International Journal of Engineering and Technical Research (IJETR)

ISSN: 2321-0869, Volume-2, Issue-11, November 2014

Polyfunctional Nanostructured Composite Materials

for LED Technology
Alexander A. Ivanov, Anatoly G. Filimoshkin, Vladimir V. Botvin, Ivan A. Shulepov

The main disadvantages of the said compositions are as

Abstract New alumosilicate filled with aluminum follows: high cost, limited selection of support bases (SB) for
oxyhydroxide (AlO(OH)) is offered as a dielectric substrate (DS) LED devices whose surface can be applied on by the
for LED devices. Obtained from these substances the DS have dielectric compositions (DiC), high sintering temperatures, as
high thermal conductivity up to = 133.61 W/mK, whose value well as the use of costly equipment for production.
depends on the amount of AlO(OH) in the DS. High thermal
Manufacturers of LED devices constantly require more new
conductivity is achieved by homogeneous distribution of a large
number of AlO(OH) nanosize particles in the crowns of the
functional composite materials (CM). The need for new
dendrimer alumosilicate ensembles. The size of the AlO(OH) highly resistant to the mechanical stress and aggressive
particles is comparable to that of the voids between the environments, to various types of radiation and high vacuum
branches in the alumosilicate crowns. As a conductive adhesive or high pressure, resistant to high or low temperatures
for fixing of LED chips on the DS the copolymer of vinyl functional CM encouraged the scientists to look for new
chloride-maleic anhydride, nano- and microparticles of silver approaches to the synthesis of the polymers and creation of
(70 wt. %) composite is offered, the volume resistivity of the special composites that meet these requirements. Traditional
wirings being up to 3.110-8 Ohmm. Adhesive strength of the synthetic methods for obtaining the CM do not always allow
filled alumosilicate (80% of AlO(OH)) applied under shear on
achieving the required performance. This, in particular,
the aluminum plate (its roughness to be 11.3 mkm) is 47 N/mm2.
applies to those cases where the structuring of the materials is
Index Terms Composite materials, nanostructures, carried out by nanoparticles.
intermolecular interactions, supramolecular structures, sol-gel The first goal is to develop a controllable chemical
products, macromolecular conformations, dielectric synthesis directly during formation and modification of the
composition, conductive polymer composition, LED bar. CM properties, as soon as the phase, nanostructural and other
features that define physical, mechanical, chemical and
I. INTRODUCTION service properties of the products are being programmed at
the very stage of the synthesis. It is not always possible to
obtain nanostructured CM of desired stoichiometry,
Undoubted advantage of LED devices over other sources
homogeneity, high purity and those of specific microstructure
of light is their unique opportunity of usage in information
using classical methods of the synthesis. It is true especially
technology, different types of lighting and in advertising
in those cases when polyfunctional materials with special
design. The basic requirement for the modern market of LEDs
consumer properties are required [1-3].
and LED technology is increasing of the light flux and life,
The second goal requires a special approach to the
heat dissipation, as well as reducing of energy consumption.
formation and producing of both the conductive and dielectric
Achieving these characteristics is possible only by using new
components of LED devices. The FILAMENT COB LED
composite materials and modern technologies. Primarily, this
lamps e.g., have LED bars of new ceramic-based generation.
requirement concerns dielectric substrates (DS) of the LED
The LED crystals are pasted on the LED bars with sequential
bars.
ultrasound splicing. At the end the contacts are to be
Market analysis suggests that the most available conductive withdrawn and the device to be embedded into proper
composition now is the EPO-TEK H20E-175 of the EPOXY luminophore. Such LED bars have an advantage over the
technology company with electrical resistivity of 410-6 polymer bars, which melt at the sealing of the glass bulb.
Ohmm. Namics and Ferro companies offer silver-pastes of However, the ceramic bars are not without drawbacks as well,
high thermal conductivity and of low electrical resistivity. because made of Al oxide by means of high temperature
Dielectric adhesives having thermal conductivity up to 2.4 sintering, the ceramic base has insufficient heat conductivity
W/mK and adhesion strength of 25 N/mm2 are available (24 30 W/mK).
from Namics and Dow Corning. The aim of the work is to develop new approaches to
manufacture of LED bars with high thermal characteristics,
Manuscript received November 17, 2014.
differing by the structure of composite materials of the
Alexander A. Ivanov, Chemical Faculty, Department of Physical dielectric substrate and by structure of the new mixtures of
Chemistry, National Research Tomsk State University, Tomsk, Russian substances to paste crystals on them.
Federation, 8-923-415-70-28.
Anatoly G. Filimoshkin, Chemical Faculty, Department of Physical
Chemistry, National Research Tomsk State University, Tomsk, Russian
Federation. II. MATERIALS AND EXPERIMENTAL PROCEDURES
Vladimir V. Botvin, Chemical Faculty, Department of Physical
Aluminum was chosen as a high thermal conductivity
Chemistry, National Research Tomsk State University, Tomsk, Russian
Federation. material for the SB of LED bars. The DiC applied on Al
Ivan A. Shulepov, National Research Tomsk Polytechnic University, surface of the SB, represents alumosilicate filled with Al
Tomsk, Russian Federation,

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 Polyfunctional Nanostructured Composite Materials for LED Technology

oxyhydroxide, which improves heat transfer to the SB was determined by the laser flash (the Parkers method). It is
extending the life of the LED light source in general. based on homogeneous pulsed heating of the sample, the
pulse tending to zero pulse duration, so that all the light
III. FILLED ALUMOSILICATE AS DIELECTRIC energy is absorbed instantly. Thermal conductivity
SUBSTRATE (W/mK) was calculated by the formula
(T) = a(T) (T) p(T),
It was mentioned, that alumosilicate filled with aluminum where: T temperature; a, cm2/s - thermal diffusivity; ,
oxyhydroxide was investigated and offered as the DS. Its g/cm3- bulk (true) density; Cp, J/kgK - specific thermal
sol-gel synthesis was carried out from preliminarily prepared capacity. The thermal diffusivity a is determined by the
oligomeric alumosilicates [4, 5]. Conformational analysis of Parkers method and heat capacity Cp - by the LFA 467 device
the latter by quantum-chemical method allowed us to find of NETZSCH company relative to the reference sample.
synthetic approaches to obtain alumosilicates with desired Experimental samples of alumosilicate filled with different
dendritic micro structure (dendrimer supramolecular AlO(OH) content were prepared in the form of cylinders with
structure) (Fig. 1) at the very stage of DS formation [6]. a diameter of 12.7 and a height of 2 mm.
Dendrimer alumosilicate has a highly branched Mathematical analysis of thermal diffusivity was carried
supramolecular structure which consists of a large number of out by a special program that uses a set of differential
interlacing short alumosilicate twigs resembling a tree mathematical models for different applications. The thermal
crown (Fig. 1a). Such supramolecular structure allows one to diffusivity a was calculated under adiabatic conditions by the
place an enormous number of nano- and microparticles of equation
aluminum oxyhydroxide (AlO(OH)) in the voids between the
l2
twigs (Fig. 1b). a 0.1388
t50
where a, m2/s - thermal diffusivity; l, m - sample thickness;
t50, s - time corresponding the temperature increase by 50%,
relative to the temperature of the rear wall of the sample.
Special program allows one to control the process of
measuring and to evaluate the results, both in manual and
fully automatic regime. Parameter t50 of the sample 1 is 11 s;
of the sample 2 5 s, and of the sample 3 0.95 s (the height
of all samples is the same: l = 0.002 m).
The volume (true) density was determined by gravimetric
method using a pycnometer; it was calculated by the formula
() mf

m m1 m2

where m, g weight of the sample; f ,g/cm3 density of the

liquid; m1,g weight of the volume meter with the material;
m2, g weight of the volume meter with the liquid and the
material.

Table 1. Heat conductivity parameters of the alumosilicate

samples with different filler contents (60, 70 and 80 wt.%)
measured by the Parkers method

(b)

Figure 1. Electron microphotographs of highly branched Sample number AlN

Parameters

dendrimeric sol-gel alumosilicate (a) and of AlO(OH) (b) to (fraction of the filler, wt.%) sintered at
1 2 3 high
be placed in between the crowns of the dendrimer ensembles. (60) (70) (80) temperature
is the
The distribution of the AlO(OH) microparticles in the crowns Reference
of alumosilicate dendrimers was performed by means of Sample
mechanochemical mixing followed by ultrasonic treatment
[7]. p (kg/m3) 3171 3197 3220 3280
The volume sizes of AlO(OH) are comparable with voids a (m2/s) 5.0510-6 11.110-6 58.4410-6 74.210-6
683 695 710 740
sizes between the branches (twigs) of alumosilicate crowns (J/kgK)
(Fig. 1b), which allows one to distribute the filler particles in 10.93 24.67 133.61 180
between the twigs and the crowns. Formed from these (W/mK)
systems, the DS have high thermal conductivity, whose value

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-11, November 2014
The maximal thermal conductivity ( = 133.61 W/mK) morphology of the CPC, i.e. can change the size and
corresponds to sample 3 with aluminum oxyhydroxide in the volume geometry of the interdomain voids acting as
amount of 80 wt.% which is optimal, if one takes into account accumulators of the electro conductive metal particles.
all other qualifying standards for the DiC. Moreover, the unique property of VC-MA macromolecules is
Comparison of the properties of the sample 3 with the their ability to increase its affinity for the surface of silver or
properties of AlN leaves no doubt about the possibility of aluminum nanoparticles due to spontaneous formation of
commissioning such LED bars. It is interesting to note, that 6-en structural units in the specific sections lengthwise the
commercial DiC Prolimatech PK-3 has the highest thermal macromolecules [8]:
conductivity (11.2 W/mK), which is nearly 12 times less
than that of sample 3 (Table 1). The commonly used DiC is
Namics XS8472, whose thermal conductivity ( = 2.4
W/mK) is almost 56 times less than that of sample 3 (Table
1).

IV. CONDUCTIVE POLYMER COMPOSITION AS AN

ADHESIVE FOR FIXING LED CHIPS ON DIELECTRIC
SUBSTRATES

Compositions based on conductive fillers and synthetic

polymer matrices are widely used as adhesives in almost all
LED devices. It is glued joints (interfaces) are in major causes
become the cause of these devices failures. In the first place Polar 6-en units increase adhesion of Ag agglomerates
this happens in the power switches operating under frequent towards the [~6-en ~] structural units located on the interface
cyclic on-load operation. The failure probability of the LED of the microparticles of Ag agglomerates and the domains
module increases exponentially with temperature increase. formed from macromolecules of VC-MA copolymer. In other
Reliability of the LED devices operation depends directly on words, presence of polar 6-en units impedes to "exude" the
heat dissipation from the chips. In other words, the microparticles out from the wirings and promote their
composition linking the crystals with the DS must have low permanent residency in the microvoids by means of strong
electric resistivity and good thermomechanical properties. intermolecular interactions. It is possible to select conditions
to control the morphology of the CPC using the package
In order to place crystals on the DS with silver containing
GAUSSIAN98 and results of hydrodynamic experiments.
composites low-temperature sintering technology (LTST) is
One of the examples is described in detail in paper [8].
used. It allows one to improve the reliability of LED modules
Visual evaluation of the microvoids geometry, as
under high temperature cyclic effects. Nano- and micro
accumulators for the electro conductive microparticles of Ag,
powders of aluminum, nickel, copper, silver, gold and
is represented illustratively in Figure 2, which clearly shows
platinum are used as the conductive components in the
that extended microvoids are formed in the VC-MA films
adhesive compositions. The desire to reduce the cost of
cast from tetrahydrofuran (Fig. 2a), while in the films cast
conductive pastes and adhesives leads to numerous attempts
from ethyl acetate (Fig. 2b) such structures are not formed at
to replace expensive metals. Sometimes, in order to reduce
all, other things being equal. In other words, the most
the cost of adhesive composites they use silver-plated copper
spacious microvoids for settlement of the silver particles are
or silver-plated nickel which does not always leads to the
formed in those solvents where the macromolecules are
desired results. In order to compare the effectiveness of nano-
uncoiled maximally. Tetrahydrofuran is such a solvent for
and micro silver powders obtained by two different methods,
VC-MA copolymers and microparticles of Ag.
i.e. by electroexplosion and by electrical discharge of silver
granules in chemically different solvents. Comparison was
carried out with aluminum and copper powders [7].
The results of thermogravimetric, dilatometric and thermal
measurements of the powders mentioned allowed to find a
method for producing a powder with the lowest sintering
temperature. Such powders are obtained by electroerosion
treatment of silver grains in water, and they may be used in the
LTST up to the degradation temperature of the polymer
matrix [6].
The vinyl chloride-maleic anhydride copolymer (VC-MA)
possessing good film forming properties and high adhesion to
metals, as the polymer matrix for the conductive polymer
compositions (CPC), was used. Amphiphilic macromolecules
of the VC-MA copolymer are flexible enough in such
solvents as dioxane, tetrahydrofuran, acetone,
dimethylformamide, alcohols, water and others. Their
flexibility changes considerably in their midst. By varying the ()
flexibility of macromolecules in solution one can control the

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 Polyfunctional Nanostructured Composite Materials for LED Technology

(b) (b)
Figure 2. Microphotographs of pure VC-MA films cast from Figure 3. Electron microphotographs of the surface of the
tetrahydrofuran () and from ethyl acetate (b). Magnification CPC, containing VC-MA copolymer as a polymeric matrix
480. (a) and nano- and microparticles of silver dispersed therein
(b)
Further to evaluate the continuity of the wirings in the CPC
we have investigated the surface topology of the CPC (Fig. 3) It is interesting to note that the specific electrical volume
by high resolution electron microscopy with secondary resistance of the wirings with 70 wt% of Ag is 3.110-8
double-beam electron field emission on the scanning Ohmm, being close to that of pure silver, whose electrical
electron-ion SMAQuanta 3D FEG microscope; the resistance measured under the same conditions is 1.610-8
accelerating voltage and the scale are shown in the pictures. Ohmm. Obviously, the wirings formed under conditions
Comparison of the size of structures on the surface of the described in [6] have continuous morphology. Microvoids of
CPC in Fig. 3 a and b suggests formation of continuous the polymer matrix display interconnected hollow channels
topology of conductive silver tracks or wirings. However, a populated by nano- and microparticles of silver, forming
definite answer to the question of the continuity of the continuous dense conductive wirings. It is interesting to note
conductive wirings can only give the experimental value of that the geometry and dimensions both of the domains and of
electrical resistivity. We measured the electrical resistivity of the interdomain voids can be diverse and even intricate [9,
about 20 samples of different conductive topologies 10].
containing from 50 to 70 wt.% of Ag by the four-probe The CPC from EPO-TEK H20E-175 EPOXY technology
method (Table. 2) and calculated the values of volume firm has electrical resistivity of 410-6 Ohmm, which is two
resistivity by the formula orders higher than that of the CPC with 70% of silver we have
RS obtained (3.1010-8 Ohmm).

l , Table. 2. Electrical resistance of the CPC with different
where R, Ohm resistance; l, m length between contacts; S, content of nano- and microparticles of silver
m2 is the cross-sectional area calculated by S = bd, where b, m
the track width; d, m track height. Sample (fraction of
nano-, micro-particles of R, * 108,
silver in the CPC, wt.%)

1 (40) 2.15 34000

2 (40) 2.06

3 (40) 2.07
4 (50) 0.0199 322
5 (50) 0.0204

6 (50) 0.0192
7 (60) 0.00175 28.8
8 (60) 0.00181
9 (60) 0.00177
10 (70) 0.000168 3.1
11 (70) 0.000201
12 (70) 0.000202
()

187 www.erpublication.org
 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-11, November 2014
* , Ohmm volume resistivity of the wirings formed [5] P. Duran, M. Villegas, F. Capel // J. Europ.Ceram.Soc. 1996. vol. 16, No.
9, pp. 945952.
in the CPC, the average of three measurements; R, Ohm
[6] A. A. Ivanov, V. V. Botvin, A.G. Filimoshkin. A New Technology for
resistance of the wiring; d = 0.00065 m the height Forming Highly Developed Aluminum Surface by Electric Pulse
(thickness) of the wiring; b = 0,005 cm width of the Ablation // Russian Journal of Applied Chemistry. 2013. vol. 86, No. 9,
wiring; l = 0.02 m the length between the contacts. The pp. 13171325. DOI: 10.1134/S1070427213090016.
height (thickness) of the wirings formed in the CPC was [7] A. A. Ivanov, V. V. Botvin, A.G. Filimoshkin. Dendrimer
Polyaluminosilicates as a Matrix for Filled Coatings Russian Journal of
determined on the eddy current thickness meter Applied Chemistry, 2014, vol. 87, No. 2, pp. 135140. DOI:
QuaNix 1500 10.1134/S1070427214020039.
[8] A. G. Filimoshkin, G. A. Terentieva, E. M. Berezina, T. V. Pavlova/
It should be added that the most important performance Novel Behavior of Copoly(vinylchloride-maleic anhydride) // A
Journal of Polymer Science, Part A: Polymer Chemistry. 1993. vol. 31,
characteristics of the DiC and the CPC include not only the pp. 1911-1914. DOI: 10.1002/pola.1993.080310731
electrical resistance and thermal conductivity, but the [9] A. G. Filimoshkin, V. F. Kosolapova, E. B. Chernov, E. M. Berezina, T.
adhesion strength as well. Thus, the adhesion strength of one V. Petrenko. Novel features of copoly(vinylacetate-maleic anhydride)
of the most common dielectric compositions Namics XS8472 microstructure // European Polymer Journal. 2003. vol. 39,
pp.14611466.
is equal to 25 N/mm2, which is not sufficient for reliable [10] A. Filimoshkin, E. Berezina, V. Manzhay, A. Kuchevskaya, A. Ivanov.
performance of the devices in many cases. // e-Polymers. 2011. No. 56, pp. 1-14. http://www.e-polymers.org
In order to determine the adhesion strength under shear on ISSN 1618-7229
the interface of the DiC, obtained from alumosilicate with [11] A. A. Ivanov, V. V. Botvin, A.G. Filimoshkin. Adhesion Strength of
Filled Polyaluminosilicates on Aluminum Surface // Russian Journal of
AlO(OH) as a filler, and the aluminum SB we have carried Applied Chemistry. 2014. vol. 87, No. 2, pp. 141150. DOI:
out preliminary studies with varying roughness of many 10.1134/S1070427214020040.
aluminum SB. Adhesive strength of 80% filled alumosilicate
applied on the aluminum plate with 3.11 microns degree of
roughness is equal to 47 N/mm2 [11]. For comparison, Alexander A. Ivanov is Postgraduate of Chemical Faculty, Department
adhesion strength of the alumosilicate applied on a smooth of Physical Chemistry, National Research Tomsk State University. Research
surface (0.05 microns roughness) is equal to 19 N/mm2. interests include investigation of new polymer composite materials.
Adhesion strength of a series of SB, both of different Anatoly G. Filimoshkin is Doctor of Chemical Science, Professor of
National Research Tomsk State University. Research interests include
degrees of roughness and of different nature of their surfaces investigation of synthetic polymers and copolymer.
are under study. Vladimir V. Botvin is Undergraduate Chemical Faculty, Department of
Physical Chemistry, National Research Tomsk State University. Research
V. CONCLUSION interests include investigation of new polymer composite materials.
Ivan A. Shulepov is Candidate of physico-mathematical science, design
engineer of the 1-st category Center of Measurements of Materials Properties
1. Dielectric composite material based on aluminum of National Research Tomsk Polytechnic University.
silicate filled with aluminum oxyhydroxide having high
thermal conductivity up to 133.61 W/mK and large adhesion
strength is obtained. It can be used for manufacturing of
light-emitting diode matrices.
2. A new conductive polymer composition, based on
mixture of vinyl chloride-maleic anhydride copolymer with
silver nano- and microparticles, can be used as adhesive for
placing LED crystals on dielectric substrates. The conductive
adhesive material has a low electrical resistivity up to 3.110-8
Ohmm, which approaches to the resistance of pure silver
(1.610-8 Ohmm).

ACKNOWLEDGEMENT

This work was supported financially by the Ministry of

Education and Science of Russia in the framework of the
project RFMEFI57714X0061.

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