Silicon nitride/silicon oxide interlayers for solar cell passivating contacts based on PECVD amorphous silicon

This Letter demonstrates improved passivating contacts for silicon solar cells consisting of doped silicon films together with tunnelling dielectric layers. An improvement is demonstrated by replacing the commonly used silicon oxide interfacial layer with a silicon nitride/silicon oxide double interfacial layer. The paper describes the optimization of such contacts, including doping of a PECVD intrinsic a‐Si:H film by means of a thermal POCl₃ diffusion process and an exploration of the effect of the refractive index of the SiN_x. The n⁺ silicon passivating contact with SiN_x /SiO_x double layer achieves a better result than a single SiN_x or SiO_x layer, giving a recombination current parameter of ～7 fA/cm² and a contact resistivity of ～0.005 Ω cm², respectively. These self‐passivating electron‐selective contacts open the way to high efficiency silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

Effective surface passivation of crystalline silicon using ultrathin Al2O3 films and Al2O3/SiNx stacks

We measure surface recombination velocities (SRVs) below 10 cm/s on p‐type crystalline silicon wafers passivated by atomic–layer–deposited (ALD) aluminium oxide (Al₂O₃) films of thickness ≥10 nm. For films thinner than 10 nm the SRV increases with decreasing Al₂O₃ thickness. For ultrathin Al₂O₃ layers of 3.6 nm we still attain a SRV < 22 cm/s on 1.5 Ω cm p‐Si and an exceptionally low SRV of 1.8 cm/s on high‐resistivity (200 Ω cm) p‐Si. Ultrathin Al₂O₃ films are particularly relevant for the implementation into solar cells, as the deposition rate of the ALD process is extremely low compared to the frequently used plasma‐enhanced chemical vapour deposition of silicon nitride (SiN_x). Our experiments on silicon wafers passivated with stacks composed of ultrathin Al₂O₃ and SiN_x show that a substantially improved thermal stability during high‐temperature firing at 830 °C is obtained for the Al₂O₃/SiN_x stacks compared to the single‐layer Al₂O₃ passivation. Al₂O₃/SiN_x stacks are hence ideally suited for the implementation into industrial‐type silicon solar cells where the metal contacts are made by screen‐printing and high‐temperature firing of metal pastes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhanced rear‐side reflection and firing‐stable surface passivation of silicon solar cells with capping polymer films

Low refractive index polymer materials have been investigated with a view to form the back surface mirror of advanced silicon solar cells. SiO_x:H or AlO_y SiO_x:H polymer films were spun on top of an ultra‐thin (<10 nm) atomic‐layer‐deposited (ALD) Al₂O₃ layer, itself deposited on low‐resistivity (1 Ω cm) p‐type crystalline silicon wafers. These double‐layer stacks were compared to both ALD Al₂O₃ single layers and ALD Al₂O₃/plasma‐enhanced chemical vapour deposited (PECVD) SiN_x stacks, in terms of surface passivation, firing stability and rear‐side reflection. Very low surface recombination velocity (SRV) values approaching 3 cm/s were achieved with ALD Al₂O₃ layers in the 4–8 nm range. Whilst the surface passivation of the single ALD Al₂O₃ layer is maintained after a standard firing step typical of screen printing metallisation, a harsher firing regime revealed an enhanced thermal stability of the ALD Al₂O₃/SiO_x:H and ALD Al₂O₃/AlO_y SiO_x:H stacks. Using simple two‐dimensional optical modelling of rear‐side reflection it is shown that the low refractive index exhibited by SiO_x:H and AlO_y SiO_x:H results in superior optical performance as compared to PECVD SiN_x, with gains in photogenerated current of ～0.125 mA/cm² at a capping thickness of 100 nm. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface passivation of In0.83Ga0.17As photodiode with high-quality SiN layer fabricated by ICPCVD at the lower temperature

The surface passivation of low-temperature-deposited SiN_x films has been investigated in PIN type In_0.83Ga_0.17As photodiodes. In contrast to SiN_x films (330 °C) fabricated by PECVD (Plasma enhanced chemical vapor deposition), the low-temperature-deposited SiN_x films (75 °C) fabricated by ICPCVD (Inductively coupled plasma chemical vapor depositon) have a good effect on passivation of In_0.83Ga_0.17As photodiodes, which caused reductions of dark current as large as 2–3 orders of magnitude at the same test temperature 200 K. The effects of low-temperature-deposited SiN_x passivations with lowrate (∼16 nm/min) model were compared to the ones with highrate (∼100 nm/min) model. SiN_x films with lowrate model have a better effect on reducing dark current of the photodiodes. The different SiN_x films were studied by SIMS. The results show that the content of oxides in SiN_x layer fabricated by PECVD is 2 orders of magnitude more than that in SiN_x layer fabricated by ICPCVD which could be the reason that low-temperature-deposited SiN_x passivation leads to higher performance. Further, the dark current density of the photodiodes with lowrate-deposited SiN_x passivations does not show the dependence on the perimeter-to-area(P/A) of the junction.     

基于等离子体增强化学气相沉积技术的光电子器件多层抗反膜的设计和制作

针对光电子器件端面抗反镀膜的要求,研究了基于等离子体增强化学气相沉积(PECVD)技术的多层抗反膜的设计和制作.首先,对影响SiN_x折射率的因素进行了实验研究,确定了具有大折射率差的SiO₂/SiN_x材料的PECVD沉积条件.根据理论计算分析,设计了四层SiO₂/SiN_x抗反膜结构,能够在70 nm的波长范围内实现低于10^-4的反射率     

Nano‐glass frit for inkjet printed front side metallization of silicon solar cells prepared by sol–gel process

Sol–gel derived nano‐sized glass frits were incorporated into the Ag conductive ink for silicon solar cell metallization. This mixture was specifically formulated for inkjet printing on textured Si wafers with 80 nm thick SiN_x anti reflection coating layers. The correlation between the contact resistance and interface microstructures were studied using scanning electron microscopy and transmission electron microscopy. In addition, the specific contact resistance between the front contact and emitter was measured at various firing conditions using the transfer length model. On an emitter with the sheet resistance of 60 Ω/sq, a specific contact resistance below 5 mΩ cm² could be achieved at a peak firing temperature around 800 °C. We found that the incorporated nano‐glass frit act as a very effective fire through agent, and an abundant amount of Ag crystallites was observed along the interface glass layer. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

The defect density of a SiNx/In0.53Ga0.47As interface passivated using (NH4)2Sx

Passivation of the electronic defect states at a SiN_x/InGaAs interface has been achieved using (NH₄)₂S_x treatments of the InGaAs surface. The X-ray photoelectron spectroscopy technique was used to investigate the mechanism of sulfur passivation. The results indicate that sulfur treatment can effectively erase the native oxides, and S-In, S-Ga and S-As bondings are formed after sulfidation. The fabrication of Au/SiN_x/InGaAs metal–insulator–semiconductor diodes has been achieved by depositing a layer of SiN_x on (NH₄)₂S_x-treated n-InGaAs using the plasma enhanced chemical vapor deposition technique. The effect of passivation on the InGaAs surface before and after annealing was evaluated by current–voltage and capacitance–voltage measurements. The results indicate that the SiN_x passivation layer exhibits good insulative properties. The annealing contributes to the decrease of the fixed charge density and the minimum surface state density, which are 4.5×10¹¹ cm^-2 and 3.92×10¹¹ cm^-2 eV^-1, respectively. A 256×1 InP/InGaAs/InP heterojunction short-wavelength infrared detector, fabricated with the sulfidation plus a SiN_x passivation layer, has shown a good response uniformity of 4.81%. PACS 73.20.At; 73.40.Kp; 73.40.Rw; 81.40.Rs; 71.55.Eq     

Growth and characterization of silicon nitride films on various underlying materials

Characteristics of silicon nitride (SiN_x:H) films, grown by plasma enhanced chemical vapor deposition (PECVD) on various metals such as Ta, IrMn, NiFe, Cu, and CoFe at various temperatures down to 100 °C, were studied using measurements of BHF etch rate, surface roughness and Auger electron spectroscopy (AES). The results were compared with those obtained for SiN_x:H films on Si. The deposition rate of SiN_x:H films increased slightly as deposition temperature decreased, and showed a weak dependence on the underlying materials. The surface of the nitride films deposited on all underlying materials at lower temperatures (below 150 °C) became rougher. In particular, a bubble-like surface was observed on the nitride film deposited on NiFe at 100 °C. At higher deposition temperatures (above 200 °C), SiN_x:H films on all the above metals had small RMS values, except for films on Cu which cracked at 250 °C. BHF (10:1) etch rate increased dramatically for nitride films deposited below 150 °C. For different underlying films, the BHF etch rate was quite different, but exhibited the same trend with decrease in deposition temperature. AES measurements showed that Si and N concentrations in the SiN_x:H films were only slightly different for the various deposition temperatures and underlying materials. AES depth profile of nitride films indicated that both surface O content and the depth of oxygen penetrating into SiN_x:H increased for low temperature-deposited films. However, there was no observed oxygen signal from within the films, even for films deposited at 100 °C, and both Si and N concentrations were uniform throughout the film. Received: 26 October 2001 / Accepted: 2 March 2001 / Published online: 20 June 2001     

Improved resistive switching phenomena observed in SiNx‐based resistive switching memory through oxygen doping process

The improvement of resistive switching (RS) phenomena of silicon‐nitride (SiN_x)‐based resistive random access memory (ReRAM) cells through oxygen doping process was investigated. As a result, compared to un‐doped SiN_x films, the oxygen doped SiN_x (SiN_x:O₂)‐based ReRAM cells show a lower current (～0.3 μA) level at a high resistance state and a smaller variation of operating voltage through the reduction of leakage current in the SiN_x:O₂ film by combining silicon dangling bonds and doped oxygen ions. Therefore, we believe that the oxygen doping process in SiN_x films can effectively improve the RS characteristics of SiN_x‐based ReRAM cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

基于Si-rich SiNx/N-rich SiNy多层膜结构电致发光特性研究

利用等离子体增强化学气相沉积法制备了富硅氮化硅/富氮氮化硅多层膜,并以此氮化硅基多层膜作为有源层构建电致发光器件,在室温下观察到了较强的电致可见发光.在此基础上,研究多层膜结构中作为势垒层的富氮氮化硅层对器件电致发光性质的影响,实验结果表明通过改变势垒层的Si/N组分,调制其势垒高度,器件的电致发光效率可得到显著地提高. 关键词： 电致发光 多层膜 氮化硅     

Improving the gas barrier properties of a-SiOxCyNz film at low temperature using high energy and suitable nitrogen flow rate

Amorphous silicon oxycarbonitride thin films were synthesized on polyethylene terephthalate (PET) substrates at low temperatures (～80 °C) by plasma-enhanced chemical vapor deposition (PECVD). A high ion flux and suitable nitrogen flow rate improved the gas barrier properties and deposition rate of the resulting a-SiO_xC_yN_z film. The a-SiO_xC_yN_z films were deposited at a high deposition rate and low water WVTR properties as a result of the high ion flux and nitrogen chemistry. The high ion flux modified the chemical structure and nitrogen atomic composition of the resulting a-SiO_xC_yN_z film coatings. The substrate temperature was characterized using a thermometer. In addition, the coating properties were characterized by Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and the water vapor transmission rate (WVTR).     

Low‐temperature synthesis and Raman scattering of Mn‐doped ZnO nanopowders

Nanocrystalline Mn‐doped zinc oxides Zn_1−xMn_xO (x = 0–0.10) were synthesized by the sol–gel technique at low temperature. The calcination temperature of the as‐prepared powder was found at 350 °C using differential thermal analysis. A thermogravimetric analysis showed that there is a mass loss in the as‐prepared powder till 350 °C and an almost constant mass till 800 °C. The X‐ray diffraction patterns of investigated nanopowders calcined at 350 °C correspond to the hexagonal ZnO structure without any foreign impurities. The average grain size of the nanocrystal that was observed around ∼25–40 nm from transmission electron microscopy matched well with the crystallite size calculated from the line shape of X‐ray diffraction. The chemical bonding structure in Zn_1−xMn_xO nanopowders was examined using X‐ray photoelectron spectroscopy techniques, which indicate substitution of Mn²⁺ ions into Zn²⁺ sites in ZnO lattice. Micro Raman spectroscopy confirmed the insertion of Mn ions in the ZnO host matrix, and similar wurtzite structure of Zn_1−xMn_xO (x < 10%) nanocrystals. Temperature‐dependent Raman spectra of the nanocrystals displayed suppression of luminescence and enhancement in full width at half maximum in pure ZnO nanocrystals with increase in temperature, which suggests an enhancement in particle size at elevated temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Interface property of silicon nitride films grown by inductively coupled plasma chemical vapor deposition and plasma enhanced chemical vapor deposition on In0.82Al0.18As

Au/silicon nitride/In_0.82Al_0.18As metal insulating semiconductor (MIS) capacitors were fabricated and then investigated by capacitance voltage (C–V) test at variable frequencies and temperatures. Two different technologies silicon nitride (SiN_x) films deposited by inductively coupled plasma chemical vapor deposition (“ICPCVD”) and plasma enhanced chemical vapor deposition (“PECVD”) were applied to the MIS capacitors. Fixed charges (N_f), fast (D_it) and slow (N_si) interface states were calculated and analyzed for the different films deposition MIS capacitors. The D_it was calculated to be 4.16 × 10¹³ cm⁻² eV⁻¹ for “ICPCVD” SiN_x MIS capacitors, which was almost the same to that of “PECVD” SiN_x MIS capacitors. The D_it value is obviously higher for the extended wavelength In_xGa_1−xAs (x > 0.53) epitaxial material as a result of lattice mismatch with substrate. Compared to the results of “PECVD” SiN_x MIS capacitors, the N_si was significantly lower and the N_f was slightly lower for “ICPCVD” SiN_x MIS capacitors. X-ray photoelectron spectroscopy (XPS) analysis shows good quality of the “ICPCVD” grown SiN_x. The low temperature deposited SiN_x films grown by “ICPCVD” show better effect on decreasing the dark current of In_xGa_1−xAs photodiodes.     

Permeation barrier properties of an Al2O3/ZrO2 multilayer deposited by remote plasma atomic layer deposition

We report the permeation barrier properties of Al₂O₃/ZrO₂ multi-layers deposited by remote plasma atomic layer deposition. Electrical Ca degradation tests were performed to derive the water vapor transmission rate (WVTR) of Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers at 50 °C and 50% relative humidity (RH). Al₂O₃/ZrO₂ multi-layers exhibit better barrier properties than Al₂O₃ and ZrO₂ layers, and when more individual layers were deposited in the same total thickness, the WVTR value was reduced further, indicating a better barrier property. The WVTR of the Al₂O₃ and ZrO₂ layers were 9.5 × 10⁻³ and 1.6 × 10⁻² g/m² day, respectively, but when deposited alternatively with 1 cycle of each layer, the WVTR decreased to 9.9 × 10⁻⁴ g/m² day. X-ray diffraction results indicated that ZrO₂ has a monoclinic structure but Al₂O₃ and Al₂O₃/ZrO₂ multi-layers show an amorphous structure. Cross sectional Al₂O₃/ZrO₂ multi-layer structures and the formation of a ZrAl_xO_y phase are observed by transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) results indicate that Al₂O₃ and ZrO₂ contain 33.7% and 37.8%, respectively, Al–OH and Zr–OH bonding. However, the ZrAl_xO_y phase contained 30.5% Al–OH and Zr–OH bonding. The results of transmittance measurement indicate that overall, Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers show high transmittance greater than 80% in the visible region.     

Structural evolution of SiNx films deposited by ECR and its light emission

Structural and optical properties of a-SiN_x films deposited by electron cyclotron resonance chemical vapor deposition (ECRCVD) have been investigated. The Fourier transform infrared (FTIR) spectroscopy shows the structural evolution of the SiN_x films, which are defined as Si-rich SiN_x and N-rich SiN_x films, also confirmed by Raman spectroscopy. The origin of the light emission for SiN_x films may be attributed to two mechanisms, i.e., quantum confinement effect (QCE) and transition of defect energy levels. The correlation between light emission and structures of SiN_x films is discussed.     

沉积参数对SiNx薄膜结构及阻透性能的影响

利用直流脉冲磁控溅射法在室温下制备无氢SiN_x薄膜.通过傅里叶变换红外光谱、台阶仪、紫外—可见分光光度计、接触角测量仪、透湿测试仪等表征技术,分析了N₂流量、Si靶溅射功率等实验参数对SiN_x薄膜成分、结构、及阻透性能、透光性能、接触角等性能的影响.研究结果表明,Si靶溅射功率固定时,在低N₂流量条件下,或N₂流量固定时,在高Si靶溅射功率条件下,制备的SiN _{关键词： x}')" href="#">SiN_x 磁控溅射 微观结构 阻透性能     

Si-rich SiNx rear passivated c-Si solar cell with a novel antimony Local Back Surface Field formed by Laser Fired Contact

Local Back Contact (LBC) crystalline silicon solar cell with novel antimony (Sb) Local Back Surface Field (LBSF) are reported. The Sb LBSF is formed at low temperature with a Laser Fired Contacts (LFC) process. To improve the solar cell parameters of Sb LBSF, the rear passivation layer with SiN_x is optimized by varying the refractive index. The Si-rich SiN_x with a refractive index (n) of 2.7 possesses high lifetime of 2 ms with reduced absorption at a longer wavelength. The increase in lifetime is analyzed with Si–H bond concentration by FTIR. A 100 nm thick Sb layer with low laser power of 44 mW resulted in a junction depth of 500 nm with a carrier concentration of 5 × 10²⁰ cm^?3. The improved rear passivation with Si-rich SiN_x, the optimized Sb thickness yielded the best electrical results, with open circuit voltage (V_oc) of 643 mV and efficiency of 19.25%, compared to the reference cell with V_oc of 625 mV and efficiency of 18.20%.     

Chemical bonding and interface analysis of ultrathin silicon-nitride layers produced by ion implantation and Electron Beam Rapid Thermal Annealing (EB-RTA)

¹⁵N ₂ ⁺ ions were implanted into c-Si with an energy of 5 keV/atom and fluences ranging from 5×10¹⁶ to 2×10¹⁷ atoms/cm² at RT to form ultrathin silicon-nitride layers (SiN _x ) with different N/Si ratios depending on the fluences (up to an overstoichiometric N/Si ratio of 1.65). The ¹⁵N depth distributions were analysed by the resonant nuclear reaction ¹⁵N(p, )¹²C(E _res=429 keV). The implanted samples were processed by Electron Beam Rapid Thermal Annealing (EB-RTA) at 1150° C for 15 s (ramping up and down 5° C/s). The chemical structure of the ¹⁵N implantation into Si was investigated by EXAFS and NEXAFS. Channeling-RBS (⁴He⁺, E ₀=1.5 MeV) measurements were performed to observe the transition region (disordered-Si layer, d-Si) being underneath of the SiN _x layer (typical values of layer thicknesses:SiN _x 24 nm, d-Si 6 nm).     

Si/Si<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>: Er/Si(100) heterostructures grown by sublimation of silicon in germane gas atmosphere

High-quality Si_{1 ? x} Ge _x :Er epitaxial layers have been grown on Si(100) substrates at a relatively low temperature (500°C) by sublimation of silicon in GeH₄ gas atmosphere. It has been established using capacitance-voltage measurements, X-ray diffraction, and secondary-ion mass spectrometry that the spread in the deposited layer thickness in the central part of the substrate (40 × 10 mm² in size) is 5%. High homogeneity of layer doping is obtained within the same area.