Optimization of the Surface Structure on Black Silicon for Surface Passivation
© The Author(s). 2017
Received: 28 November 2016
Accepted: 9 February 2017
Published: 16 March 2017
Black silicon shows excellent anti-reflection and thus is extremely useful for photovoltaic applications. However, its high surface recombination velocity limits the efficiency of solar cells. In this paper, the effective minority carrier lifetime of black silicon is improved by optimizing metal-catalyzed chemical etching (MCCE) method, using an Al2O3 thin film deposited by atomic layer deposition (ALD) as a passivation layer. Using the spray method to eliminate the impact on the rear side, single-side black silicon was obtained on n-type solar grade silicon wafers. Post-etch treatment with NH4OH/H2O2/H2O mixed solution not only smoothes the surface but also increases the effective minority lifetime from 161 μs of as-prepared wafer to 333 μs after cleaning. Moreover, adding illumination during the etching process results in an improvement in both the numerical value and the uniformity of the effective minority carrier lifetime.
Black silicon (b-Si), also called nanostructured surface silicon, shows much lower light reflection losses than conventional random pyramids  and thus is an extremely promising material for photovoltaic applications . Up to now, there are three kinds of way to fabricate b-Si: laser texturing , reactive ion etching (RIE) , and metal-catalyzed chemical etching (MCCE) . Among these, RIE and MCCE techniques have obtained high expectations. However, from the point of view of industry matching and cost-effectiveness, MCCE method is much more suitable for large-scale production, since the conventional texturing process is also based on wet chemical etching .
Ye et al. reported a novel nanoscale pseudo-pyramid texture formed by a MCCE technique and an additional NaOH solution treatment : step 1, wafers were dipped into AgNO3/HF mixed solution to grow Ag nanoparticles on surface; step 2, wafers were steeped in the HF/H2O2 mixed solution to do the MCCE process; step 3, wafers were immersed in dense HNO3 to remove Ag ions; and step 4, a NaOH solution treatment to reduce the surface area and convert the microporous layer into a nanoscale pseudo-pyramid texture. This method has been proven as an efficient way to obtain high-efficiency black multi-crystalline (mc) silicon solar cells. Nevertheless, there still is a room for optimization.
Firstly, etching process increases the surface recombination, so it is necessary that only the front side of the wafer is etched while the rear side gets protected. Normally, the rear side can be protected by a mask before step 1 and the mask will be washed off after step 4 . However, the preparation of the mask increases the process steps. Therefore, in our experiments, the spray method was used to deposit the AgNO3/HF mixed solution onto the wafer surface. Since the spray method is applied to only one side of the sample, no preparation of the mask is necessary. Secondly, NaOH solution used in step 4 needs to be washed with HCl solution to remove Na+. If NH4OH/H2O2/H2O in the standard RCA cleaning is used, not only the alkaline treatment can be achieved but also the cleaning step can be omitted. Thirdly, in order to improve the reaction rate and the uniformity of the etching process, it is possible to refer to the photo-induced plating (LIP) technique by adding illumination during the etching process . In the absence of illumination, because of the electrochemical potential of the oxidant (H2O2) being much more positive than the valence band of Si, silver ions act as a catalyst to rapidly reduce H2O2 and produce copious number of holes injected into the valence band of Si . If a certain amount of illumination is provided, the number of photo-generated holes can be comparable with or higher than the holes obtained by reducing H2O2, thus accelerating the etching rate .
In order to improve the efficiency of solar cells, b-Si needs excellent surface passivation . Although a wide variety of films can be selected, such as SiNx  and SiO2 , the Al2O3 thin film deposited by atomic layer deposition (ALD) is the best choice for passivating b-Si . On the one hand, ALD, which has a conformal growth on surface with high aspect ratio features  and pinhole-free nature , is the natural choice for the coating of nanostructured surfaces. On the other hand, Al2O3 is a suitable surface passivation material for silicon-based photovoltaic applications . Al2O3 layer not only enables excellent chemical passivation due to strong coordination of Si and O  and selective hydrogenation leading to a low interface state density after annealing , but also, it provides a strong field effect passivation through a high concentration of fixed negative charges  that leads to repulsion of charge carriers from the entire surface .
After the post-etch treatments, samples were sequentially washed with H2SO4/H2O2 mixed solution (H2SO4:H2O2 = 4:1 vol) at 80 °C for 10 min, DI water rinse and HF-dip (1 vol%) at room temperature for 60 s. Al2O3 thin film was deposited on both sides of wafers by plasma-enhanced atomic layer deposition (PE-ALD) at 200 °C. Trimethylaluminium (TMA, Al2(CH3)6) was chosen as aluminum source and plasma oxygen as the oxidant. Polished samples (without b-Si) were also processed as references. The thickness of the thin film was about 10 nm, measured by ellipsometry on polished wafers. The passivation was activated by post-annealing at the temperature of 450 °C for 10 min in ambient air.
Results and Discussions
Effect of the Etch Solution
The AM1.5G-weighted reflectance of samples etched by solutions A and B with different post-etch treatments, using polished wafer as a reference
Weighted reflectance (%)
A 10 min
B 5 min
B 10 min
NaOH (0.05 wt%)
NH4OH:H2O2:H2O = 0.5:1:5
For as-prepared samples, the volume ratio of HF/H2O2 in etch solutions A and B did not significantly affect the weighted reflectance at the same etching time. In etching for 10 min, samples show weighted reflectance of 8.4 and 8.6%, respectively, which are basically the same. Compared with the sample etched for less time, the value of the weighted reflectance decreases as the etching time increases.
However, samples etched by different solution shows different performance after the post-etch treatment, taking samples with an etching time of 10 min as example. In post-etch treated by NaOH mixed solution, all samples show an increasing weighted reflectance, but samples etched by solution A increase more. In post-etch treated by NH4OH/H2O2/H2O mixed solution, sample etched by solution A still shows an increasing of weighted reflectance. However, the weighted reflectance of sample etched by solution B decreased after NH4OH/H2O2/H2O post-etching treatment and, finally, obtained the minimum value of weighted reflectance of 6%. This value is evidently better than the ones obtained in industrial alkaline-textured single crystalline silicon wafers or even the inverted pyramids of 15% without antireflection coating .
Effect of the NH4OH Content in Post-etch Treatment
An NH4OH/H2O2/H2O mixed solution having three different levels of volume ratio was used, in which NH4OH content was adjusted in 0.2:1:5, 0.5:1:5, and 1:1:5. During the preparation of these samples, the Ag+ concentration in the AgNO3/HF mixed solution was increased in order to strengthen the degree of etching to further reduce the reflectance. The weighted reflectance of as-prepared sample decreased from 8.4% of the original AgNO3/HF mixed solution to 6.8% of the new.
Post-etch treatment smoothes the surface, and increasing NH4OH content in mixed solution will enhance the smoothness. Technically, this process will usually lead to increased reflectance. But because of the deep structure of nanowires, the effect of increasing NH4OH content on the reflectance is not obvious. However, increasing NH4OH content can greatly improve the effective minority carrier lifetime. This means increasing the NH4OH content in mixed solution can improve the electrical properties of b-Si without sacrificing the optical properties.
Effect of the Illumination in Etching Process
In order to further improve the reaction rate of the etching process, bulb illumination was added on the basis of indoor lighting during MCCE process in the HF/H2O2 mixed solution. According to the etching principle of MCCE method, the number of holes injected into the valence band of Si has a great influence on the etching rate. In indoor lighting conditions, because the intensity of illumination is low, so the etching rate depends on the concentration of silver ions acting as a catalyst and H2O2 acting as an oxidant . However, adding a bulb illumination on the basis of indoor lighting, because the intensity of illumination is high enough to obtain a sufficient number of minority carriers, so the etching rate is accelerated by photo-generated carriers.
Black silicon was fabricated on n-type solar grade silicon wafers using an optimized MCCE method and passivated using an ALD-deposited Al2O3 thin film, post-annealed. Spray method for the deposition of silver ions results in a single-side etching without using masks. After post-etch treatment, b-Si exhibits a low reflectance of 6–10%. The use of NH4OH/H2O2/H2O in place of NaOH as post-etch treatment to smooth the surface not only achieves higher effective minority carrier lifetime of 333 μs but also eliminates the need for the Na+ removal step. At the same time, increasing the NH4OH content in the post-etch solution can improve the effective minority carrier lifetime without significantly increasing the reflectance. Also, an effective surface recombination velocity of 38 cm/s is achieved on sample post-etch treated by NH4OH/H2O2/H2O (volume ratio 1.0:1:5) mixed solution, while the value of polished reference is 22 cm/s. Moreover, by adding illumination during the etching process, the etching rate can be increased, and a finer uniform surface can be obtained, resulting in an improvement in both the numerical value and the uniformity of the effective minority carrier lifetime.
The project was supported by the National High Technology Research and Development Program of China (Grant No. 2015AA050302).
XJ performed the sample characterization, analyzed the results, and wrote the manuscript. CZ carried out the sample preparation and helped in drafting the manuscript. WW participated in the discussion of experimental results and coordination. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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