Ultrathin Porous Silicon Films

Brahim Bessaı̈s

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Preparation of Ultrathin PS Films for XRR Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
XRR Analyses of Ultrathin PS Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

Abstract
Investigations of the structure and morphology of ultrathin PS films are reviewed,
of relevance to the technological control of miniaturized PS-based devices. Several
characterization tools with high reliability and precision are available; however,
many of them are destructive or could affect the ultrathin PS structure. Grazing
incidence X-ray reflectivity (XRR) is a powerful tool to probe the structural and
morphological characteristics of ultrathin PS films. Homogeneity, thickness, sur-
face and interface roughness, porosity, and density of ultrathin PS films were
accurately determined using XRR. Nonetheless, prior to XRR measurements,
ultrathin PS films should be submitted to complementary nondestructive morpho-
logical and optical examinations (thickness, roughness, oxidation, etc.).

Introduction

Since the discovery of the room temperature photoluminescence (PL) in 1990

(Canham 1990), porous silicon (PS) has raised a strong interest owing to its potential
applications in electronic and optoelectronic devices (see handbook chapter
“▶ Porous Silicon Application Survey”). The physical properties and performance

B. Bessaı̈s (*)
Research and Technology Centre of Energy, Borj-Cedria Technopark, Hammam-Lif, Tunisia
e-mail: Brahim.bessais@crten.rnrt.tn

# Springer International Publishing Switzerland 2014 143

L. Canham (ed.), Handbook of Porous Silicon,
DOI 10.1007/978-3-319-05744-6_14
144 B. Bessaı̈s

Table 1 Methods used for the characterization of thin PS films

Technique Parameters Comments References
Gravimetry Average porosity, Lower accuracy with (Pickering et al. 1984;
thickness thin layers Brumhead et al. 1993)
SEM Thickness, pore Destructive (Riley and Gerhardt 2000;
morphology Dittrich et al. 1995)
TEM Pore and crystallite Destructive (Berbezier and Halimaoui
size distribution 1993; Gardelis et al. 2008)
AFM Surface roughness Accuracy in tapping (von Behren et al. 1995;
mode Striemer et al. 2007)
SE Optical index, Nondestructive (Pettersen et al. 1998;
absorption, porosity Wongmanerod et al. 2001)
gradient
XPS Chemical Destructive at high (Hardeman et al. 1985; Lees
composition X-ray dose, formation et al. 2003)
of Si oxides
XRR Porosity, density, Quasi-nondestructive, (Sama et al. 2001; Ennejah
thickness, interface possible reduction of et al. 2011)
roughness the porosity
UV–vis–NIR Thickness, Homogeneity, optical (Pickering et al. 1984; von
absorption absorption, aging, etc. Behren et al. 1995; Butturi
coefficient et al. 1997)

of these devices often crucially depend on their interfacial structures. Thereby,

characterization of the structure of ultrathin films became increasingly important.
With the continuing minimization of thin film devices, characterization techniques
with high reliability and precision are required (Isao and Boquan 1999).
Nanoengineered PS films have many advantages in lab-on-chip devices, separa-
tions/filtrations, and nanoelectromechanical and nanofluidic systems applications
(Whitby and Quirke 2007; Tong et al. 2004; Hinds et al. 2004). The handbook
chapter “▶ Porous Silicon for Microdevices and Microsystems” focuses on such
uses. For most applications, the main important performance goals of membrane-
like PS films are high permeation rate and good selectivity, which are achieved by
high porosity, narrow pore size distribution, and small thickness (Kavalenka
et al. 2012). The thickness of the films is a crucial parameter that influences most
of the film properties; hence, most of technological applications require thin films of
precise and definite thickness. In this context, the control of the structure and
morphology of ultrathin PS films (porosity, crystallite sizes, homogeneity, etc.) is
of prime importance to achieve powerful miniaturized PS-based devices. In Table 1,
we summarize the main methods used for the characterization of ultrathin PS films.
The technique of grazing incidence X-ray reflectivity represents a quasi-
nondestructive method for the determination of thicknesses less than 250 nm (with
a precision of about 1–3 Å of one or several ultrathin PS films), electronic densities,
and surface and interfacial roughnesses and porosities (Chamard et al. 2001). The
value of the porosity of the PS film is very sensitive to the preparation conditions
together with the employed determination method. XRR measurements are highly
Ultrathin Porous Silicon Films 145

successful when the investigated films are deposited on polished substrates

(a condition also needed for SE investigations) (Tompkins and Irene 2005; Ennejah
et al. 2011). Furthermore, XRR is a well-adapted technique for measurements of thin
PS films (Eymer et al. 1999; Keissing 1931), if one can visualize Keissing interfer-
ential fringes (Parratt 1954). The latter could only be observed if the PS film has a flat
and homogeneous thickness not exceeding 250–300 nm and a surface roughness less
than 3 nm, which approximately corresponds to 1 % of the maximum allowed
thickness (Isao and Boquan 1999; Ennejah et al. 2011; Eymer et al. 1999). One may
guess that these conditions are not so simple to obtain with ultrathin PS films; this is
why sets of PS samples should be prepared in order to optimize the electrochemical
etching (EE) conditions (Guilinger et al. 1995; Ennejah et al. 2011; Eymer et al. 1999).
These special precautions could be satisfied by varying the anodization time at a
rather low current density (Ennejah et al. 2011). Accordingly, XRR can be consid-
ered as a powerful characterization method. In order to take benefit of the effec-
tiveness of XRR, one needs to estimate the chemical species, the homogeneity, the
surface roughness, and the thickness of the PS films by performing infrared
spectroscopy, SE, AFM, and UV–vis–NIR characterizations. Therefore, care
should be taken to protect the ultrathin PS films against oxidation prior to XRR
investigations. The aim of this review is to focus on the early-stage formation
kinetic of EE-based ultrathin PS films using the glazing angle XRR.

Preparation of Ultrathin PS Films for XRR Analysis

Homogeneous ultrathin PS films may be prepared by electrochemical etching

(EE) of p-type monocrystalline Si wafers, in HF-based solutions during short
periods and optimized current densities allowing to get various thicknesses
(Ennejah et al. 2011; Guilinger et al. 1995) and an average porosity of about
50–75 %. For a general review of this fabrication technique, see handbook chapter
“▶ Porous Silicon Formation by Anodization.” In order to observe Keissing fringes,
the ultrathin PS thickness should be lower than 250 nm and the surface roughness as
low as 3 nm (Ennejah et al. 2011). An example consists of lowering the surface
reflectivity of pyramidal-textured Si solar cells by forming ultrathin nanoporous
films on the pyramidal facets (Kim et al. 2009; Fig. 1a) using the EE technique.
New ways of structuring rather uniform ultrathin nano-PS films having various pore
shapes consist of HNO3/HF vapor etching of silicon (Fig. 1b) or crystallizing a thin
amorphous silicon film (Kavalenka et al. 2012; Striemer et al. 2007; Saadoun
et al. 2002; Fig. 1c).
For PS films prepared from the EE method, one should optimize anodization
conditions and check and/or estimate the silicon oxide content (SiOx) in the PS
films before performing XRR characterization. In fact, freshly prepared PS films are
generally covered with Si–H bonds; nevertheless formation of Si–O bonds always
takes place at the early stages of PS formation (Ennejah et al. 2011).
On the other hand, one should have a rough idea on the homogeneity of the PS
films by checking their diffuse and specular reflectivity (Fig. 2a, b).
146 B. Bessaı̈s

Fig. 1 (a) EE-based nanoporous pyramidal plane applied in pyramidal-textured Si solar cells
(Kim et al. 2009). (b) SEM cross-sectional view of a gold-coated thin PS film prepared from
HNO3/HF vapor etching (Ben Jaballah et al. 2005). (c) Cross-sectional SEM image of porous
nanocrystalline (pnc) Si membrane imaged on the surface of a metalized silicon wafer revealing
the cylindrical nature of the pores (Kavalenka et al. 2012)

a b 60
10s
Specular Reflectivity (%)

8
Diffuse Reflectivity (%)

10s 40s
50
7 40s 50s
6 50s 40 120s

5 30

4 20
3 10
400 600 800 1000 1200 400 600 800 1000 1200
Wavelength (nm) Wavelength (nm)

Fig. 2 Variation of (a) diffuse and (b) specular optical reflectivity of ultrathin PS films with
anodization time (Ennejah et al. 2011)

One may notice that for anodization time ranging from 10 to 50 s, the diffuse
reflectivity is lower than the specular one. As anodization time (i.e., thickness)
increases, the interference fringes (Fig. 2b) become closer to each other indicating
at a first sight the formation of relatively smooth and homogeneous PS films.
Ultrathin Porous Silicon Films 147

To evaluate the surface roughness, AFM microscopy characterizations were

made on the same samples (Ennejah et al. 2011). By examining the AFM surface
topography of ultrathin PS films in tapping mode, Ennajeh et al. (2011) found
that the PS surfaces have a root-mean-square (rms) roughness not exceeding
1.5 nm (Ennejah et al. 2011), whatever the anodization time may be, indicating
an etching time independence of the surface roughness. In fact, short anodization
times do not allow deep etching of early formed surface structures, suggesting
an almost invariable roughness. For current densities not exceeding 5 mA/cm2
and etching times ranging from 10 to 1,200 s, the rms does not exceed
1.5 nm (Ennejah et al. 2011). Spectroscopic ellipsometry (SE) measurements of
thickness, optical index, and optical absorption require modeling the PS films. In
that case, the Bruggeman (1935) model may be adopted, if one considers the PS
film formed of two phases (e.g., silicon and vacuum) having different volume
percentages. The PS thickness evaluated from SE varies from tens of nanometers
to a few hundreds of nanometers, with a quasi-constant porosity value (Ennejah
et al. 2011).

XRR Analyses of Ultrathin PS Films

For X-rays, the matter refraction index is slightly lower than unity. The reflection of
the X-rays occurring at the interface separating two media could be estimated from
the Snell–Descartes law, which reveals total reflection below a critical angle
depending on the electronic density of the material (Abramof et al. 2006). This
critical angle has a very small value in the grazing X-ray technique (Abramof
et al. 2006). The analysis of the reflected X-ray intensity and shape in the total
reflection region (i.e., angles smaller than the critical one) (Fig. 3a) provides
information on the surface structure from ten to several hundred angstroms deep.
One may point out two critical angles θcPS and θcSi related to reflection at the
interfaces air/PS and PS/silicon, respectively (Ennejah et al. 2011; Fewster 1996).
One may also notice that θcPS is smaller than θcSi due to lower density of the PS
films.
In the total reflection zone, the reflected X-ray intensity is sensitive to electron
density variation of the characterized material and is independent of the amorphous
or crystalline structure or the crystallites orientation at the surface (Chamard
et al. 2002). If the surface of the sample presents two or more homogeneous
media, the reflection curve shows peculiarities associated to the electronic property
of each media and to the different interface behaviors. For angles higher than the
critical one, the X-rays are absorbed by the material and the reflected intensity
drops abruptly. In the case of stratified homogeneous media having smooth bound-
ary interfaces, one may observe reflected rays presenting Keissing fringes (Fig. 2b),
which give information about film thickness and density variation between media
and interface states. In the conditions of Ennejah et al. (2011), the Keissing fringes
vanish at anodization time exceeding 50 s (Fig. 3b). The porosity of the PS films can
be estimated from the relation (Buttard et al. 1998):
148 B. Bessaı̈s

a b
107 106
X-Ray reflected intensity (counts/s)

X-ray reflected Intensity (counts/s)

θcSi 10 s
20 s
30 s
θcSP 105
106 40 s
50 s
100 s
10 s
40 s 104
105 100 s

103
0.1 0.2 0.3 0.4 0.5 0.6 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3
Grazing incidence angle 2θ (°) Grazing incidence angle 2θ (°)

Fig. 3 (a) XRR measurements on thin PS films etched for 10, 40, and 100 s in the total reflection
region, (b) XRR measurements of thin PS films in the X-ray penetration region (Ennejah
et al. 2011)
h
 i
Pð%Þ ¼ 1  ðθcSP =θcSi Þ2  100

Figure 4 shows the variation of porosity, thickness, and roughness, determined

from XRR patterns versus anodization time. In fact, pore initiation proceeds
spontaneously on smooth silicon substrate yielding 1010/cm2 tiny etch pits after
only a few seconds of anodization; many of these pits merge to form approximately
106/cm2 to 108/cm2 stable pores, which then continue to grow into the substrate
(Buttard et al. 1998; Zhang 1991), leading to a final stable porosity. The porosity of
ultrathin PS films, determined from Keissing fringes, grows almost linearly for
short anodization time (Fig. 4a); then it tends to a stable porosity value (Ennejah
et al. 2011). The thickness of EE-prepared ultrathin PS films (Fig. 4b), determined
from XRR, exhibits a linear growth for short and long anodization times; the
estimated values (Fig. 4b) are almost similar to that determined from SE or
electronic microscopy (Guilinger et al. 1995) and even gravimetry for rather thick
PS films (Guilinger et al. 1995). Riley and Gerhardt (2000) observed the same linear
thickness behavior for thin p-type PS (Fig. 4b), although a nonlinear growth was
depicted on n+-type PS films at short anodization times while using gravimetric
analysis (Brumhead et al. 1993). It seems to be obvious that in case of homogeneous
EE, the porosity of p-type PS films remains stable and etching is time independent,
while the thickness grows linearly within etching time (Bessaı̈s et al. 2000).
From XRR, one may evaluate the PS surface roughness and the PS/Si interface
roughness (Fig. 4c). The PS surface roughness fluctuates in the range of 0.4–1 nm
and is always less than unity; it tends to a constant value (equivalent to that
determined from AFM for a virgin silicon wafer) with increasing anodization
time (Guilinger et al. 1995; Ennejah et al. 2011), results in agreement with that
obtained from AFM and TEM analysis (Guilinger et al. 1995). The interface
roughness could be determined in the XRR specular geometry, where only the
direction perpendicular to the sample surface is investigated, allowing to probe the
interface state evolution associated to progressive pore nucleation.
Ultrathin Porous Silicon Films 149

a b 200
70
160

Thickness (nm)
Porosity (%)

60
120

50 80

40 40

0 20 40 60 80 100 10 20 30 40 50
Anodization time (s) Anodization time (s)

c 7
Interface roughness (nm)

6
5
4
3 roughness at SP/Si interface
roughness at PS surface
1.0
0.5

10 20 30 40 50
Anodization time (s)

Fig. 4 (a) Porosity, (b) thickness, and (c) interface roughness versus anodization time (Ennejah
et al. 2011)

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