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Thin Solid Films, 64 (1979) 479-483


Elsevier Sequoia S.A., Lausanne--Printed in the Netherlands




Minsk Radioengineering Institute, Podlesnaja Str. 6, Minsk (U.S.S.R.)

(Received April 23, 1979; accepted June 1, 1979)

The formation of porous silicon (PS) during the anodic treatment of monocrystalline silicon in 24~ aqueous HF has been investigated. Three specific regions were identified in the electrode potential curves. Furthermore, it was observed that the density of the PS formed decreases with depth. The thickness of the PS increases according to a linear law. Taking into account these data and using the known chemical reactions at the silicon-electrode interface, a model of the formation of PS was developed.


Anodic treatment of monocrystalline silicon in HF at a current density J below the critical value is accompanied by formation of porous silicon (PS). PS is chemically very reactive and is used to form dielectrics, and doped and gettering layers in semiconductor electronics 1-3. It is necessary to control the structure and density of the PS to use it successfully. It has been reported 4' s thn't the structure of PS varies with depth; however, no explanation of this effect has been given in previous literature. In this paper, the formation of PS in 249/0 aqueous HF has been studied to determine its properties.


Silicon wafers used for this work were p-type (boron doped) with a resistivity of 0.1 f~ cm and were made by the Czochralski method. The wafer thickness was 400 ~tm. The crystal orientation of the silicon used was on the (111) plane. The anodic treatment was carried out in an electrolytic cell6 using a horizontal anode and the solution was stirred. The distance between the anode and cathode (platinum) was 3 cm and the area under treatment was 2 cm 2. A constant current source was used. The reference electrode was a saturated calomel electrode. The electrolyte consisted of 100 m1489/00HF and 100 ml H20. The PS density p was obtained by measuring the weight difference before and after anodic treatment and the actual volume of the PS. The PS thickness l was

* Paper presented at the International Conferertce on Metallurgical Coatings, San Diego, California, U.S.A., April 23-27, 1979.



determined by investigation of the cross section perpendicular to the wafer surface. The surface layer structure of the PS was studied by transmission electron microscopy (TEM) with simultaneous examination of the microdiffraction pattern. The PS film of thickness I ~ 1000/~ was removed for TEM investigation by briefly raising the current above 1 A. The inner structure of PS was investigated by the observation of the surface using a two-stage replication method after which the PS was completely removed.


Figure I shows the relationship between the electrode potential ~o of the silicon anode and the reaction time t for current densities J of 5, 10 and 40 mA cm- 2. As can be seen from the figure, there are three distinct regions for all J values. Region I corresponds to a sharp increase of cp when the current is applied. The electrode potential decreases in region II and the reaction time is about 20-40 s. During the anodic treatment q~decreases for J = 5 and 10 mA cm- 2 in region III but for J = 40 mA cm- 2 cp is roughly constant. The relationship between q~ and t indicates the complex character of the electrode process taking place at the anode-solution interface during PS formation.








~ Ji k



t (mLn)



Fig. 1. The electrode potential ~ vs. the anodic treatment time t for various current densities J of(l) 40

mA cm - 2, (2) 10 mA cm-:

and (3) 5 mA cm- 2


















Fig. 2. The variation of PS thickness I with anodic treatment time t for current densities J of 5 mA cm- 2


Fig. 3. Variation of PS density p with depth for current densities J of 5 mA cm- 2 (0), 10 mA cm- 2 (A) and 40 mA cm-2 (x).

10 mA cm- 2 (A.) and 40 mA cm- 2 ( x ).



The relation between l and t for different values of J is shown in Fig. 2. The increase of thickness with t is strictly linear. It is seen that the rate of formation of PS increases with increasing J and, in the range of I examined, the formation rate remains constant during the reaction time. Figure 3 shows the variation of the PS density with depth for different values of J. A specific feature of the PS formation process is the decrease of p with depth. This phenomenon is particularly pronounced for J = 5 and 10 mA cm -2. Structural investigation revealed that the size of the pores and their distribution changed during PS formation. For example, Figs. 4(a)-4(d) contain micrographs illustrating the PS structures obtained at J = 10 mA cm-2 and for the values of l marked A, B, C and D in Figs. 1-3. A selected area diffraction picture and TEM micrograph ofa PS film (l ~ 1000 A) are shown in Fig. 4(a). It is seen that this film is monocrystalline and has a complex system of pores. Figures 4(b)-4(d) show the surface features of the silicon anode after removal of PS. For I ~ 0.5 lam (Fig. 4(b))





Fig. 4. (a) Microdiffraction pattern and TEM micrographs of a PS film of thickness 1 ~ 1000 A. (b)-(d) Surface features of the silicon anode after removal of PS of thicknesses (b) 0.5 ~tm, (c) 5 lam and (d) 15 lain. The current density J was 10 mAcm- 2 in all cases.



many circular "traces" are observed. The sizes of these "traces" are not strictly equal and vary in the range 200-800 A. When t increases up to 5 Ixm(Fig. 4(c)), the average size of the pore "traces" increases to 1000-1500 A. For I ~ 15 lxm (Fig. 4(d)) the size of the pore "traces" continues to grow and grain-like boundaries are observed. All this is due to spreading of the pores. For other values of J, spreading of the pores with increasing thickness is similar, but for J = 5 mA cm-2 it is more pronounced and for J = 40 mA cm- 2 it is slight.


During anodic treatment the following reactions are known 6-9 to occur on the silicon electrode:

Si+2HF+2e + -~ SiF2+H 21"


2SiF2 --} Siamoq,hou~+ SiF,

SiF, + 2HF ~




SiF 2 +



SiO 2 + 2HF + H 2 "f

SiO 2+ 4HF --, SiF, + 2H20


SiF, + 2HF ~ H2SiF6

Reactions (1), (2) and (3) proceed simultaneously. However, it has been reported 6, s, 9 that reactions (1) and (2) play the main role and reaction (3) is of minor importance while PS is being formed. On the basis of the experimental data (Figs. 1- 4) and reactions (1), (2) and (3), the formation of PS may be explained as follows. Reaction (1) starts on the silicon surface when current is applied. At the initial stage, the concentrations of reagents in the reaction region are equal to their concentrations in the solution volume. Reaction (1) occurs at local points of the silicon surface on an atomic scale*' 5. A low conductivity SiF2 film is formed as a result of reaction (1), which leads to an increase in ~0(region I, Fig. 1). Then the SiF 2 film partially dissolves according to reactions (2) and (3), leading to the appearance of pores and a decrease in p. The solution penetrates the pores to inner regions of the monocrystal where reaction (1) is going on. After 25-40 s (region II, Fig. 1) a dynamic balance between reactions (1), (2) and (3) is achieved and these reactions then take place simultaneously. The thickness of PS increases (region III, Fig. 1) and the silicon crystalline structure remains almost intact. Some of the reaction products (H2SiF6 and H2) are removed through the pores to the bulk solution and amorphous silicon is deposited on the pore surfaces. Regions I and II (Fig. 1), in which sharp changes in tp are observed, correspond to the initial stages of local crystal lattice destruction. The PS thickness increases in region II (Fig. 1) and the electrode potential is equal to the sum of the potential drop across the silicon-PS interface and that across the layer of solution in the pores. Thus, the exchange of reagents between the bulk solution and the inner PS regions occurs through the outer PS. This exchange becomes more difficult when the PS thickness increases and the reaction conditions within the PS may differ from those on the surface at the initial stage. The concentration of F- ions in the reaction



region inside the pores will decrease owing to limited reagent exchange 6. This leads to a greater contribution of reaction (3) to the process and hence the SiF2 dissolution rate increases and the PS density decreases. The concentration of F- ions within the PS in the thickness range examined will decrease slightly; this decrease will only affect reactions (2) and (3). This is established by the data of Fig. 2, which shows that, in the range examined, the PS thickness increases linearly. This is characteristic of processes with a rate that is determined by a surface reaction at a solid-solution interface 1°. However, when the PS thickness exceeds 50-100 Ixm, the reaction conditions in PS are so different from those at the surface that the PS growth is parabolic L4. This is characteristic of heterogeneous systems with very limited diffusion 1°. For such layers (l > 50 lam) the PS density will be expected to be lower.


During the anodic treatment of silicon wafers in HF solution three distinct regions are observed in the electrode potential curves. These regions correspond to different stages of PS formation. PS formation is accompanied by a decrease of the concentration of F- ions in the reaction region owing to limited reagent exchange through the PS. This leads to a change in the relation between the chemical reactions within the PS.


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