Characteristics of colloidal copper particles

prepared by using Polyvinyl pyrrolidone (PVP)

and Polyethylene glycols (PEG) in chemical
reduction method
Chinh Dung Trinh
1
Dung !y Thi Dang
1
Tuyet Thu Thi "e
1
Eric
#ribourg$%lanc
&
'oang %a "e Tran
1
and Chien !au Dang
1
1
"aboratory for (anotechnology Vietnam (ational )niversity 'o Chi
!inh City Community * "inh Trung +ard Thu Duc District 'o Chi
!inh City Vietnam, Email- dtmdung.vnuhcm/edu/vn
&
CE0$"ET1 !1(0TEC Campus 12 rue des !artyrs 34567 Grenoble
Cede8 9 #rance
0bstract
A simple chemical reduction method is used to prepare colloidal copper nanoparticles. In this
method we use polyethylene glycols (PEG) and polyvinyl pyrrolidone (PVP) as stabilizer size
controller and capping agents and !a"#$ as the reducing agent .%he obtained copper
nanoparticles were characterized by powder &'ray di((raction ()*+) transmission electron
microscopy (%E,) and -V'visible spectrophotometry (-V'vis). %he main purpose o( this paper
is to report about the large improvement in replacing PEG by PVP in the reduction synthesis o(
copper nanoparticles. .rom the %E, results we (ound that colloidal copper nanoparticles
prepared by using PVP and PEG are well'dispersed and (rom the -V'vis results sur(ace plasmon
pea/ is very stable over time at 012 nm whereas when using (PEG) the pea/ shi(ts (rom 012 to
034 nm. %his comparison also shows that copper nanoparticles in the solution using (PVP) have
smaller size and the uni(ormity o( their distribution in particle size is better. %hen it is observed
that the o&idation time o( copper nanoparticles at room temperature (or solution using (PVP) is
over twenty days while solution using (PEG) ta/es place in two days. %he protection level
provided by PVP is there(ore much higher than with PEG.
:ey;ords- copper nanoparticle inert gas protection solvents chemical synthesis
1/ 1ntroduction
In recent years metallic and
semiconductive nanoparticles have been
widely investigated. In nanostructure
(orm materials e&hibit speci(ic
properties not present in their (orm.
!anoparticles are studied (or a long time
and almost all monoatomic materials
including gold 52$6 silver 5276 or copper
521'236 due to their potential
applications as optical sensors 5226
biological labels 528 496 or conducting
deposits 5426.
!owadays according to the new trend o(
electronic industry metallic
nanoparticles are used to ma/e
conductive in/s 5296 that can be used to
print electrical paths on di((erent types
o( substrates. %here have been many
success(ul studies on in/s based on
silver (Ag) as metallic nanoparticles.
:ilver nanoparticles have many special
characteristics that are o( great
advantage to ma/e and preserve in/.
#owever the limitation o( silver nano
in/ is o( having a high cost ma/es it
di((icul in developping widespread
products. %here(ore we have been
studying the replacement o( Ag
nanoparticles by copper nanoparticles in
order to reduce the production cost o(
in/. %here are many methods (or copper
nanoparticles synthesis including
chemical reduction 54 76 thermal
decomposition 5$ 06 polyol 52 16 laser
ablation 536 electron beam irradiation
5;6 and in situ chemical synthetic route
586. <e have succeeded in ma/ing
copper nanoparticles with an average
diameter o( less than 29 nm by chemical
reduction method. #owever ma/ing
copper nanoparticles (or use in
conductive in/ presents many
di((iculties which stem (rom peculiar
properties o( copper such as= easy
agglomeration (ast o&idation in
atmosphere and low stability o( copper
nanoparticles in solution. %here(ore
(ollowing our previous study 5re(6 we
modi(ied the capping agent (PEG) (or
PVP in the chemical reduction synthesis
in order to study its e((ect on the
properties o( copper nanoparticles.
2. Experimental
2.1 Material
All chemicals were analytical grade as
purchased and used without (urther
puri(ication. >opper (II) sul(ate
pentahydrate salt >u:?
$
.0#
4
? with
8;.9 @ 294.9 A in purity (,erc/) was
dissolved in deionized water.
Polyethylene glycol 1999 (PEG 1999 '
,erc/) and Polyvinyl pyrrolidone (PVP
average molecular weight o( $9 999)
were used as the capping agent. :odium
borohydride (!a"#
$
' *eagent Plus
88A :igma'Aldrich) was used as the
main reducing agent while ascorbic acid
(88.3A Prolabo) was used as
antio&idant o( colloidal copper. :odium
hydro&ide !a?# (B 8;A >hina) was
also used to adCust the p# and accelerate
the reduction reaction in water.
2.2 Synthesis of copper
nanoparticles
2.2.1 Using PVP 40000
>opper (II) sul(ate pentahydrate salt
>u:?
$
.0#
4
? (9.92 ,) is (irst dissolved
in deionized water to obtain a blue
colored solution. %hen polyvinyl
pyrrolidone (PVP) $9999 (9.997,) is
dissolved in water and added to the
aDueous solution containing the copper
salt while vigorously stirring. Ascorbic
acid (9.94 ,) and sodium hydro&ide
(9.2 ,) are dissolved in water in a
separate bea/er and added to the
synthesis solution. >olor change
occurres in the aDueous phase (rom
white to yellow. %his solution was
stirred (or 89 minutes. .inally a solution
o( !a"#
$
(9.2 ,) in deionized water
was prepared and added to the solution
under continuous rapid stirring. An
instant color change occurred in the
aDueous phase (rom yellow to violet.
%he mi&ture was (urther stirred rapidly
(or around 29 minutes at ambient
atmosphere to allow the reaction to
complete.
&/&/& )sing PEG *555
<e prepared ascorbic acid solution by
dissolving ;.; mg o( PEG in 0 ml o(
deionized water. At the same time a
solution o( copper (II) sul(ate
pentahydrate >u:?
$
E 0#
4
? (9.92 ,) in
deionized water was prepared separately
and added to the solution o( ascorbic
acid under strong magnetic stirring. PEG
1999 was then poured (ollowed by the
dropwise addition the solution o( !a?#
(9.2 ,) in deionized water to adCust the
p# up to 24. %he mi&ture was stirred at
room temperature (or about 20 minutes.
%hen a solution o( !a"#$ (9.2 ,) in
deionized water was added to the
mi&ture under continuous strong stirring
(or about 29 min in order to complete the
reaction.
2.3 Characteriation
:ynthesized samples were studied by
-V'vis absorption spectroscopy (rom a
double'beam spectrophotometer (Varian
>ary 299) in the wavelength range (rom
289 to 2299 nm. Particle size was
studied by using %ransmission Electron
,icroscopy (%E,). :amples (or %E,
measurements were suspended in
ethanol and ultrasonically dispersed.
+rops o( the suspensions were placed on
a copper grid coated with carbon.
3/ <esults and discussion
3/1/ =tability
-V'vis absorption spectra o( copper
nanoparticles are shown in Fgure 2 (PEG
capping) and 4 (PVP capping). %he
plasmon absorption band (or copper
nanoparticles has been reported to be in
the range o( 099@199 nm 5246. In the
present study we have been able to
prepare sur(ace capped copper
nanoparticles and it is shown that the
sur(ace plasmon resonance can be
maintained over time. %he spectra were
measured immediately a(ter synthesis
then a(ter 2 day 4 days and 7 days (rom
sample preparation. .or the PVP case
the spectra were measured immediately
a(ter synthesis and a(ter 2 day 4 days 7
days and 49 days (rom sample
preparation.
0
0.3
0.6
0.9
1.2
1.5
400 450 500 550 600 650 700
Wavelength (nm)
A
b
s
o
r
b
a
n
c
e

(
a
.
u
)
After 20 a!s
0
0.3
0.6
0.9
1.2
1.5
400 450 500 550 600 650 700 750
Wavelength (nm)
A
b
s
o
r
b
a
n
c
e

(
a
.
u
)
"mme#atel!
After 1 a!
After 2 a!s
After 3 a!s
0
0.5
1
1.5
2
2.5
450 500 550 600 650 700 750
Wavelength (nm)
A
b
s
o
r
b
a
n
c
e

(
a
.
u
)
"mme#atel! After 1 a!
After 2 a!s After 3 a!s
#ig/1 %he -V'vis spectra o( colloidal copper nanoparticles synthesized in solution
prepared with (PEG) at di((erent times.

#ig/& %he -V'vis spectra o( colloidal copper nanoparticles synthesized in solution
prepared with (PVP) at di((erent times. %he insert is the -V'vis spectra o( the colloidal
copper nanoparticles a(ter 49 days.
Table 1. Plasmon resonance o( colloidal copper nanoparticles synthesized in solution
prepared with (PEG) at di((erent times.
1mmediately
after synthesis
after 1 day after & days after 3 days
Colloidal copper
nanoparticles
prepared ;ith
PEG
01; 013 039 unidenti(ied
Table &. Plasmon resonance o( colloidal copper nanoparticles synthesized in solution
prepared with (PVP) at di((erent times.
.ig. 2 and %able 2 show that colloidal
copper nanoparticles in solution
prepared with PEG absorbed at 01; nm
013 nm and 039 nm wavelength (or the 7
measurements. ?n the third day pea/s
o( the spectra disappeared. %his means
that colloidal copper nanoparticles in
solution prepared with PEG are only
protected within 4 days. .rom the third
day they are almost o&idized completely
as seen by a blac/ agglomerate at the
bottom o( the container. .ig 4 shows that
the aborption o( copper nanoparticles
synthesized with PVP as capping agent
display a broadband behavior especially
toward smaller wavelengths. As shown
in table 4 the plasmon pea/ is stable one
day a(ter synthesis at 012 nm. According
to the attached chart in .ig 4 there still
is an absorbing pea/ at 034 nm
wavelength on the twentieth day despite
less pronounced. %his proves that
colloidal copper nanoparticles prepared
using PVP as capping agent present
much better stability over time. <ith
PVP acting as a capping agent 52;6
copper nanoparticles seem to be
protected against o&idization over time.
.ig.2 also shows that the intensity o( the
spectra pea/s tends to decrease over
time. %his means the number o(
absorption center (colloidal copper
nanoparticles) decreases over timeG it
also means that colloidal copper
nanoparticles prepared with PEG are
only well protected at the beginning but
Duic/ly start to modi(y in solution. In
.ig.4 the intensity o( the spectra pea/s
increases over time in the (irst days a(ter
1mmediately
after synthesis
after 1 day after & days after 3 days
Colloidal copper
nanoparticles
prepared ;ith
PVP
039 012 014 012
synthesis. %his might be related to a
slow evolution o( the nanoparticles
which are not completely stabilized a(ter
synthesis. %his is then (ollowed by a
decrease o( the intensity o( the plasmon
pea/ which we thin/ is slowly wea/ened
by o&idation o( copper nanoparticles.
3/& )niformity and dispersity

#igure 3 %ransmission electron micrographs o( >u nanoparticles synthesized in solution
using PEG
:
i
z
e

d
i
s
t
r
i
b
u
t
i
o
n

(
A
)
0
2
4
6
8
10
12
14
16
18
20
0 10 20 30 40 50
Particle size (nm)
#igure 7 %ransmission electron micrographs o( >u nanoparticles synthesized in solution
using PVP
In (igure $ the copper nanoparticle
particularly are rather de(ined. "ut on
the opposite the particles in (igure 7
cluster together to become hardly
distinguishable. %he size distribution
diagram was determined manually by
de(ining by hand the nanoparticles (rom
the %E, picture using contrast. .rom
the above observation we see that the di
stribution o( copper nanoparticles in
solution using PVP is better than in
solution using PEG. %his is an
interesting improvement to the
application o( copper nanoparticles in
the (uture manu(acture o( conductive
in/.
.rom the two diagrams o( particle size
distribution o( .igure 7 and $ it can be
e&tracted that the copper nanoparticles in
solution using PEG and PVP have an
average diameter o( o( 43 nm and 24 nm
respectively. .urthermore the particle
size distribution o( nanoparticles in the
sample using PVP is narrower than the
sample using PEG.
.rom diagrams in .igure 7 and $ we can
see that there is well'uni(orm in copper
nanoparticles in the two samples. %he
dispersity in sample using PVP is better
than in sample. In sample using (PVP)
the amount o( particles having size at
29nm 24nm 2$nm and 21nm mainly
whereas particles with di((erent sizes
hold insigni(icant portion. In the sample
0
5
10
15
20
25
30
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
: i z e
d i s t r
i b u t
i o n
( A )
Particle size (nm)
using (PEG) as capping agent the size o(
particles is more diversi(ied and uneven
than in sample using (PVP). <e can
conclude that in sample using (PVP)
copper nanoparticles have better
dispersity than in sample using (PEG).
7/ Conclusion
In this paper copper nanoparticles were
success(ully synthesized by chemical
reduction method with 4 di((erent
capping molecules namely PEG and
PVP. -sing PVP as a capping agent
showed an interesting improvement in
the stability over time in solution at
ambient atmosphere and in dispersity.
>ompared to PEG capped nanoparticles
the PVP copper nanoparticles show a
ten'(old improvement in time stability/
+espite this can not be considered
enough (or a real world application in
conductive in/ synthesis it lays the
ground (or (uture development towards a
better control on copper nanoparticles
synthesized by chemical reduction.
0c>no;ledgment
%he authors appreciate the Fnancial
support o( Vietnam !ational -niversity
in #o >hi ,inh >ity.
<eferences
526 <oo H Him + Him I : Jim : and
,oon I 4998 In/'Cet printing o( >uKAg'
based highly conductive trac/s on a
transparent substrate Langmuir &6 $48'$77
546 <u > ,osher " P and Leng % 4991
?ne'step green route to narrowly dispersed
copper nanocrystals Journal of Nanoparticle
Research 4 810'818
576 Mu < )ie # >hen J Ji M and Lhang >
4998 :ynthesis and >haracterization o(
,onodispersed >opper >olloids in Polar
:olvents Nanoscale Res. Lett. 7 $10'$39
5$6 !iasari , : +avar . 4998 :ynthesis o(
copper and copper(I) o&ide nanoparticles by
thermal decomposition o( a new precursor
Material Letters *3 $$2'$$7
506 !iasari , : .ereshteh L +avar . 4998
:ynthesis o( oleylamine capped copper
nanocrystals via thermal reduction o( a new
precursor Polyhedron &4 241@279
516 Par/ " H Him + Ieong : ,oon I Him
I : 4993 +irect writing o( copper
conductive patterns by in/'Cet printing Thin
Solid Films 616 3391@3322
536 %ila/i * , IraCizad A and ,ahdavi : ,
4993 :ize composition and optical
properties o( copper nanoparticles prepared
by laser ablation in liDuids Appl. Phys. A 44
$20'$28
5;6 Lhou * <ua ) #ao ) Lhou . Ji #
and *ao < 499; In(luences o( sur(actants
on the preparation o( copper nanoparticles
by electron beam irradiation Nuclear
Instruments and Methods in Physics
Research &** 088'197
586 ,allic/ H <itcomb , I and :currell ,
: 4991 In situ synthesis o( copper
nanoparticles and poly(o'toluidine)= A
metal@polymer composite material
!uropean Polymer Journal 7& 139@130
5296 Jee M >hoi I * Jee H * :tott ! E
and Him + 499; Jarge'scale synthesis o(
copper nanoparticles by chemically
controlled reduction (or applications o(
in/Cet'printed electronics Nanotechnology
19 $2019$
5226 <u > ,osher " P and Leng % 4990
:imple one'step synthesis o( uni(orm
disperse copper nanoparticles Mater. Res.
Soc. Symp. Proc. 429E L1.7.2'1
5246 ,allic/ H <itcomb , I and :currell
, : 49 91 Eur. Polym. I. $4 139
5276 :ougata :ar/ar 0tish Dipan>ar ?ana
=amir :umar =amanta Golam !ostafa
&552 synthesis o( silver nano particles
Polyhedron &* $$28'$$41
52$6 Iie +ing ong&ia <ang %ong Jin
"in Jee 499; Electroless synthesis o( nano
structured gold particles using conducting
polymer nanoparticles Synthetic Metals 164
0;0'0;8
@16A >ai&ia :ong ,aoli Mang +ebao
<ang Lhengshui #u 4929 :ynthesis and
optical properties o( Ln: hollow spheres
(rom single source precursor Materials
Research ulletin 76 2942'2940
5216 ,usta(a "iNer Ol/ay PiQman 4929
>ontrolled synthesis o( copper nano using
ascorbic acid in aDueous >%A" solution
Po"der Technology 194 438@4;$
5236 )in(ang Ji +ongsheng Lhu )ianCu
<ang 4993 Evaluation on dispersion
behavior o( the aDueous copper nano'
suspensions Journal of #olloid and
Interface Science 315 $01@$17
52;6 L.V. .eng I. J. Jyon I.:.>roleyet al
4998 :ynthesis and >atalytic Evaluation o(
+endrimer Encapsulated >u !anoparticles
Journal of chemical education 4* 7
5286 Geo((rey %. >risp Ie((rey Gore 2883
Preparation o( biological labels with
acetylenic lin/er arms Tetrahedron 63 2090'
2044
5496 ,ichele ,enotta *ita >rinelli Elisa
>arloni ,arzia "ianchi Elisa Giacomini
-go Valbusa ,auro ,agnani 4929 Jabel'
(ree Duanti(ication o( activated !.'R" in
biological samples by atomic (orce
microscopy iosensors and ioelectronics
&6 4$89'4$81
5426 P. Veluchamy ,. %suCi %. !ishio %.
Aramoto #. #iguchi :. Humazawa :.
:hibutani I. !a/aCima %. Arita #.
?hyama A. #ana(usa %. #ibino H. ?mura
4992 A pyrosol process to deposit large'area
:n?4=. thin (ilms and its use as a transparent
conducting substrate (or >d%e solar cells
Solar !nergy Materials and Solar #ells *2
238'2;0