing at temperatures between 1200 and 1600 °C. A modified Johnson-Mehl-Avrami-Kolmogorov (JMAK) formalism was used to describe the isothermal transformation of amorphous SiC into β-SiC as an interface controlled, three-dimensional growth processes from pre-existing small crystallites in the order of 10 nm. These pre-existing crystallites are formed in a transient process in the early stages of crystallization. For films deposited on the silicon substrate, the obtained rate constants of crystallite growth obey an Arrhenius behavior with an activation enthalpy of 4.1 ± 0.5 eV in accordance with literature data. Films deposited on glassy carbon show an increased stability of amorphous SiC films, which is reflected in smaller rate constants of crystallite growth of several orders of magnitude at low temperatures and a higher activation enthalpy of 8.9 ± 0.9 eV. A model is proposed, where the faster crystallization of films on silicon substrates can be explained with the presence of superabundant point defects, which diffuse from the substrate into the film and accelerate the incorporation of atoms from the amorphous into the crystalline phase.     

Thickness influence on surface morphology and ozone sensing properties of nanostructured ZnO transparent thin films grown by PLD

Transparent zinc oxide (ZnO) thin films with a thickness from 10 to 200 nm were prepared by the PLD technique onto silicon and Corning glass substrates at 350 °C, using an Excimer Laser XeCl (308 nm). Surface investigations carried out by atomic force microscopy (AFM) and X-ray diffraction (XRD) revealed a strong influence of thickness on film surface topography. Film roughness (RMS), grain shape and dimensions correlate with film thickness. For the 200 nm thick film, the RMS shows a maximum (13.9 nm) due to the presence of hexagonal shaped nanorods on the surface. XRD measurements proved that the films grown by PLD are c-axis textured. It was demonstrated that the gas sensing characteristics of ZnO films are strongly influenced and may be enhanced significantly by the control of film deposition parameters and surface characteristics, i.e. thickness and RMS, grain shape and dimension.     

Influence of deposition pressure on structural, optical and electrical properties of nc-Si:H films deposited by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited using HW-CVD technique at various deposition pressures. Characterisation of these films from Raman spectroscopy revealed that nc-Si:H thin films consist of a mixture of two phases, crystalline phase and amorphous phase containing small Si crystals embedded therein. We observed increase in crystallinity in the films with increase in deposition pressure whereas the size of Si nanocrystals was found ∼2 nm over the entire range of deposition pressure studied. The FTIR spectroscopic analysis showed that with increasing deposition pressure the predominant hydrogen bonding in the films shifts from, Si-H to Si-H₂ and (Si-H₂)_n complexes and the hydrogen content in the films was found in the range 6.2-9.3 at% over the entire range of deposition pressure studied. The photo and dark conductivities results also indicate that the films deposited with increasing deposition pressure get structurally modified. It has been found that the optical energy gap range was between 1.72 and 2.1 eV with static refractive index between 2.85 and 3.24. From the present study it has been concluded that the deposition pressure is a key process parameter to induce the crystallinity in the Si:H thin films using HW-CVD.     

Alumina capped ZnO quantum dots multilayer grown by pulsed laser deposition

To extend the applicability of ZnO, with the bulk band gap of about 3.3 eV, into deep UV region, we have grown a multilayer of alumina capped ZnO quantum dots of mean in-plane sizes in the range of ∼1.8-3.6 nm at room temperature using alternate Pulsed Laser Deposition. Size dependent blue shift of the band gap of these dots up to ∼4.5 eV is observed in the optical absorbance spectra. The observed blue shift can be understood using the effective mass approximation in weak and strong confinement regimes.     

Crystallization of hydrogenated amorphous silicon carbon films with laser and thermal annealing

The crystallization of silicon rich hydrogenated amorphous silicon carbon films prepared by Plasma Enhanced Chemical Vapor Deposition technique has been induced by excimer laser annealing as well as thermal annealing. The excimer laser energy density (E_d) and the annealing temperature were varied from 123 to 242 mJ/cm² and from 250 to 1200 °C respectively. The effects of the two crystallization processes on the structural properties and bonding configurations of the films have been studied. The main results are that for the laser annealed samples, cubic SiC crystallites are formed for E_d ≥ 188 mJ/cm², while for the thermal annealed samples, micro-crystallites SiC and polycrystalline hexagonal SiC are observed for the annealing temperature of 800 and 1200 °C respectively. The crystallinity degree has been found to improve with the increase in the laser energy density as well as with the increase in the annealing temperature.     

MICROSTRUCTURE OF SiOx:H FILMS PREPARED BY PLASMA ENHANCED CHEMICAL VAPOR DEPOSITION

The micro-Raman spectroscopy and infrared (IR) spectroscopy have been performed for the study of the microstructure of amorphous hydrogenated oxidized silicon (a-SiO_x:H) films prepared by Plasma Enhanced Chemical Vapor Deposition technique. It is found that a-SiO_x:H consists of two phases: an amorphous silicon-rich phase and an oxygen-rich phase mainly comprised of HSi-SiO₂ and HSi-O₃. The Raman scattering results exhibit that the frequency of TO-like mode of amorphous silicon red-shifts with decreasing size of silicon-rich region. This is related to the quantum confinement effects, similar to the nanocrystalline silicon.     

Correlation between Light Emissions from Amorphous-Si：H/SiO2 and nc-Si/SiO2 Multilayers

We investigate the properties of light emission from amorphous-Si：H/SiO2 and nc-Si/SiO2 multilayers （MLs）. The size dependence of light emission is well exhibited when the a-Si：H sublayer thickness is thinner than 4 nm and the interface states are well passlvated by hydrogen. For the nc-Si/Si02 MLs, the oxygen modified interface states and nanocrystalline silicon play a predominant role in the properties of light emission. It is found that the light emission from nc-Si/SiO2 is in agreement with the model of interface state combining with quantum confinement when the size of nc-Si is smaller than 4 nm. The role of hydrogen and oxygen is discussed in detail.     

纳米硅薄膜光吸收谱的研究

用恒定光电导法测量了纳米硅(其晶粒尺寸为3-5nm,晶态成分比X_c为45％—50％)薄膜在0.9—2.5eV范围的光吸收谱。分析了在不同光子能量范围可能存在的对光电导作主要贡献的几种光跃迁过程,以及随着X_c的增加,材料由非晶、微晶转变为纳米硅薄膜时光吸收谱的变化。发现纳米硅晶粒之间的界面区(平均厚度约为1nm)中载流子的跃迁及传输过程对整个范围的光吸收谱起主导作用。联系纳米硅的这种特殊结构解释了有关实验结果。 关键词：     

Degradation analysis of thin film photovoltaic modules

Five thin film photovoltaic modules were deployed outdoors under open circuit conditions after a thorough indoor evaluation. Two technology types were investigated: amorphous silicon (a-Si:H) and copper indium gallium diselenide (CIGS). Two 14 W a-Si:H modules, labelled Si-1 and Si-2, were investigated. Both exhibited degradation, initially due to the well-known light-induced degradation described by Staebler and Wronski [Applied Physics Letters 31 (4) (1977) 292], and thereafter due to other degradation modes such as cell degradation. The various degradation modes contributing to the degradation of the a-Si:H modules will be discussed. The initial maximum power output (P_MAX) of Si-1 was 9.92 W, with the initial light-induced degradation for Si-1 ∼30% and a total degradation of ∼42%. For Si-2 the initial P_MAX was 7.93 W, with initial light-induced degradation of ∼10% and a total degradation of ∼17%. Three CIGS modules were investigated: two 20 W modules labelled CIGS-1 and CIGS-2, and a 40 W module labelled CIGS-3. CIGS-2 exhibited stable performance while CIGS-1 and CIGS-3 exhibited degradation. CIGS is known to be stable over long periods of time, and thus the possible reasons for the degradation of the two modules are discussed.