Ley 1259 de 2008

4.3. Infrared and Raman spectroscopy 4.4. Nitrogen-sorption measurements 4.5. Electron microscopy

4.6. Other characterization techniques 4.6.1. Dynamic light scattering (DLS) 4.6.2. Thermogravimetric analysis (TGA)

4.1. Introduction

Nanostructured materials are characterized by a variety of instrumental methods. No single technique is capable of providing complete characterization of a specific material. There are three main categories of physical techniques that may be used to characterize nanostructured materials; these are diffraction, microscopic, and spectroscopic techniques. In addition others, such as sorption of gases, thermal analysis, or physical property measurements, may give valuable information.

The purpose of this Chapter is to summarize different characterization techniques that have been used in this study with emphasis on the characterization methods used for thin films and nanostructured materials. It is assumed that the fundamental knowledge behind all the methods is well known.

4.2. X-ray diffraction (XRD)

An X-ray powder diffraction pattern of a crystalline substance is a set of lines, each of different intensity and position (d-spacing or Bragg angle, θ). For a given substance the line positions and intensities are fixed and characteristic and can be used as a finger print to identify that substance. The basic equation of the X-ray diffraction is the Bragg law. It is defined as:

Chapter 4. Characterization techniques for nanostructured materials

where λ is the wavelength of the X-rays, n is an integer number, d is the distance between the adjusted crystal planes and θ the Bragg angle. At the Bragg conditions (conditions satisfying the Bragg law), a constructive interference occurs between the reflected incoming X-ray beams, which results in an increase in the intensity called reflection.

In a common powder set up with the diffractometer (in θ – θ geometry), the source of monochromatic X-rays (usually X-ray tube) and the detector (scintillator or semiconductor detector) will scan along θ degrees (giving a plot of intensities against 2θ°) to record the so- called XRD pattern (Figure 4.1). Because a powder is usually randomly oriented and the various lattice planes are also presented in every possible orientation, cones of diffraction are created rather than “spots”. Nevertheless, with the usage of the diffractometer, because of the one-dimensional detection, only well resolved lines (Bragg peaks, reflections) are recorded when the Bragg conditions are fulfilled.

scanning direction

Sample holder scanning direction

X-ray tube detector

transmitted beam diffracted beam incident beam θ θ θ θ d

Figure 4.1. Schematic representation of the reflection XRD experiment (θ - θ

geometry).

All powder diffraction studies in the course of this work were obtained using a Scintag XDS 2000 reflection (θ - θ) diffractometer with a Cu K source, a stationary sample

Chapter 4. Characterization techniques for nanostructured materials

positioned horizontally, and a solid-state, liquid-nitrogen-cooled germanium semiconductor detector. The powder XRD pattern was used to identify the structure of powdered mesoporous materials and crystalline nanostructured materials prepared in the course of this study. The XRD patterns of mesoporous thin films positioned horizontally were also measured with the same set-up, and are referred to films measured in reflection-XRD (RXRD) geometry.

The X-ray powder diffraction data may be used to calculate the average crystal size in a powder sample provided that the average diameter is less than about 200 nm. The lines in the powder diffraction pattern are of finite width; additional broadening of the diffracted X- ray beams occurs when the particle size approaches the nanometer region. The commonly accepted equation to calculate particle sizes from the X-ray diffraction data is Scherrer’s formula:

T = 0.9λ/BcosθB (4.2.)

T is the thickness of the crystal in Angstrom, λ the X-ray wavelength, θB the Bragg angle.

The line broadening, B, is measured from the extra peak width at the half peak height and is obtained from the formula:

B2 = B2m – B2s (4.3)

where Bm is the measured peak width in radians at the half peak height and Bs is the

corresponding width of the peak of a standard material of high crystallinity and micron crystal size. The lower limit of detection with XRD occurs when the peaks become so broad that they disappear in the background radiation.

It is necessary to make an important comment about the evaluation of the diffraction data from the RXRD experiment for thin mesoporous films. The RXRD geometry in many cases is not useful to directly identify the mesophase structure because only the structural information in the direction perpendicular to the film plane (in the direction of the specularly reflected X-ray beam, see below) can be obtained. For example, in numerous publications it has been shown that the two-dimensional hexagonally ordered mesoporous films with channels aligned parallel to the film surface show only two reflections (first and second order

Chapter 4. Characterization techniques for nanostructured materials

peaks of the 100 planes) instead of three reflections typical for the hexagonally ordered MCM-41 or SBA-15 materials (see Chapter 2.2. and references therein). The absence of the (110) reflection in the RXRD comes from the orientational alignment of the mesoporous channels1. Only the (100) face is parallel to the surface and can therefore be recorded in reflection geometry, and the (110) face in this case does not contribute to the observed diffraction pattern (see Figure 4.2b). The (110) reflection could be observed if a different arrangement of the mesoporous channels in respect to the substrate surface is obtained (see Figure 4.2c). Full disappearance of any structural information in the RXRD experiment would correspond to complete alignment of the mesoporous channels perpendicular to the substrate surface (see Figure 4.2a). Of course, in many cases the lack of structural information cannot be directly accepted as proof for the mesochannel-alignment; other reasons, such as distortion of the mesophase structure or complete loss of mesophase order, are also possible. Similar problems hinder the direct identification of the mesophase structure for other known structural configurations. For example, the three-dimensional hexagonal (similar to SBA-2 material, see Chapter 2.2.) structure or several different three-dimensional cubic mesophase structures could be indexed because usually only one or several (not well- resolved) reflections were obtained in the RXRD geometry2_.

Figure 4.2. Schematic representation of the alignment of the channels in the two-dimensional hexagonally ordered (p6m) mesoporous film with the corresponding RXRD patterns1.

Chapter 4. Characterization techniques for nanostructured materials

Summarizing, the need to use diffraction measurements in other geometries (for example, grazing-incidence) instead of conventional reflection-mode X-ray diffraction to determine the mesophase structure of the films is important because in oriented films all the crystallographic planes may not be oriented in a way that the diffracted beam is detectable in the RXRD experiment. In this study, grazing-incident diffraction (GID) with 2D detection (CCD camera) was used to identify the mesophase structure and to determine the orientation of the mesoporous channel system.

Grazing-incidence diffraction (GID) is a scattering geometry combining the Bragg condition with the conditions for X-ray total external reflection from surfaces when the incident angle of the X-rays is small enough (typically 0.05 – 3°, depending on the substrate electron density and the X-ray energy), close to the so called critical angle αc. At this point

the surface is not entirely invisible to the X-rays, but only an evanescent wave penetrates and scatters from it3. Let some set of crystallographic planes be oriented perpendicular to the substrate surface and fulfill the Bragg condition (forming a Bragg angle θ between the plane of the incident beam and the crystallographic planes), thus preserving the small grazing-exit angle αf; this will generate a diffraction wave in the plane of the substrate. These conditions

provide superior characteristics of GID as compared to other diffraction schemes in the studies of thin surface layers4,5,6. In order to perform grazing-incidence diffraction, a highly intense, parallel, and stable X-ray beam is desirable that can be obtained only by using Synchrotron radiation.

The geometry of the GID experiment with 2D detection is shown in Figure 4.3. The 6-circle diffractometer at beam-line ID01 at the ESRF (www.esrf.fr) in Grenoble, France, was used for all GID experiments. The X-ray beam is focused on the film surface with the help of the single crystal monochromator at an incident-angle of αi = 0.3 degrees, which is

higher than the critical angle for silica (αc = 0.1), where the total external reflection is

observed. The structural information as a function of the film thickness depends on the penetration depth of the X-rays at constant incidence angle. It was calculated that at this incident angle the whole film thickness was scanned. In forward direction the specularly reflected beam is observed at the grazing exit angle αf, together with the diffracted wave (out

Chapter 4. Characterization techniques for nanostructured materials

of plane diffraction) coming from the planes that are parallel to the substrate surface (as in the RXRD experiment where the speculary reflected and diffracted beams are overlapping).

2 θ o mesoporous film sample horizon primary beam αf qy qx qz CCD beam stop out of plane diffraction

2θo αi substrate specularly reflected beam incident beam in plane diffraction

Figure 4.3. Schematic representation of the scattering geometry of GID in real space.

As explained earlier at these incident angles it is possible to have total external reflection and to obtain in-plane diffraction from planes oriented perpendicular to the substrate surface (grazing-incident diffraction). With the help of a 2D detector (CCD camera) set perpendicular to the incident beam and the grazing incident geometry, it was possible to obtain structural information from both the qz and qy components of the structural vector Q at

the same time. Thus, correct indexing of the mesophase structure and determination of the orientation of the mesoporous system is possible. The distance between the sample and the recording plane was 650 mm. The resolution of the measurement is given by the number of pixels of the CCD camera per degree, which was 0.005 degree per pixel. Alignment of the X- ray beam to the sample surface was performed before every measurement. The specular reflectivity was masked with a circular beam stop to avoid saturation of the detector. The positions of the Bragg spots were calculated from the position of the primary beam in the CCD camera taking into account that one pixel corresponds to 0.005 2θ degrees.

Chapter 4. Characterization techniques for nanostructured materials