Pore formation in p-type silicon in solutions containing different types of alcohol
© Urata et al.; licensee Springer. 2012
Received: 30 April 2012
Accepted: 5 June 2012
Published: 21 June 2012
Macroporous structure of silicon can be obtained with anodization in hydrogen fluoride (HF) solution. The macropore formation in the presence of alcohol was studied. Macroporous layer formation in a low-concentration HF solution is stabilized with the increasing number of carbon in alcohol. The dissolution at the topmost part of the porous layer is observed though the behavior depends upon the type of alcohol. Meanwhile, the total mass loss of dissolved silicon is almost constant. Such dissolution at the top surface occurs only when the concentration of HF is low. Adding organic solvents to the HF solution also leads to the suppression of the pore wall dissolution. The type of alcohol and HF concentration in solution affect the formation of porous silicon.
Anodization of silicon in hydrogen fluoride (HF) solution below the critical current density produces a porous silicon layer. The size and shape of the pores are dependent on wafer resistivity, current density, and solution composition. According to the pore diameter, pores are mainly classified into three groups, micropores (<2 nm), mesopores (2–50 nm), or macropores (>50 nm). The macroporous structure in n-type silicon substrate was, for the first time, discovered using aqueous HF solution by Theunissen in 1972 . However, it was in 1994 that Propst and Kohl observed first macropores in p-type silicon . They used anhydrous HF solution with acetonitrile (MeCN) as electrolyte for this macropore formation. Later, further studies regarding macropores in p-type silicon were performed either in aqueous HF  or HF mixed with organic solvents .
HF solutions mixed with various organic solvents have become a widely used solution for the pore formation. For example, some organic solvents such as MeCN or dimethylformamide (DMF) facilitate macropore formation in p-type silicon. The effect of organic solvents has been discussed from various points of view over the years. Though Lehmann and Rönnebeck reported that the presence of an organic solvent in the electrolyte is not essential for macropore formation , it is generally accepted that organic solvents essentially suppress the electrochemical oxidation of silicon in comparison to an aqueous electrolyte . The formation of macropore with MeCN is different from that with DMF and dimethyl sulfoxide . Actually, it has been shown that some organic solvents can act as a mild oxidizing reactant for silicon .
For micro or mesoporous silicon formation, an electrolyte usually contains alcohol as a solvent. The effect of the presence of alcohol has been considered that it helps to reduce the surface tension or to keep away from coverage of H2 bubbles on the porous layer, but alcohol does not react with silicon directly. Alcohol also became to be used for macropore formation. But the effects of alcohol upon the pore formation have attracted little attention. In the present work, the effects of the presence of alcohol on porous layer formation in p-type silicon are studied.
Single crystalline silicon wafers oriented to (100), used in this study, were p-type boron-doped with a resistivity of 10–20 Ωcm, and they were prepatterned. Etch pits orthogonally aligned at an 8 μm interval were created on the silicon wafer by standard photolithographic patterning and subject to subsequent alkaline etching in a 25 wt.% tetramethylammonium hydroxide aqueous solution for 5 min at 358 K. All wafers were rinsed in acetone and ultra pure water, and afterward dipped in 5 wt.% HF aqueous solution to remove the native oxide layer.
Electrochemical anodization was performed galvanostatically in a cell made of trifluoroethylene resin using a two-electrode setup with a platinum rod serving as the counter electrode. The ohmic contact was achieved by painting Ga-In alloy on the backside of the wafer with a copper current collector. The exposed surface area of the silicon electrode was 0.2 cm2. Anodization was carried out at 14 mA cm−2. Duration of the anodization was 1 h in all cases. The solution was a mixture of aqueous HF solution (47 wt.%), ultra pure water, and the following alcohols with a composition of 5:6:29 (ca. 8 wt.% HF) or 22:6:12 (ca. 30 wt.% HF) in volume: methanol (MeOH), ethanol (EtOH), 2-propanol (PrOH), and t-butanol (BuOH). In some experiments diethyl ether (Et2O), which has a much low polarity, was added. This solution contained 47 wt.% HF aqueous solution, ultra pure water, alcohol, and Et2O with a composition of 5:6:15:14 in volume, meaning that the concentration of HF was kept at a constant value.
The porous structures were observed using a field emission type scanning electron microscope (SEM, JSM-6500 F, JEOL Ltd., Tokyo, Japan). The profile of the surface was determined by a line scan using a pin-type profilometer (P-12, KLA-Tencor Corporation, Milpitas, CA, USA). The scan speed of 200 μm s−1, scan length of 12 mm, and stylus force of 10 mg were the main parameters for the scanning. SEM observations were also performed for the determination of the surface topography.
with MSi being the atomic mass of silicon, Q the electrochemical charge, and F the Faraday constant.
Results and discussion
Mass loss of silicon during anodization
Mass loss of silicon/mg
As the number of carbon in alcohol increases, stable macropore formation is achieved when silicon is anodized in low-concentration HF solution. Macropores formed with alcohol become stable against the surface dissolution, as the carbon chain becomes longer in alcohol. Though the dissolution of the top surface appears in ca. 8 wt.% HF solution with alcohol, this dissolution is not observed on the sample anodized in ca. 30 wt.% solution with alcohol. These results indicate that the top surface dissolves only in the low concentration of HF. Silicon can be dissolved via oxide when the low-concentration HF solution is used . Also, some organic solvents can oxidize silicon . The top surface may dissolve via oxide during formation of porous layer.
When Et2O is added to the HF solutions with alcohol, stable macroporous layers are obtained even with MeOH, though macropores are not formed in MeOH solution without Et2O. As discussed above, macropore growth becomes stable with the increasing number of carbon atoms in alcohol. In addition, Et2O also stabilizes the macropore formation. The polarity of alcohol becomes lower with the increasing number of carbon in alcohol. Et2O also has low polarity. A polarity of the solvent seems to play a decisive role for the macropore formation. The pore wall is hydrophobic because the wall surface is hydrogen-terminated. Then alcohol having a long carbon chain and Et2O are likely to be accommodated in the vicinity of pore walls, and the state leads to a low density of water and/or HF on the wall surface. When alcohol which has a long carbon chain or together with Et2O is used, the dissolution rate on the silicon surface becomes low because of the low density of HF in the vicinity and stable pore formation is achieved. Chao et al. reported that amphiphilic surfactants adsorbed on the surface of the electrode with their nonpolar tails attached on the hydrophobic surface; the adsorption may protect the sidewalls against dissolution . On the other hand, with alcohol having a short carbon chain and without Et2O, relatively high concentration of HF can be expected in the vicinity compared with the low polar solvents. Therefore, a high polar solvent such as MeOH results in the nearly uniform distribution of HF on the surface, i.e., the concentration of HF seems to be not so different at the pore bottom and elsewhere. That is the reason why macropores cannot be obtained when those types of alcohol are used.
The tetravalent dissolution sometimes occurs via oxide [10, 12]. In this study, the measured valence is around 2.5. The value over two implies that tetravalent dissolution or electrochemical etching takes place partially. The preferential site should be the pore tip because the current collector is located at the back of the silicon substrate, and the pore tip has the small curvature. An oxide formation at the pore tip and its dissolution therefore leads the pore growth to a vertical direction. Besides, the dissolution along this direction can prevail over other directions, since water or HF tends to be provided for the oxide which is hydrophilic. As of now, we have not studied the details yet. This subject will be studied in the future.
As the number of carbon in alcohol in a low concentration HF solution increases, the stable macropore formation is achieved. Macropores also become stable against the surface dissolution under the same condition. The dissolution of the top surface is caused by the presence of alcohol in the low HF concentration solution. When the solution containing Et2O is used, the dissolution of pore walls is suppressed. It is confirmed that the type of alcohol has a significant effect on the pore formation. Not only current density or concentration of HF solution but also the type of alcohol affects the pore structure. The property of organic solvents is crucially important for the porous layer formation.
This work was partially supported by the Grant-in-Aid from the Japan Society of Promotion of Science for Scientific Research (B) under grant no. 22350092. The authors wish to thank K Ogata (Nitta Haas Incorporated) for the profilometer measurements and T Jalkanen and R Koda for their invaluable discussion.
- Theunissen MJJ: Etch channel formation during anodic dissolution of n-type silicon in aqueous hydrofluoric acid. J Electrochem Soc 1972, 119: 351–360. 10.1149/1.2404201View Article
- Propst EK, Kohl PA: The electrochemical oxidation of silicon and formation of porous Si in acetonitrile. J Electrochem Soc 1994, 141: 1006–1013. 10.1149/1.2054832View Article
- Wehrspohn RB, Chazalviel J-N, Ozanam F, Solomon I: Electrochemistry and photoluminescence of porous amorphous silicon. Thin Solid Films 1997, 297: 5–8. 10.1016/S0040-6090(96)09362-5View Article
- Ponomarev EA, Lévy-Clément C: Macropore formation on p-type Si in fluoride containing organic electrolytes. Electrochem Solid St 1998, 1: 42–45.View Article
- Lehmann V, Rönnebeck S: The physics of macropore formation in low-doped p-type silicon. J Electrochem Soc 1999, 146: 2968–2975. 10.1149/1.1392037View Article
- Carstensen J, Christophersen M, Föll H: Pore formation mechanisms for the Si-HF system. Mater Sci Eng B 2000, 69–70: 23–28.View Article
- Harraz FA, Kamada K, Kobayashi K, Sakka T, Ogata YH: Random macropore formation in p-type silicon in HF-containing organic solutions—host matrix for metal deposition. J Electrochem Soc 2005, 152: C213-C220. 10.1149/1.1864292View Article
- Song JH, Sailor MJ: Dimethyl sulfoxide as a mild oxidizing agent for porous silicon and its effect on photoluminescence. Inorg Chem 1998, 37: 3355–3360. 10.1021/ic971587uView Article
- Hamm D, Sasano J, Sakka T, Ogata YH: Silicon anodization in HF ethanoic solutions—competition between pore formation and homogeneous dissolution. J Electrochem Soc 2002, 149: C331-C337. 10.1149/1.1473778View Article
- Christophersen M, Carstensen J, Voigt K, Föll H: Organic and aqueous electrolytes used for etching macro- and mesoporous silicon. Phys Status Solidi A 2003, 197: 34–38. 10.1002/pssa.200306464View Article
- Chao KJ, Kao SC, Yang CM, Hseu MS, Tsai TG: Formation of high aspect ratio macropore array on p-type silicon. Electrochem Solid St 2000, 3: 489–492.View Article
- Föll H, Leosner M, Cojocaru A, Carstensen J: Macroporous semiconductors. Materials 2010, 3: 3006–3076. 10.3390/ma3053006View Article
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.