Flash-lamp-crystallized polycrystalline silicon films with high hydrogen concentration formed from Cat-CVD a-Si films

We investigate residual forms of hydrogen (H) atoms such as bonding configuration in poly-crystalline silicon (poly-Si) films formed by the flash-lamp-induced crystallization of catalytic chemical vapor deposited (Cat-CVD) a-Si films. Raman spectroscopy reveals that at least part of H atoms in flash-lamp-crystallized (FLC) poly-Si films form Si-H₂ bonds as well as Si-H bonds with Si atoms even using Si-H-rich Cat-CVD a-Si films, which indicates the rearrangement of H atoms during crystallization. The peak desorption temperature during thermal desorption spectroscopy (TDS) is as high as 900 °C, similar to the reported value for bulk poly-Si.     

Precursor Cat-CVD a-Si films for the formation of high-quality poly-Si films on glass substrates by flash lamp annealing

Amorphous Si (a-Si) films with lower hydrogen contents show better adhesion to glass during flash lamp annealing (FLA). The 2.0 µm-thick a-Si films deposited by plasma-enhanced chemical vapor deposition (PECVD), containing 10% hydrogen, start to peel off even at a lamp irradiance lower than that required for crystallization, whereas a-Si films deposited by catalytic CVD (Cat-CVD) partially adhere even after crystallization. Dehydrogenated Cat-CVD a-Si films show much better adhesion to glass, and are converted to polycrystalline Si (poly-Si) without serious peeling, but are accompanied by the generation of crack-like structures. These facts demonstrate the superiority of as-deposited Cat-CVD a-Si films as a precursor material for micrometer-thick poly-Si formed by FLA.     

Poly-Si films with long carrier lifetime prepared by rapid thermal annealing of Cat-CVD amorphous silicon thin films

Polycrystalline silicon (poly-Si) films thicker than 1.5 μm, consisting of dense small grains called nano-grain poly-Si (ngp-Si), are formed by flash lamp annealing (FLA) of amorphous silicon (a-Si) films prepared by catalytic chemical vapor deposition (Cat-CVD) method. Crystallinity of the ngp-Si films can be controlled by changing lamp irradiance. Secondary ion mass spectroscopy (SIMS) profiles of dopants in the ngp-Si films after FLA shows no serious diffusion. A minority carrier lifetime of over 5 μs is observed from these ngp-Si films after defect termination process using high pressure water vapor annealing (HPWVA), showing possibility of application for high-efficient thin film solar cells.     

Crystallization by excimer laser annealing for a-Si:H films with low hydrogen content prepared by Cat-CVD

Crystallization by excimer-laser annealing (ELA) for hydrogenated amorphous silicon (a-Si:H) films with low hydrogen content (C_H) prepared by catalytic chemical vapor deposition (Cat-CVD) was systematically studied. From optical microscopy images, no hydrogen bubbling was observed during ELA, even without a dehydrogenation process. As the laser energy density was increased to 300 mJ cm⁻², the full width at half-maximum of the Raman signal from the crystalline phase decreased to approximately 4 cm⁻¹. This value is almost equal to or even smaller than that reported for polycrystalline Si (poly-Si) films prepared from plasma-enhanced CVD (PECVD) a-Si:H films by ELA so far. The average grain size, estimated from scanning electron microscopy, was approximately 500 nm for C_H of 1.3 at.%. On the other hand, the grain size of poly-Si films prepared from PECVD a-Si:H films with a dehydrogenation process was only 200 nm. The technique using Cat-CVD films is expected to be used for fabrication of low-temperature high-mobility thin-film transistors.     

Influence of annealing temperature on the properties of polycrystalline silicon films formed by rapid thermal annealing of a-Si:H films

In this work, rapid thermal annealing (RTA) was employed to crystallize the amorphous silicon films deposited by hot-wire chemical vapor deposition. The influence of annealing temperature on structural and electrical properties was studied by Raman spectroscopy, X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy and temperature-dependent conductivity measurement. The results show that the amorphous silicon films can be successfully crystallized by RTA in a very short time. The crystallinity and electrical properties of the poly-Si films was greatly improved as the RTA temperature increasing. When the temperature higher than 900 °C, the poly-Si films obtained the crystalline fraction above 95 %, and the hydrogen atoms almost disappeared in the poly-Si films. At the temperature of 1,100 °C, polycrystalline silicon films with conductivity of 16.4 S cm^?1 is obtained, which is seven orders in magnitude higher than that of the film annealed at 700 °C.     

Drastic suppression of the optical reflection of flash-lamp-crystallized poly-Si films with spontaneously formed periodic microstructures

Polycrystalline Si (poly-Si) films formed by flash lamp annealing of precursor a-Si films on glass substrates have periodic surface roughness spontaneously formed through crystallization, which effectively acts to decrease optical reflection. The surface roughness initially decreases, and then reversely increases with increase in the duration of wet etching, performed to modulate the surface morphology and to reduce optical reflectance. This curious phenomenon can be understood as the selective removal of surface projections, which contain a number of voids, and as different etching rates of large-grain and fine-grain regions. The antireflection effect is enhanced not by the variation of the surface roughness, but rather by the removal of the voids near the surface. The etched poly-Si films covered with antireflection films show remarkably low average reflectance of 3% without any complicated texturing processes, which will lead to the fabrication of high-efficiency solar cells by a simple process.     

Fabrication of polycrystalline silicon thin films on glass substrates using fiber laser crystallization

Laser crystallization of amorphous silicon (a-Si), using a fiber laser of λ = 1064 nm wavelength, was investigated. a-Si films with 50 nm thickness deposited on glass were prepared by a plasma enhanced chemical vapor deposition. The infrared fundamental wave (λ = 1064 nm) is not absorbed by amorphous silicon (a-Si) films. Thus, different types of capping layers (a-CeO_x, a-SiN_x, and a-SiO_x) with a desired refractive index, n and thickness, d were deposited on the a-Si surface. Crystallization was a function of laser energy density, and was performed using a fiber laser. The structural properties of the crystallized films were measured via Raman spectra, a scanning electron microscope (SEM), and an atomic force microscope (AFM). The relationship between film transmittance and crystallinity was discussed. As the laser energy density increased from 10-40 W, crystallinity increased from 0-90%. However, the higher laser density adversely affected surface roughness and uniformity of the grain size. We found that favorable crystallization and uniformity could be accomplished at the lower energy density of 30 W with a-SiO_x as the capping layer.     

射频功率对非晶硅膜固相晶化效果的影响

于不同射频功率下制备出非晶Si膜并对其进行真空退火处理,采用XRD、TEM和少子寿命测试仪等检测手段分析了退火前后薄膜的微观结构及电学性能。研究发现,随着射频功率的增加,薄膜的中程有序度和少子寿命均呈先增后减的趋势。经真空退火处理后,非晶硅膜得以晶化,少子寿命较退火前有大幅提高;另外,退火后薄膜的晶化率和少子寿命随射频功率的变化趋势与退火前一致,说明同一热力学条件下薄膜的中程有序度越高越容易发生晶化。     

Large-grain polycrystalline silicon thin films obtained by low-temperature stepwise annealing of hydrogenated amorphous silicon

Large grained polycrystalline silicon thin films have been prepared by low-temperature solid phase crystallisation of sputter-deposited hydrogenated amorphous silicon (a-Si:H), with relatively short processing times, and a considerably low thermal budget. Various a-Si:H samples, deposited under different conditions and with varying hydrogen concentrations and hydrogen bonding configurations, were simultaneously annealed. Only a particular set of deposition conditions led to crystallisation. The a-Si:H thin film which was successfully crystallised was prepared in an argon-hydrogen mixture, in which the last few minutes of film deposition occurred in a hydrogen-rich atmosphere. For that film, the hydrogen concentration profile resulted in a much higher hydrogen content on the sample surface than in the bulk, and H-Si bonds were predominantly of the weak type. Crystallisation was accomplished by low-temperature stepwise annealing from 200°C to 600°C at 100°C steps, with samples being cooled down to room-temperature between each annealing step. This resulted in large grained (> 10 μm range) polycrystalline silicon after the 600°C annealing step for a 1.1 μm thick sample. Fourier transform infrared (FTIR) spectroscopy, elastic recoil detection analysis (ERDA) and scanning electron microscopy (SEM) techniques were used to analyse samples before and after crystallisation.     

Preparation of high quality polycrystalline silicon thin films by aluminum-induced crystallization

High quality polycrystalline silicon (poly-Si) thin films without Si islands were prepared by using aluminum-induced crystallization on glass substrates. Al and amorphous silicon films were deposited by vacuum thermal evaporation and radio frequency magnetron sputtering, respectively. The samples were annealed at 500 °C for 7 h and then Al was removed by wet etching. Scanning electron microscopy shows that there are two layers in the thin films. After the upper layer was peeled off, the lower poly-Si thin film was found to be of high crystalline quality. It presented a Raman peak at 521 cm^− 1 with full width at a half maximum of 5.23 cm^− 1, which is similar to c-Si wafer.     

铝诱导晶化真空蒸镀多晶硅薄膜的研究

采用真空蒸镀的方法在玻璃衬底上沉积1层非晶硅薄膜,再通过铝诱导晶化的方法制备出晶粒分布较均匀、晶粒尺寸0.5～5μm、晶化率达到89%的多晶硅薄膜。研究了衬底距离、衬底温度、退火温度对薄膜表面形貌、晶粒尺寸和分布及晶化率的影响。结果表明适中的衬底距离下得到的薄膜晶粒分布均匀,表面平整度好,薄膜厚度较大。薄膜的晶化率随着衬底温度和退火温度的提高而增大;随着退火温度的进一步提高,薄膜的晶化率达到最大值然后降低。     

Effects of annealing temperature on crystallisation kinetics and properties of polycrystalline Si thin films and solar cells on glass fabricated by plasma enhanced chemical vapour deposition

Solid-phase crystallisation of Si thin films on glass fabricated by plasma enhanced chemical vapour deposition is compared at different annealing temperatures. Four independent techniques, optical transmission microscopy, Raman and UV reflectance spectroscopy, and X-ray diffraction, are used to characterise the crystallisation kinetics and film properties. The 1.5 μm thick films with the n+/p−/p+ solar cell structure have incubation times of about 300, 53, and 14 min and full crystallisation times of about 855, 128, and 30 min at 600 °C, 640 °C, and 680 °C respectively. Estimated activation energies for incubation and crystal growth are 2.7 and 3.2 eV respectively. The average grain size in the resulting polycrystalline Si films measured from scanning electron microscopy images gradually decreases with a higher annealing temperature and the crystal quality becomes poorer according to the Raman, UV reflection, and X-ray diffraction results. The dopant activation and majority carrier mobilities in heavily doped n+ and p+ layers are similar for all crystallisation temperatures. Both the open-circuit voltage and the spectral response are lower for the cells crystallised at higher temperatures and the minority carrier diffusion lengths are shorter accordingly although they are still longer than the cell thickness for all annealing temperatures. The results indicate that shortening the crystallisation time by merely increasing the crystallisation temperature offers little or no merits for PECVD polycrystalline Si thin-film solar cells on glass.     

T型发射区单晶硅太阳电池的输出特性研究

利用TCAD半导体器件仿真软件对具有T型发射区结构的单晶硅太阳电池进行了仿真研究。全面系统地分析了在不同衬底少子寿命情况下,不同T型发射区深度对太阳电池外量子效率、短路电流密度、开路电压、填充因子及转换效率的影响。仿真结果表明:采用T型发射区结构可在一定程度上提高常规均匀发射区太阳电池的电学性能;T型发射区结构对700~1200nm长波段入射光的外量子效率具有明显的改善作用;当衬底少子寿命一定时,太阳电池短路电流密度、填充因子均随T型发射区深度的增大而增大,而开路电压随T型发射区深度的增大而减小;当T型发射区深度大于80μm时,对于低衬底少子寿命的单晶硅太阳电池,T型发射区结构对其转换效率的改善效果最为显著。     

Rapid thermal-plasma annealing of ZnO:Al films for silicon thin-film solar cells

Rapid thermal annealing of sputter-deposited ZnO and Al-doped ZnO (AZO) films with and without an amorphous silicon (a-Si) capping layer was investigated using a radio-frequency (rf) argon thermal plasma jet at atmospheric pressure. The resistivity of bare ZnO films on glass decreased drastically from 10⁶ to 10³ Ω·cm at maximum surface temperatures T_max above 650 °C, whereas the resistivity increased from 10^− 4 to 10^− 3-10^− 2 Ω·cm for bare AZO films. On the other hand, the resistivity of AZO films with a 30-nm-thick a-Si capping layer remained below 10^− 4 Ω·cm, even after TPJ annealing at a T_max of 825 °C. X-ray diffraction and X-ray photoemission electron studies revealed that the film crystallization of both AZO and a-Si layers was promoted without the formation of an intermixing layer. Additionally, the crystallization of phosphorous- and boron-doped a-Si layers at the sample surface was promoted, compared to that of intrinsic a-Si under identical plasma annealing conditions. The role of the a-Si capping layer on sputter-deposited AZO and ZnO films during TPJ annealing is demonstrated. The effects of the mixing of phosphorous and boron impurities in a-Si:H during TPJ annealing of flat and textured AZOs are also discussed.     

Electrical and optical properties of semi-insulating polycrystalline silicon thin films: the role of microstructure and doping

We have investigated the relationship between microstructure and electrical conductivity in semi-insulating polycrystalline silicon (SIPOS) with oxygen concentrations in the 2–35 at.% range and the effect of doping with boron, phosphorus, arsenic and erbium by ion implantation. SIPOS thin films are mixtures of silicon and silicon oxide phases. The chemical and morphological evolution of these phases upon annealing is emphasized. Electrical conductivity measurements are interpreted in terms of a physical model containing few free parameters related to the material microstructure. A direct extension of this model explains also the conductivity increase in SIPOS doped with elements of the third or the fifth group. In the last part of the paper, data of electroluminescence at 1.54 μm in Er-implanted SIPOS due to intra-4f transitions of the Er³⁺ ion are shown and discussed.     

Contact resistivity measurements of the buried Si-ZnO:Al interface of polycrystalline silicon thin-film solar cells on ZnO:Al

An experimental method is developed for contact resistivity measurements of a buried interface in polycrystalline silicon (poly-Si) thin-film solar cell devices on aluminum doped zinc oxide (ZnO:Al) layers. The solar cell concept comprises a glass substrate covered with a temperature-stable ZnO:Al film as transparent front contact layer, a poly-Si n⁺/p⁻/p⁺ cell, as well as a metal back contact. Glass/ZnO:Al/poly-Si/metal test stripe structures are fabricated by photolithographic techniques with the ZnO:Al stripes locally bared by laser ablation. The high-temperature treatments during poly-Si fabrication, e.g. a several hours lasting high-temperature step at 600 °C, are found to have no detrimental impact on the ZnO:Al/Si interface contact resistivity. All measured ρ_C values range well below 0.4 Ω cm² corresponding to a relative power loss ΔP below 3% for a solar cell with 500 mV open circuit voltage and 30 mA/cm² short circuit current density. By inclusion of a silicon nitride (SiN_x) diffusion barrier between ZnO:Al and poly-Si the electrical material quality of the poly-Si absorber can be significantly enhanced. Even in this case, the contact resistivity remains below 0.4 Ω cm² if the diffusion barrier has a thickness smaller than 10 nm.     

Crystallization of amorphous silicon thin film by using a thermal plasma jet

Amorphous silicon (a-Si) films deposited on glass substrates were crystallized using a thermal plasma jet and the treated films are analyzed to find the relationship between plasma characteristics and crystallization process conditions. The crystallization process conditions were found to have different optimal operating regimes depending on the nozzle geometry. Numerical analysis of the thermal plasma jets showed that the different operating regimes for crystallization were caused by modifications of the plasma characteristics by the nozzle geometry. It is revealed that a stepped-divergent nozzle is more efficient for the thermal plasma annealing process than the conventional cylindrical one due to the broadened high-temperature region and the lowered axial velocity in the plasma jet.     

Low-temperature preparation of flexible a-Si:H solar cells with hydrogenated nanocrystalline silicon p layer

In this paper we report on flexible a-Si:H solar cells prepared on polyethylene naphthalate (PEN) substrates using p-type hydrogenated nanocrystalline silicon thin films (p-nc-Si:H) as the window layer. The p-nc-Si:H films were prepared at low temperature (150 °C) using trimethylboron (TMB) as a dopant gas. The influence of the silane concentration (SC) on the electrical and structural properties of ultra-thin p-nc-Si:H as well as the performance of solar cells on PEN was investigated. The results show that the crystalline fraction and conductivity of p-nc-Si:H thin films diminished, while the deposition rate and RMS roughness of films increased, when the SC increases from 0.53% to 0.8%. For the a-Si:H solar cells on PEN with the non-textured electrodes, the best efficiency of 6.3% was achieved with the p-nc-Si:H thin films deposited at SC = 0.67%.     

Preparation of ITO thin films applied in nanocrystalline silicon solar cells

ITO thin films were prepared by changing the experimental parameters including gas flow ratio, sputtering pressure and sputtering time in DC magnetron sputtering equipment. The stable experimental parameters of Ar flow at 70 sccm, O₂ flow at 2.5 sccm ∼ 3.0 sccm, sputtering pressure around 0.5 Pa, and sputtering time of 80 s were obtained. Under these parameters, we had achieved the ITO thin films with low resistivity (<4 × 10⁻⁴ Ω ? cm) and high average transmissivity (95.48%, 350 nm ∼ 1100 nm). These ITO thin films were applied in nanocrystalline silicon solar cells as top transparent conductive layer. The solar cell test result showed that the open circuit voltage (Voc) was up to 534.9 mV and the short circuit current density (Jsc) was 21.56 mA/cm².     

Band gap profiles of intrinsic amorphous silicon germanium films and their application to amorphous silicon germanium heterojunction solar cells

Intrinsic amorphous silicon germanium (i-a-SiGe:H) films with V, U and VU shape band gap profiles for amorphous silicon germanium (a-SiGe:H) heterojunction solar cells were fabricated. The band gap profiles of i-a-SiGe:H were prepared by varying the GeH₄ and H₂ flow rates during the deposition process. The use of i-a-SiGe:H with band gap profile in an absorber layer for a-SiGe:H heterojunction solar cells was investigated. The solar cell using a VU shape band gap profile shows a higher efficiency compared to other shapes. The highest efficiency obtained for an a-SiGe:H heterojunction solar cell using the VU shape band gap profile technique was 9.4% (V_oc = 0.79 V, J_sc = 19.0 mA/cm² and FF = 0.63).