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Small metal nanoparticle recognition using digital image analysis and high resolution electron microscopy A.B. Flores a , L.A. Robles a , M.O. Arias a , J.A. Ascencio b, * a  Instituto Nacional de Astrofı ´ sica, O ´  ptica y Electro ´ nica Code 51 and 216, Puebla 72000, Mexico b Programa de Investigacio ´ n y Desarrollo de Ductos, Instituto Mexicano del Petro ´ leo, Eje Central La ´  zaro Ca ´ rdenas 152 Col. San Bartolo Atepehuaca ´ n, CP 07730, Mexico, D.F., Mexico Received 10 April 2002; revised 5 August 2002; accepted 7 February 2003 Abstract In this paper, we present a system developed to identify metal nanoparticles at different orientations, using digital image processing and analysis. The correct identication is important in nanotechnology, where it is possible to build structures for different purposes at the nanometric level. The recognition system computes automatically different characteristics such as: nanoparticle area, polygons, symmetry and molecular arrays (twins) in order to recognize different nanostructures. All these characteristics are obtained through the use of morphological, texture (co-occurrence matrix) and region analysis. Complexity issues, advantages, and results are presented and discussed. q 2003 Elsevier Science Ltd. All rights reserved. Keywords: Pattern recognition; Nanotechnology; Image analysis and processing 1. Introduction Nanotechnology is, without doubt, the technology of this new century, based (for example ) on molec ular systems with no more than thousands of atoms and a scale range of 10 29 m (Ascencio et al., 1998). Nanotechnology has a big range of applications, from photonic to electronic, catalysis, and many ot hers (Jose ´-Yacama ´ n, 1996). The use of  nanoparticles (Andres et al., 1996), nanorods, and nanotubes with different elements leads to a variety of properties that can be used in many new devices. In thi s new tec hno log y, the par ame ter s of ele mental composition, size, shape, and internal structure determine the nal property of the atomistic system. The character- iza tion of nanost ruc tures is ver y imp ort ant and many tec hni que s hav e bee n use d in nanopa rti cle res ear ch, in order to characteriz e the atomic dis tri but ion in the nanometric scale (Jose ´ -Yacama ´n, 1996). Because of the size of these particles, high resolution electron microscopy (HREM) has been considered one of the best tools for getting information about their structure (As cencio et al ., 1998). Th is te chni que is ba se d on the tra nsmiss ion of an ele ctr on bea m thr ough a sample and the analysis of the scattered signal, which is function of the sample st ruc ture and compos iti on (Jose ´ -Yacama ´ n and Asc enc io, 200 0). HREM part ic ul arl y re fe rs to a resolu tio n limit clo se to 2 A ˚ tha t mak es it pos sible to obse rve detai ls of latti ce spaci ng in cryst allin e mater ials (Williams and Carter, 1996). However, the images obtained by HREM show di f fe re nt problems such as poor contrast , noise , and image overl ap that complic ate correct patte rn ident ica tion (Ascencio, 2000). Until now, the common method for the recognition of nanoparticles is based on a visual inspection that requires a skil led technician with experi ence; theref ore the pr ocess is ti me cons uming and is pr one to er rors. These pro blems sug ges t the necess ity of an automa ted system for ide nti fyi ng nanopa rti cle s in a mor e ef ci ent and faster way. Because of its impor tance, several works in the literature, have reported analysis of nanoparticle structure using HREM and the Fourier transform ( Ascencio et al., 1998; Ascencio, 2000; Schaf et al., 1997). However, these advances have opened up more possibilities of application; in this case, we applied pattern recognition tools for digital images in order to so further, towards the automatization of the recognition process. 0968-4328/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0968-4328(03)00006-4 Micron 34 (2003) 109–118 www.elsevier.com/locate/micron * Correspond ing author. E-mail address: ascencio@imp.mx (J.A. Ascencio ).
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Small metal nanoparticle recognition using digital image analysisand high resolution electron microscopy

A.B. Floresa, L.A. Roblesa, M.O. Ariasa, J.A. Ascenciob,*

a Instituto Nacional de Astrofı sica, O  ptica y Electro nica Code 51 and 216, Puebla 72000, MexicobPrograma de Investigacio n y Desarrollo de Ductos, Instituto Mexicano del Petro leo, Eje Central La  zaro Ca rdenas 152 Col. San Bartolo Atepehuaca n,

CP 07730, Mexico, D.F., Mexico

Received 10 April 2002; revised 5 August 2002; accepted 7 February 2003

Abstract

In this paper, we present a system developed to identify metal nanoparticles at different orientations, using digital image processing and

analysis. The correct identification is important in nanotechnology, where it is possible to build structures for different purposes at the

nanometric level. The recognition system computes automatically different characteristics such as: nanoparticle area, polygons, symmetry

and molecular arrays (twins) in order to recognize different nanostructures. All these characteristics are obtained through the use of 

morphological, texture (co-occurrence matrix) and region analysis. Complexity issues, advantages, and results are presented and discussed.

q 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Pattern recognition; Nanotechnology; Image analysis and processing

1. Introduction

Nanotechnology is, without doubt, the technology of this

new century, based (for example) on molecular systems

with no more than thousands of atoms and a scale range of 

1029 m (Ascencio et al., 1998). Nanotechnology has a big

range of applications, from photonic to electronic, catalysis,

and many others (Jose-Yacaman, 1996). The use of  

nanoparticles (Andres et al., 1996), nanorods, and nanotubes

with different elements leads to a variety of properties that

can be used in many new devices.In this new technology, the parameters of elemental

composition, size, shape, and internal structure determine

the final property of the atomistic system. The character-

ization of nanostructures is very important and many

techniques have been used in nanoparticle research, in

order to characterize the atomic distribution in the

nanometric scale (Jose-Yacaman, 1996).

Because of the size of these particles, high resolution

electron microscopy (HREM) has been considered one of 

the best tools for getting information about their structure

(Ascencio et al., 1998). This technique is based on

the transmission of an electron beam through a sample

and the analysis of the scattered signal, which is function

of the sample structure and composition (Jose-Yacaman

and Ascencio, 2000). HREM particularly refers to a

resolution limit close to 2 A that makes it possible to

observe details of lattice spacing in crystalline materials

(Williams and Carter, 1996). However, the images

obtained by HREM show different problems such as

poor contrast, noise, and image overlap that complicate

correct pattern identification (Ascencio, 2000).

Until now, the common method for the recognition of nanoparticles is based on a visual inspection that requires

a skilled technician with experience; therefore the

process is time consuming and is prone to errors.

These problems suggest the necessity of an automated

system for identifying nanoparticles in a more efficient

and faster way.

Because of its importance, several works in the

literature, have reported analysis of nanoparticle structure

using HREM and the Fourier transform (Ascencio et al.,

1998; Ascencio, 2000; Schaf et al., 1997). However, these

advances have opened up more possibilities of application;

in this case, we applied pattern recognition tools for digital

images in order to so further, towards the automatization of the recognition process.

0968-4328/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.

doi:10.1016/S0968-4328(03)00006-4

Micron 34 (2003) 109–118www.elsevier.com/locate/micron

* Corresponding author.

E-mail address: [email protected] (J.A. Ascencio).

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Our proposed solution is based on the design of a system

that discriminates characteristics for every nanoparticle,

such as regional properties (convexity, roundness, etc.),

perimeter, parallel line arrangements, symmetry and

polygonal contour. Based on these characteristics, it ispossible to identify the nanoparticles from an HREM image.

2. The general problem

Nanoparticles are arrangements of atoms with controlled

size and shape, involving sizes that allow researchers to

develop new materials or structures with improved optical,

electronic and magnetic properties (Andres et al., 1996).

However, due to the size of nanostructures, the correspond-

ing contrast is complicated to distinguish. For example in

Fig. 1, a common image with many gold nanoparticles is

shown; in the inset a structure of around 1.2 nm is observed.

The particle corresponds to a cubic like structure, showing

no more than 10 white dots in an hexagonal array, that

correspond to columns of atoms. The inset nanoparticle has

,120 atoms and is clearly difficult to recognize with only

this information.

In this case, the white dots contrast is produced by the

columns of atoms and the possibility to have this contrast in

the opposite way (black dots over a white matrix) is function

of the defocus condition. There is a direct relation between

the defocus and the corresponding contrast transfer

depending also of the acceleration voltage, the optimum

condition is known as Scherzer defocus that produce the

maximum contrast in white dots from the column atoms

corresponding to the (111) and (200) planes for the case of 

gold (by instance Scherzer defocus for a microscope with400 keV and spherical aberration of  C S ¼ 1 mm; is

D f  ¼ 40:5 nm), there is a second maximum of contrast

black dots instead the white ones (at D f  ¼ 70:2 nm for the

mentioned microscope). Each microscope has different

maximum depending on its parameters and operation

conditions (Williams and Carter, 1996).

In fact, Fig. 1 shows a relatively simple orientation, but

the probability of having it is low. The main reason is that

the nanoparticles to be analyzed are deposited over an

amorphous carbon substrate and the orientation can change

greatly because the irregularity of the carbon substrate, as

can be seen in Fig. 2. The orientations (relative to the

electron beam incident direction) of the nanoparticles vary

significantly and reorientation of the sample becomes

almost impossible because, at the needed magnification, a

small amount of tilt can result in losing the nanoparticle

from the field of view. This implies the necessity of 

recognizing each structure at different orientations. In a

previous paper (Ascencio et al., 1998), we reported a full

catalog of simulated images that allows relating the

observed contrast with a particular configuration and its

specific orientation.

Clearly, HREM nanoparticle images can have higher-

index orientations (Ascencio et al., 1998), where it is

Fig. 1. High resolution transmission electron microscopy image for a

common sample of nanoparticles. The inset shows the dotting contrast

produced by a nanostructure around 1.2 nm in size.

Fig. 2. Nanoparticles on a substrate. Orientation with respect to the electron beam is random because of the relatively irregular surface on which they are

deposited.

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difficult to observe specific characteristics. These elementscomplicate further the recognition of the nanoparticles,

since the images look very different from the different

orientations, even if changes are minimal. Therefore, the

specific characteristics of the changes for different orien-

tations complicate the use of only one pattern-recognition

technique, like Fourier transform (Ascencio et al., 1998) or

correspondence analysis (Van Heel and Frank, 1980).

Another problem is that, due to the complexity of the

nanostructured construction, different characteristics will be

present in every cluster of nanoparticles, as will be

discussed in this paper.

3. Nanoparticle characteristics

The nanostructure models being studied are indicated

in Fig. 3. FCC (face-centered-cubic) particles have three

basic shapes: the cubo-octahedron (a), the truncated

octahedron (b) and the special truncated octahedron with

the entire edge lengths equal, which is commonly named

tetrakaidecahedron (c). These shapes will be designatedas CO, TO and TKD, respectively. In the case of the

decahedron, there are also has three cases. First the

decahedron or pentagonal bipyramid (d), with the second

and third cases being variations of the original decahe-

dron called Ino’s decahedron (e) and the truncated Marks

decahedron (f), called Dh, I-Dh and t-Dh, respectively.

Another cluster shape is shown in (g), which corresponds

to the icosahedron named Ih. The final shapes considered

in (h) are amorphous clusters of 55 atoms.

An important characteristic in decahedral and icosahe-

dral particles is the presence of defects in system regularity

that produce a change in the atomic orientation sequence,

called twins. These twins are excellent discriminators,because they are not present in shapes like FCC or

amorphous.

The main characteristics of the configurations con-

sidered are shown in Table 1. Our work involves 86 HREM

images, 11 different orientations for every structure, with

exception of amorphous clusters, which have just nine

orientations. The characteristics in Table 1 are the basis for

Fig. 3. Models of nanoparticles. (a) Cubo-octaedral particle; (b) truncated octahedral particle; (c) tetrakaidecahedron; (d) pentagonal bipyramid; (e) Ino

decahedron; (f) Marks decahedron; (g) Icosahedron; and (h) amorphous clusters.

Table 1

Characteristics presented for every shape of nanoparticles

FCC nanoparticles

Cubo-octahedron Truncated-octahedron Tetrakaidecahedron

Characteristics: well-defined structures, like square or hexagon shape and the presence of arrays. In low index orientation, images present a structure showing

only black dots representing the columns of atoms

Twins nanoparticles

Decahedron Icosahedron

Pentagonal by-pyramid Ino decahedron Marks decahedron Icosahedron

Characteristics: twins presence, polygons with 4–8 sides, zig-zag arrays and

symmetry in some cases. In low index orientation, images present a structure

showing only black dots representing the columns of atoms

Characteristics: length equal sides hexagons, decagons in orientations

[1,1,1] and high symmetry in all the images

Amorphous nanoparticles

Amorphous

Characteristics: amorphous structure, therefore the absence of well-defined structures

 A.B. Flores et al. / Micron 34 (2003) 109–118 111

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the development of the recognition system presented in this

work.

4. Proposed system

The scheme for the proposed system is shown in Fig. 4.

The system works as follows: First, the recognition system

reads the HREM image to be identified and increases the

image contrast 25%, in order to get a better definition of 

the atom column (black dots) against the background, due to

the difference between the zones where the electrons are

scattered versus the sites where the electrons are transmitted

(Williams and Carter, 1996).

The second system block detects the region of thenanoparticle that corresponds to its area, eliminating the

noise background produced by the carbon substrate, on

which the nanoparticle was mounted. This action increases

the efficiency because image analysis can then be

concentrated just on the nanoparticle region instead of the

full image.

After the nanoparticle area is selected, the system works

with the reduced region of interest and a dynamic threshold

is carried out over the original and inverted image; only the

result with higher information will be selected. This

processing is necessary because the HREM images are

variable in all their parameters: illumination, contrast,

background and focus are not always the same from one

image to another.

Dynamic threshold, morphological operators and anal-

ysis region techniques (Del Bimbo, 1999) are applied in this

stage. The threshold process uses a smoothed version of the

original image (mean or gauss filter) as the local threshold,

and a comparison between the original and the smoothed

version gray values, produces those regions in which thepixels fulfill a threshold condition that corresponds

dynamically to the smoothed image. In order to refine

these regions the use of closing and opening morphological

operators with a circle mask of 9 pixels is used. Finally,

Fig. 4. Scheme for the proposed system for automatic recognition.

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the area and circularity of each region is used in order to

eliminate those regions that not correspond to the area of the

nanoparticles.

At this point, the system has obtained two important

pieces of information: regions representing the structure of 

the nanoparticle, and a contour that could be interpreted as a

first approximation to the polygon that corresponds to its

overall shape.

4.1. Region analysis

The next step is to analyze regions and find a polygon

that represents the contour obtained in the above steps.

Region analysis is done with the objective of finding

information that will be of use in the identification process

(this information search is based on the already mentioneddata). Region analysis parameters like compactness,

circularity, eccentricity, area, angles and Euclidean distance

(Van Heel and Frank, 1980), it is possible to find the

following:

† Number of atoms well defined (no overlapping).

† Low-index orientation.

† Number of parallel arrays.

† Angles and dimensions of every parallel array.

† Split result regions in circular and non-circular regions.

4.2. Polygon search

Another important characteristic is the polygon that

forms the contour of the region of interest found in the

previous action. The polygon search works as follows: first a

new region enclosing only the pixels that could represent the

vertex of a side is selected. The difference between the

region of interest and the same region reduced by 40%

produces this new region. Analyzing the position in columns

and rows of candidates in the new region, it is possible to

find only those regions that better adjust to the contourpreviously found. The process is further explained as

follows.

† Analyze row of pixels and select only those pixels thatare in the maximum or minimum intensity in the image.

If there are points very close to Rm or /and Rl ( Rm and Rl

correspond to maximum and minimum row, respect-

ively) then it means that there is a polygon side at an

angle very close to 08 (908 for columns), joining these

points; analyze angles between lines and decide if there

is only one side or more.

† The same analysis is done in the column axis. The

ideal case is when there are four points Rm – Rl and

C m 2 C l (C m and C l correspond to maximum and

minimum column, respectively), but it only happens

infrequently.

† These points allow creation of a polygon with theselected pixels, as shown in Fig. 5.

† Analyze the points outside the polygon created and

decide if there could be another vertex of the polygon.

This is done by analyzing the normal distance between

one point and the side ‘observed’ by the point; if the

point is as far as its longer length distance, a new vertex

is added, otherwise it is eliminated.

† Repeat the last step until all remaining pixels have been

analyzed (generally only one more search).

† Finally, the sides of the polygon will be analyzed for

searching lines joined by more than two points. If thiscase is present, it will be necessary to eliminate those

intermediate points that belong to the line.

After the system can obtain the corresponding polygon

for the nanoparticle profile, two more characteristics must

be found: number of sides and length proportion between

every polygon side.

4.3. Texture analysis

Texture analysis is carried out by using the polygon

found in the previous process and parameters that can be

obtained from a co-occurrence matrix (Haralick andShapiro, 1992; Pratt, 1991; Jain et al., 1995; Anzai, 1989).

Co-occurrence of gray values is specified in a kxk  matrix

with relative frequencies Pij (k corresponds to the number of 

gray values, i and j; correspond to index pixels). Parameters

like energy, correlation, local homogeneity, entropy, and

contrast were obtained from a co-occurrence matrix with a

direction of 08 grades and a scale of 256 different gray

values. Definitions of these parameters are:

X

i; j

Pði; jÞ2 Energy

Xi; j

ði2

m Þð j2

m ÞPij

s 2

m ¼X

i; j

iPij Correlation

Fig. 5. Polygon searching. A contour is shown with more than four

identified points. A1 and A2 illustrate the case of columns, while D1, D2 and

D3 correspond to rows. B and C show the dot limit (maximum andminimum) for rows and columns, respectively.

 A.B. Flores et al. / Micron 34 (2003) 109–118 113

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X

i; j

Pði; jÞ1 þ li 2 jl

Local homogeneity

X

i; j

Pði; jÞlogPði; jÞ Entropy

X

i; j

ði 2 jÞ2

Pði; jÞ Contrast

Analyzing texture parameters will allow the system to find

characteristics of symmetry and twins. The method is

based on splitting the polygon or the area of interest in

two equal parts. For every part a quantitative texture

measurement is obtained. If both parts are similar intexture (co-occurrence matrix parameters), it means that

the nanoparticle has symmetry or twins. Cuts are made

using vertex and center sides as references points. In cases

where the polygon method fails after reviewing all region

cuts the system does not find any symmetry or twins) cuts

are done every 150 from þp /2 to 2p /2 using the contour

obtained in the early stages of the process. Both methods

are illustrated in Fig. 6.

After all the cuts have been analyzed, the system will

find a nanoparticle with the symmetry characteristic from

the data base, only if more than 95% of the cuts have the

same parameters. In cases where twins are present in

nanoparticles, the parameters will be the same only in oneor two cases.

4.4. Image identification

The previously extracted characteristics produce a set of 

parameters that makes it possible to recognize a nanopar-

ticle from its own structure and orientation. The recognition

process is carried out in three different branches, one for

FCC nanoparticles, another for nanoparticles with twins

(icosahedron and decahedrons), and a final one dedicated

only to amorphous particles. The search split is done

because every group has a specific characteristic set and the

system will just use the set of characteristics that produces a

correct identification.

Cubic nanoparticles. Recognition is done by searchingthe following characteristics: parallel lines arrays, polyg-

onal analysis, where it is only possible to have circular or

linear regions. A more complete description of the

characteristics belonging to each group is presented in

Table 2.

 Nanoparticles with twins. Recognize nanoparticles that

belong to this group, the characteristics used are polygonal

and texture analysis, symmetry, and presence of twins. A

complete description is presented in Table 3.

 Amorphous. In this case, using only characteristics

provided by region analysis is enough for their recognition.

Since amorphous nanoparticles do not present a well defined

shape, it is not possible to find similar characteristics toanother group.

Fig. 6. Texture analysis. (a) Selecting a well defined polygon; (b) selecting a region of interest in cases where the first search fails.

Table 2

Characteristics identified and used by the proposed system in the recognition of a fcc nanoparticles

Parallel arrays Polygons Low index orientations

Cubo-octahedron Seven uniform lines with one more

line in the center of the structurea

4, 6 and 7 sides with equal lengths In side view: 22 columns of atoms.

In top view: 49 columns of atomsa

Truncated octahedron Six uniform lines, with the same lengths.

Nine uniform lines with different lengthsa6, 7 and 8 sides with equal lengths In side view: 34 columns of atoms.

In top view: 57 columns of atomsa

Tetrakai-decahedron Seven uniform lines with the same lengths.

Nine uniform lines with the same lengthsa

6 and 7 sides with no equal lengths.

8 sides with equal lengths

In side view: 43 columns of atoms.

In top view: 69 columns of atomsa

a The number corresponds to the particles used in the analysis; however this can change depending on the nanoparticle size.

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5. Results

The system was implemented using C and Halcon

developer-software. The implementation and tests were

carried out in a Pentium III 450 MHz PC-computer. To test

the proposed system 86 images were used. These images

present problems like bad contrast, noise, and bad focus in

the peripheral and overlapping atoms that will complicate a

correct identification.

In Fig. 7, the case of the cubic nanoparticle analysis is

shown. For each image, the corresponding orientation is

marked in fcc nomenclature. Fig. 7a shows the extracted

characteristics at the different orientations of the cubocta-

hedron, while in Fig. 7b and c, the cases for the truncated

octahedron and a particular tetrakaidecahedron are shown,respectively. In the figures, CO at [0,0,1] orientation shows

a well defined 908 angle polygon, while both TO and TKD

cases show 1358 angle polygons. However, the proportion

between the boundary length sides makes the identification

possible because when the size length is similar, the image

must correspond to TKD. Furthermore, in the case of the[0,1,1] orientation, it is possible to distinguish the

configuration based on the proportion of side length, having

the CO a similar proportion for each side, the TKD has a

2n 2 1 to n proportion (where n is the number of 

distinguished dots) and the TO shows a different relation.

For the rest of the orientations, the way to distinguish

between these structures is only by analyzing the roundness,

because TKD tends to have rounded profiles and CO has flat

sides. However, this recognition is not easy, since in this

group it is not possible to find presence of twins since they

show regular and symmetric images.

Results for the decahedral configurations are shown in

Fig. 8 for three cases (the pentagonal bypiramid, the Ino’sdecahedron and the truncated decahedron) in (a), (b) and (c),

respectively. The coordinates used are based on the

rhombohedral geometry. The pentagonal structures present

mainly multiples of five sides in the polygon analysis and

Table 3

Characteristics identified and used by the proposed system in the recognition of twinned nanoparticles

Twins Polygons Orientations

Pentagonal by-pyramide Twins detection in pentagons. Twins or

symmetry presence in squares

4 and 5 sides with equal

lengths

In top view: 51 columns of atoms*

Ino’s decahedron Twins or symmetry presence in all

orientations

5, 6 and 7 sides with

equal lengths

Due its structure the top view is similar

to the Pentagonal by-pyramid

Marks decahedron Twins presence in all orientations, except

in [1,1,0] where a symmetry characteristic

is presented

6, 7 and 9 sides with

different lengths

In top view: Well defined columns of 

atoms, with truncation in the corners

Symmetry in all orientarions 6 and 10 sides with length

sides

Not defined

Fig. 7. Nanoparticle identification. The examples show the main orientations for: (a) cubo-octaedral; (b) truncated octaedral and (c) tetrakaidecahedron.

 A.B. Flores et al. / Micron 34 (2003) 109–118 115

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the symmetry axes. For Dh, all the analyzed images are

decagons or rhombs, with only alterations to the proportion

of the sides, that allow the identification of small

differences. This can be seen in the decagons from [0,0,1],

[1,1,2] and [0,2,1], where the side length and internal angles

change depending on the rotation axis, tending to rhombic

polygons; they can have two symmetry axes as in the [1,1,0]orientation, while the [0,2,0] and [3,3,1] orientations show

 just one symmetry axis. This symmetry pattern evidence is

also observed for the images of I-Dh and t-Dh. However, in

I-Dh, the characteristic polygon is a symmetric hexagon and

similarly to Dh, the length and angles of the sides change

depending on the orientation. The t-Dh case also shows

close-to-rhomb polygons for these mentioned orientations.

Furthermore the I-Dh profiles tend to a pentagon in the

[1,1,2] and [0,2,1]; however there is a clear evidence of 

a error when the program cannot resolve the corners and it

looks like irregular hexagons by the edge effects. This error

is also present in the t-Dh images, where the profiles tend to

show 15 sides, but the program does not identify all thecorners. However, for bigger particles this mistake is not

observed and the polygons found have multiple sides

produced because of the negative curvature, which is

characteristic only of this kind of truncated particle

(Ascencio et al., 1998; Ascencio, 2000). The texture

analysis is similar in these configurations.

Icosahedron resolved images are shown in Fig. 9, where

the coordinates correspond to body centered orthorhombic,

which are the most suitable to this geometry. The case shows

interesting properties based on the symmetry that is

evidenced in all the profiles, which are regular hexagonswith proportioned sides with exception of the [1,1, 2 1],

which is known as the five-fold orientation. In the five-fold

orientation, the particle shows a decagon (dotted line), which

is unique. Besides thepolygonal study,the texture is different

to any other structure, mainly because it does not present any

well defined compared to the previously analyzed structures.

A commonerror in therecognitionwas to finda triangle in the

interior of the image (shown with the arrow), which can be

identifiedas a product of poor contrast in the particle contour.

The program identifiesthe internal dots as significant because

the external image details are not discrete; it looks like a

continuous pattern. Finally, in the amorphous case the image

analysis corresponded directly to no symmetry and texturedefined, producing an easy way to identify that physically

imply it real sense, the no defined patterns.

Table 4 shows the time taken by the system in the

recognition of different nanoparticles. Only two samples per

Fig. 8. Nanoparticle identification. (a) Pentagonal bipyramid [0,2,1]; (b) Ino decahedron [3,3,1]; (c) Marks decahedron [21,1,0].

Fig. 9. Nanoparticle identification of an icosahedral particle at the main orientations.

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group are shown. An average of all images showed that the

time per sample was 11.16 s. The times are not the same dueto the different searches that the system executed. Some

cases are simple, as in Truncated Octahedral [1,2,3], while

in others are more complex, as in Marks Decahedron [1,1,3].

This means that the Marks decahedron has a more complex

structure than the truncated octahedral nanoparticle.

The experimental particles recognition is well improved

with this recognition system, in the case of gold

nanoparticles, the 89% of well cleaned particles in

HREM images and when the noise over the image is

bigger, the recognition capacity is reduced. An example of 

recognition of experimental images is shown in Fig. 10, an

relatively easy identification is the truncated octahedron at

[0,1,1] orientation as shown in Fig. 10a, the no twins andsides proportion allows the system to recognize it without

problems. In the case of decahedrons, the system delayed

more in the image of  Fig. 10b, where couple of sides werelost, as can be seen in the figure, however the software

recognized it as a Marks decahedron at the [0,0,1]

orientation. In more complicated images, when the

particles are bigger, the recognition was also successful

as in the images shown in Fig. 10c and d as Ino’s

decahedrons at [3,3,1] orientation and [21,3,1] respect-

ively. In Fig. 10e, an icosahedral particle is recognized by

the system, based on the hexagonal profile and an internal

texture that clearly shows multiple twins. In the case of all

the HREM images the previous processing showed to be

critical for the optimal identification. In all cases, three

steps of the process are illustrated in order to show the

profile, texture and symmetry search and the final foundstructure for each cluster.

Table 4

Processing time for the case of representative nanoparticles. Two samples are shown for each group

Nanoparticle (orientation) Processing time (s) Nanoparticle (orientation) Processing time (s)

Cubo-octahedron [0,1,1] 15 Ino Decahedron [1,1,3] 25

Cubo-octahedron [1,1,3] 15 Ino Decahedron [-1,2,0] 15

Truncated octahedron [0,1,1] 11 Marks Decahedron [1,1,0] 25

Truncated octahedron [1,2,3] 5 Marks Decahedron [1,1,3] 23

Tetrakaidecahedron [0,1,1] 15 Icosahedron [1, 2 1,1] 15

Tetrakaidecahedron [1,0,4] 5 Icosahedron [21,3,1] 15

By-pyramide [0,2,1] 12 Amorphous [0,0,1] 10

By-pyramide [0,2,0] 13 Amorphous [1,0,0] 10

Fig. 10. Examples of nanoparticle identification for experimental images. (a) Truncated octahedron at [0,1,1], (b) Marks decahedron at [001], Ino’s decahedron

at [3,3,1] and [21,3,1], and finally an icosahedron at [1, 2 1,1] orientation.

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6. Conclusions

A system that allows the recognition and locating

characteristics of HREM images of nanoparticles was

presented. The structure of the system was found with the

help of digital image analysis and processing. Techniques

like co-occurrence matrix (texture analysis), morphological

operators, dynamic threshold, and region analysis were

used together with the polygon, symmetry and twins-

detection algorithms in the characteristics search and

identification process. The use of texture was well suited

for the analysis and characterization of symmetry and

twins, especially in images with difficult problems. The

results presented show the efficiency and efficacy of the

system.

A search for new characteristic is proposed for afurther work using another source of information, where

illuminations, contrast, defocus could be characterized for

every nanoparticle studied. Another alternative is the

inclusion in the system of 3D computer vision techniques

to quantify the depth of the nanoparticle, obtaining

information about its orientation and how it is mounted

on the substrate.

After reading all the images, the present system could

recognize 92% of the set and from experimental images of 

several different elements. Some images that were not

identified by the system have an abundance of the problems

mentioned above; therefore it was difficult therefore to find

those discriminating characteristics that would produceidentification. This system can be applied for nanoparticles

from different elements and even for bimetallic clusters,

where the contrast has an extra parameter fixed from the

differences of scattering from each element, however after

an contrast improving, the identification can be obtained and

also the parameters from other crystalline systems can be

included from the manipulation of the geometrical con-

sideration of external shape and internal texture. This last

condition allows this pattern recognition system to be

parameterized and improved for other cluster types.

References

Andres, R.P., Bein, T., Dorogi, M., Feng, S., Henderson, J.I., Kubiak, C.P.,

Mahoney, W., Osifchin, R.G., Reifenberger, R., 1996. Coulomb

staircase at room temperature in a self-assembled molecular nanos-

tructure. Science 272, 1323.

Anzai, Y., 1989. Pattern Recognition and Machine Learning, Academic

Press, Boston.

Ascencio, J.A., Gutierrez-Wing, C., Espinosa, M.E., Marın, M., Tehuaca-

nero, S., Zorrilla, C., Jose-Yacaman, M., 1998. Structure determination

of small particles by HREM imaging: theory and experiment. Surface

Sci. 396, 349.

Ascencio JA. PhD Thesis Disertation. ININ-UAEM, Mexico; 2000.

Del Bimbo, A., 1999. Visual Information Retrieval, Morgan Kaufmann,

California.

Haralick, R.M., Shapiro, L.G., 1992. Computer and Robot Vision, vol. 1.

Addison-Wesley, Massachusetts.

Jain, R., Kasturi, R., Schunck, B.G., 1995. Machine Vision, McGraw-Hill,

New York.

Jose-Yacaman , M., 1 99 6. H ig h Res ol ut io n T EM S tu di es o f  

Nanocrystalline Materials Processing and Properties of Nano-

crystalline Materials, Minerals, Metals and Materials Soc (TMS),

pp. 145– 151.

Jose-Yacaman, M., Ascencio, J.A., 2000. Electron Microscopy and its

Application to the Study of Archaeological Materials and Art

Preservation, Analytical Methods in Art and Archeology. Chemical

Analysis Series, vol. 155. Wiley, New York.

Pratt, W.K., 1991. Digital Image Processing, Wiley, New York.

Schaf, T.G., Schafgullin, M.N., Khoury, J.T., Vezmar, I., Whetten, R.L.,

Alvarez, M.M., First, P.N., Gutierrez-Wing, C., Ascencio, J.A., Jose-

Yacaman, M., 1997. Isolation of smaller nanocrystal Au molecules:

robust quantum effects in optical spectra. J. Phys. Chem. B 101, 7885.

Van Heel, M., Frank, J., 1980. Classification of particles in noisy electron

micrographs using correspondence analysis. In: Gelsema, E.S., Kanal,

L.N. (Eds.), Pattern Recognition in Practice, North-Holland, New York,

pp. 235–243.

Williams, D.B., Carter, C.B., 1996. Transmission Electron Microscopy: A

Textbook for Materials Science, Plenum Press, New York.

 A.B. Flores et al. / Micron 34 (2003) 109–118118


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