Plasma hydrogenated,reactively sputtered aluminium oxide for silicon surface passivation

The intentional addition of hydrogen during reactive sputtering of AlO_x films has led to a dramatic improvement of the surface passivation of crystalline silicon wafers achieved with this technique. The 5 ms effective minority carrier lifetime measured on 1.5 Ω cm n‐type CZ silicon wafers is close to the 6 ms of a control wafer coated by atomic layer deposition (ALD) of AlO_x. Hydrogen‐sputtered films also provide excellent passivation of 1 Ω cm p‐type silicon, as demonstrated by an effective lifetime of 1.1 ms. It is likely that the improved passivation is related to the formation of an interfacial silicon oxide layer, as indicated by FTIR measurements. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Contact passivation in silicon solar cells using atomic‐layer‐deposited aluminum oxide layers

Atomic‐layer‐deposited aluminum oxide (AlO_x) layers are implemented between the phosphorous‐diffused n⁺‐emitter and the Al contact of passivated emitter and rear silicon solar cells. The increase in open‐circuit voltage V_oc of 12 mV for solar cells with the Al/AlO_x/n⁺‐Si tunnel contact compared to contacts without AlO_x layer indicates contact passivation by the implemented AlO_x. For the optimal AlO_x layer thickness of 0.24 nm we achieve an independently confirmed energy conversion efficiency of 21.7% and a V_oc of 673 mV. For AlO_x thicknesses larger than 0.24 nm the tunnel probability decreases, resulting in a larger series resistance. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystalline silicon surface passivation investigated by thermal atomic-layer-deposited aluminum oxide

Atomic-layer-deposited(ALD) aluminum oxide(Al_2O_3) has demonstrated an excellent surface passivation for crystalline silicon(c-Si) surfaces, as well as for highly boron-doped c-Si surfaces. In this paper, water-based thermal atomic layer deposition of Al_2O_3 films are fabricated for c-Si surface passivation. The influence of deposition conditions on the passivation quality is investigated. The results show that the excellent passivation on n-type c-Si can be achieved at a low thermal budget of 250℃ given a gas pressure of 0.15 Torr. The thickness-dependence of surface passivation indicates that the effective minority carrier lifetime increases drastically when the thickness of Al_2O_3 is larger than 10 nm. The influence of thermal post annealing treatments is also studied. Comparable carrier lifetime is achieved when Al_2O_3 sample is annealed for 15 min in forming gas in a temperature range from 400℃ to 450℃. In addition, the passivation quality can be further improved when a thin PECVD-SiN_x cap layer is prepared on Al_2O_3, and an effective minority carrier lifetime of2.8 ms and implied Voc of 721 mV are obtained. In addition, several novel methods are proposed to restrain blistering.     

Plasma enhanced atomic layer deposition of gallium oxide on crystalline silicon: demonstration of surface passivation and negative interfacial charge

Herein we report on the passivation of crystalline silicon by gallium oxide (Ga₂O₃) using oxygen plasma as the oxidizing reactant in an atomic layer deposition (ALD) process. Excess carrier lifetimes of 2.1 ms have been measured on 1.75 Ω cm p‐type silicon, from which a surface recombination current density J₀ of 7 fA cm^–2 is extracted. From high frequency capacitance‐voltage (HF CV) measurements it is shown that, as in the case of Al₂O₃, the presence of a high negative charge density Q_tot/q of up to –6.2 × 10¹² cm^–2 is one factor contributing to the passivation of silicon by Ga₂O₃. Defect densities at midgap on the order of ～5 × 10¹¹ eV^–1 cm^–2 are extracted from the HF CV data on samples annealed at 300 °C for 30 minutes in a H₂/Ar ambient, representing an order of magnitude reduction in the defect density compared to pre‐anneal data. Passivation of a boron‐diffused p⁺ surface (96 Ω/□) is also demonstrated, resulting in a J₀ of 52 fA cm^–2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Surface passivation of crystalline silicon by sputter deposited hydrogenated amorphous silicon

This letter shows that intrinsic hydrogenated amorphous silicon (a‐Si:H) films deposited by RF magnetron sputtering can provide outstanding passivation of crystalline silicon surfaces, similar to that achieved by plasma enhanced chemical vapour deposition (PECVD). By using a 2% hydrogen and 98% argon gas mixture as the plasma source, 1.5 Ω cm n‐type FZ silicon wafers coated with sputtered a‐Si:H films achieved an effective lifetime of 3.5 ms, comparable to the 3 ms achieved by PECVD (RF and microwave dual‐mode). This is despite the fact that Fourier transform infrared spectroscopy measurements show that sputtering and PECVD deposited films have very different chemical bonding configurations. We have found that film thickness and deposition temperature have a significant impact on the passivation results. Self‐annealing and hydrogen plasma treatment during deposition are likely driving forces for the observed changes in surface passivation. These experimental results open the way for the application of sputtered a‐Si:H to silicon heterojunction solar cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydrogen passivation of multi—crystalline silicon solar cells

The effects of hydrogen passivation on multi-crystalline silicon (mc-Si) solar cells are reported in this paper. Hydrogen plasma was generated by means of ac glow discharge in a hydrogen atmosphere. Hydrogen passivation was carried out with three different groups of mc-Si solar cells after finishing contacts. The experimental results demonstrated that the photovoltaic performances of the solar cell samples have been improved after hydrogen plasma treatment, with a relative increase in conversion efficiency up to 10.6\%. A calculation modelling has been performed to interpret the experimental results using the model for analysis of microelectronic and photonic structures developed at Pennsylvania State University.     

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 in n-type silicon and its application in silicon drift detector

Based on the surface passivation of n-type silicon in a silicon drift detector(SDD), we propose a new passivation structure of SiO2/Al2O3/SiO2 passivation stacks. Since the SiO2 formed by the nitric-acid-oxidation-of-silicon(NAOS)method has good compactness and simple process, the first layer film is formed by the NAOS method. The Al2O3 film is also introduced into the passivation stacks owing to exceptional advantages such as good interface characteristic and simple process. In addition, for requirements of thickness and deposition temperature, the third layer of the SiO2 film is deposited by plasma enhanced chemical vapor deposition(PECVD). The deposition of the SiO2 film by PECVD is a low-temperature process and has a high deposition rate, which causes little damage to the device and makes the SiO2 film very suitable for serving as the third passivation layer. The passivation approach of stacks can saturate dangling bonds at the interface between stacks and the silicon substrate, and provide positive charge to optimize the field passivation of the n-type substrate.The passivation method ultimately achieves a good combination of chemical and field passivations. Experimental results show that with the passivation structure of SiO2/Al2O3/SiO2, the final minority carrier lifetime reaches 5223 μs at injection of 5×10¹⁵ cm^-3. When it is applied to the passivation of SDD, the leakage current is reduced to the order of nA.     

Effect of rapid thermal oxidation on structure and photoelectronic properties of silicon oxide in monocrystalline silicon solar cells

This paper concerns the topic of surface passivation properties of rapid thermal oxidation on p-type monocrystalline silicon wafer for use in screen-printed silicon solar cells. It shows that inline thermal oxidation is a very promising alternative to the use of conventional batch type quartz tube furnaces for the surface passivation of industrial phosphorus-diffused emitters. Five minutes was the most favorable holding time for the rapid thermal oxidation growth of the solar cell sample, in which the average carrier lifetime was increased 19.4 μs. The Fourier transform infrared spectrum of the rapid thermal oxidation sample, whose structure was Al/Al-BSF/p-type Si/n-type SiP/SiO₂/SiN_x/Ag solar cell with an active area of 15.6 cm², contained an absorption peak at 1085 cm⁻¹, which was associated with the Si–O bonds in silicon oxide. The lowest average reflectance of this sample is 0.87%. Furthermore, for this sample, its average of internal quantum efficiency and conversion efficiency are respectively increased by 8% and 0.23%, compared with the sample without rapid thermal oxidation processing.     

Ultra high amorphous silicon passivation quality of crystalline silicon surface using in‐situ post‐deposition treatments

A parametric study of post‐deposition hydrogen plasma treatment of intrinsic a:Si:H films is performed. We demonstrate a significant improvement in passivation of c‐Si(100) promoting epitaxy after an in‐situ hydrogen plasma treatment depending mainly on the pressure and slightly on the power. Plasma diagnostic indicates an increase of H_α* signal with high power and low pressure. However, our analysis reveals a better hydrogen incorporation with high pressure and a slight increase in monohydride with high power. Longer H₂ plasma duration up to 50 s shows no detrimental effect on the passivation quality. Optimizing the in‐situ H₂ plasma treatment, high minority carrier lifetime over 15 ms was achieved after short thermal annealing. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Excellent Si surface passivation by low temperature SiO2 using an ultrathin Al2O3 capping film

It is demonstrated that the application of an ultrathin aluminum oxide (Al₂O₃) capping film can improve the level of silicon surface passivation obtained by low‐temperature synthesized SiO₂ profoundly. For such stacks, a very high level of surface passivation was achieved after annealing, with S_eff < 2 cm/s for 3.5 Ω cm n‐type c‐Si. This can be attributed primarily to a low interface defect density (D_it < 10¹¹ eV^–1 cm^–2). Consequently, the Al₂O₃ capping layer induced a high level of chemical passivation at the Si/SiO₂ interface. Moreover, the stacks showed an exceptional stability during high‐temperature firing processes and therefore provide a low temperature (≤400 °C) alternative to thermally‐grown SiO₂. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of hydrogenated AlN as an anti‐reflective coating and for the effective surface passivation of silicon

Stacks of aluminum oxide and silicon nitride are frequently used in silicon photovoltaics. In this Letter, we demonstrate that hydrogenated aluminum nitride can be an alternative to this dual‐layer stack. Deposited on 1 Ω cm p‐type FZ silicon, very low effective surface recombination velocities of 8 cm/s could be reached after firing at 820 °C. This excellent passivation is traced back to a high density of fixed charges at the interface of approximately –1 × 10¹² cm^–2 and a very low interface defect density below 5 × 10¹⁰ eV^–1 cm^–2. Furthermore, spectral ellipsometry measurements reveal that these aluminum nitride layers have ideal optical properties for use as anti‐reflective coatings. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

后退火增强氢化非晶硅钝化效果的研究

在本征氢化非晶硅(a-Si:H(i))/晶体硅(c-Si)/a-Si:H(i)异质结构上溅射ITO时, 发现后退火可大幅增加ITO/a-Si:H(i)/c-Si/a-Si:H(i)的少子寿命(从1.7 ms到4 ms). 这一增强效应可能的三个原因是: ITO/a-Si:H(i)界面场效应作用、退火形成的表面反应层影响以及退火对a-Si:H(i)材料本身的优化, 但本文研究结果表明少子寿命增强效应与ITO和表面反应层无关; 对不同沉积温度制备的a-Si:H(i)/c-Si/a-Si:H(i)异质结后退火的研究表明: 较低的沉积温度(<175 ℃)后退火增强效应显著, 而较高的沉积温度(>200 ℃)后退火增强效应不明显, 可以确定“低温长高温后退火”是获得高质量钝化效果的一种有效方式; 采用傅里叶红外吸收谱(FTIR)研究不同沉积温度退火前后a-Si:H(i)材料本身的化学键构造, 发现退火后异质结少子寿命大幅提升是由于a-Si:H(i)材料本身的结构优化造成的, 其深层次的本质是通过材料的生长温度和退火温度的优化匹配来控制包括H含量、H键合情况以及Si原子无序性程度等微观因素主导作用的一种竞争性平衡, 对这一平衡点的最佳控制是少子寿命大幅提升的本质原因.     

Stacked and nanolaminated Al2O3/TiO2 for surface passivation and encapsulation of silicon

Silicon solar cells passivated with Al₂O₃ require a capping layer that protects the passivation layer from humidity because of sensitivity of Al₂O₃ to moisture. Al₂O₃/TiO₂ stacks obtained by atomic layer deposition have been known to provide a high level of passivation layers because of their excellent field‐effect passivation. In this work, degradation of this Al₂O₃/TiO₂ stack, when exposed to humidity, is examined, and an attempt is made for a humidity‐resistant encapsulation layer by adding Al₂O₃/TiO₂ nanolaminates that can be deposited in‐situ without breaking vacuum. Placing the nanolaminate on top of the TiO₂ and Al₂O₃ stack is found to lead to almost no degradation even after 10 days of humidity exposure. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of PECVD SiN_x/SiO_yN_x–Si interface property on surface passivation of silicon wafer

It is studied in this paper that the electrical characteristics of the interface between Si O_y N_x/Si N_x stack and silicon wafer affect silicon surface passivation. The effects of precursor flow ratio and deposition temperature of the Si O_y N_x layer on interface parameters, such as interface state density Ditand fixed charge Qf, and the surface passivation quality of silicon are observed. Capacitance–voltage measurements reveal that inserting a thin Si O_y N_x layer between the Si N_x and the silicon wafer can suppress Qfin the film and Ditat the interface. The positive Qfand Ditand a high surface recombination velocity in stacks are observed to increase with the introduced oxygen and minimal hydrogen in the Si O_y N_x film increasing. Prepared by deposition at a low temperature and a low ratio of N_2O/Si H_4 flow rate, the Si O_y N_x/Si N_x stacks result in a low effective surface recombination velocity(Seff) of 6 cm/s on a p-type 1 ?·cm~(–5) ?·cm FZ silicon wafer.The positive relationship between Seffand Ditsuggests that the saturation of the interface defect is the main passivation mechanism although the field-effect passivation provided by the fixed charges also make a contribution to it.     

Silicon heterojunction solar cell with amorphous silicon oxide buffer and microcrystalline silicon oxide contact layers

This Letter reports on the fabrication and characterization of silicon heterojunction solar cells with silicon oxide based buffer (intrinsic amorphous silicon oxide) and contact layers (doped microcrystalline silicon oxide) on flat p‐type wafers. The critical dependency of the cell performance on the front and rear buffer layer thickness reveals a trade‐off between the open circuit voltage V_oc and the fill factor FF. At the optimum, the highest efficiency of 18.5% (active area = 0.67 cm²) was achieved with V_oc = 664 mV, short circuit current J_sc = 35.7 mA/cm² and FF = 78.0%. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effective surface passivation of crystalline silicon by rf sputtered aluminum oxide

In recent years, excellent surface passivation has been achieved on both p‐type and n‐type surfaces of silicon wafers and solar cells using aluminum oxide deposited by plasma‐assisted atomic layer deposition. However, alternative deposition methods may offer practical advantages for large‐scale manufacturing of solar cells. In this letter we show that radio‐frequency magnetron sputtering is capable of depositing negatively‐charged aluminum oxide and achieving good surface passivation both on p‐type and n‐type silicon wafers. We thus establish that sputtered aluminum oxide is a very promising method for the surface passivation of high efficiency solar cells. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of temperature-pressure treatment on heavily hydrogenated silicon surface

Microstructure and related properties of hydrogenated silicon samples, Si:H, treated at high-temperature (HT) up to 1270 K under hydrostatic argon pressure (HP) up to 1.1 GPa are investigated. To prepare Si:H, Czochralski grown 0 0 1 oriented single crystalline Si wafer with 50 nm thick surface SiO₂ layer was heavily implanted with hydrogen using the immersion plasma source of hydrogen ions with energy 24 keV.The surface of HT-HP treated Si:H was characterised by scanning electron microscopy. Reflectivity pattern measurements in the wavelength range of 350-2000 nm have been performed to analyse their surface and bulk properties. The volume averaging method for a model of layer-like structure has been used to simulate the HT-HP treated Si:H. The analysis of Si:H samples suggests the multi-layer structure composed of Si, Si:H, SiO, SiO₂, and of porous Si layers in the sub-surface region. The porous Si:H samples model is in good consistency with experimental data from reflectance measurements.     

Excellent passivation of thin silicon wafers by HF‐free hydrogen plasma etching using an industrial ICPECVD tool

In this work, hydrogen plasma etching of surface oxides was successfully accomplished on thin (～100 µm) planar n‐type Czochralski silicon wafers prior to intrinsic hydrogenated amorphous silicon [a‐Si:H(i)] deposition for heterojunction solar cells, using an industrial inductively coupled plasma‐enhanced chemical vapour deposition (ICPECVD) platform. The plasma etching process is intended as a dry alternative to the conventional wet‐chemical hydrofluoric acid (HF) dip for solar cell processing. After symmetrical deposition of an a‐Si:H(i) passivation layer, high effective carrier lifetimes of up to 3.7 ms are obtained, which are equivalent to effective surface recombination velocities of 1.3 cm s^–1 and an implied open‐circuit voltage (V_oc) of 741 mV. The passivation quality is excellent and comparable to other high quality a‐Si:H(i) passivation. High‐resolution transmission electron microscopy shows evidence of plasma‐silicon interactions and a sub‐nanometre interfacial layer. Using electron energy‐loss spectroscopy, this layer is further investigated and confirmed to be hydrogenated suboxide layers. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)