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SEMICONDUCTOARE PE BAZ

DE TI TANAT DE BARIU
IMPURIFICAT CONTROLAT
(Partea I-a)

SEMICONDUCTORS BASED ON
CONTROLLED DOPED BARI UM
TI TANATE (1st Part)
*

**

Alexandru MANIU , Irina APOS TOL


*

"Transilvania" University of Brasov, Romania


**
IPEE Curtea de Arges, Romania

Rezumat. Acest studiu prezint rezultat ele experimentale


ale doprii titanatului de bariu n scopul de a obine un
semiconductor. Material ele semiconducto are p e baz de
titanat de bariu impuri ficat controlat sunt materiale
termosensibile cu o depend en puterni c a rezistivitii
electrice cu temp eratura (efect PTCR) i pot fi utilizate
pentru obinerea d e compon ente electroni ce. Aceste
materiale pot fi el aborate prin metoda reaciei n stare
solid. Impurificarea controlat a titanatului de bariu, care
n stare pur este un izolator, poate conduce spre proprieti
semiconductoare sau dielectrice n funcie de tipul
elementelor de aliere i nivelul d e impuri fi care. S-au
folosit ca el emente de aliere Pb, Ca, Co, Se, Zr. Pulberile
calcinat e i compactele sinterizate au fost caracterizate
microstructural prin tehni ci de di fracie cu raze X i
msurate electric. Aplicabilitatea acestor materi ale este
vast: n industria electronic i electrotehnic,
telecomunicaii, automatizri, industria de automobile.

Abstract. This paper presents the exp erimental results of


doping barium titanate in order to obtain a
semiconductor. The semi conducting materials based on
controlled doped b arium titanate are termosensible
materials with a strong dep enden ce o f el ectric resistivity
with temperature (PTCR effect) and m ay be used for
obtaining electronic components. These materi als can be
elaborat ed by method of solid state reaction. The
controlled doping of barium titanate, which is an
insulating material in its pure state, can lead to
semiconductorial or dielect rical properties in terms of the
type of doping elem ents and the level o f doping. There
were used as doping elements Pb, Ca, Co, Se, Zr. The
calcined powders and sintered compacts were micro
structurally charact erized by X-Ray diffractometry and
electric measured. The application o f thes e materi als is
large: in electronic and electro techni cal industry,
telecommunication, automatization, automobile industry.

Cuvinte cheie: semiconductoare, titanat de bariu,


impurificare control at

Key words: semiconductors, barium titanate, controlled


doping

1. Introducere

1. Introduction

T itanatul de bariu este un material feroelectric.


Rezistivitatea titanatului de bariu utilizat ca
dielectric sau piezoelectric este mai mare de 10 10
cm, adic considerabil mai mare dect
rezistivitatea semiconductorilor (10 -4 10 10 ) cm.
n stare pur acest material este un izolator, dar dac
n componena lui se introduc microadaosuri de
elemente de aliere el devine semiconductor.
Semiconductibilitatea este obinut prin
impurificarea controlat n vederea obinerii unui
numr specific de electroni liberi, care fac materialul
conductiv. Structura materialului este policristalin
de tip perovskitic. La grania dintre cristalite, se
formeaz bariere electrice de potential ce mpiedic
electronii liberi s difuzeze n arii adiacente,
rezultnd astfel o rezistivitate mare. Rezistivitatea
materialului este compus din rezistivitatea
cristalitelor individuale i rezistivitatea granielor
grauntelui. Rezistena graniei gruntelui este
puternic dependent de temperatur, iar la
temperaturi mari se produce o cretere puternic a
barierelor de potenial i prin urmare a rezistenei.
Cnd prezint o structur policristalin se

Barium titanate is a ferro-electric material. The


resistivity of barium titanate used as dielectric or
piezoelectric is bigger than 10 10 cm, so
considerable bigger than the resistivity of
semiconductors (10 -4 1010) cm. In pure state
this material is an insulating, but it may become a
semiconductor if introduce inside of it some micro
additions of doping elements
The semi conductibility is obtained by controlled
doping in order to obtain a specific number of free
electrons which transforms the material in a
conductive one. The structure of the material is
polycrystalline of perovskite type. At the boundaries
between crystallites it is formed electric potential
barriers which impede free electrons to diffuse into
adjacent areas and so results a high resistivity. The
resistivity of the material is composed by the
resistivity of individual crystallites and the resistivity
of grains boundaries. The resistance of grains
boundary is strong dependent of temperature, but at
high temperature it is produced an important rise of
potential barriers and also of resistance.
When presents a polycrystalline structure it can

128

RECENT, Vol. 8, nr. 2 (20), Iulie, 2007

Semiconductors Based on Controlled Doped Barium Titanate (1st Part)


observ o modificare esenial a conductivitii
electrice, caracterizat printr-un coeficient de
temperatur pozitiv al rezistivitii. Astfel, la o
anumit temperatur, care este strns legat de
natura elementelor de aliere i de gradul de
impurificare, se produce o cretere foarte abrupt a
rezistivitii (efect PT CR). Acest efect se produce la
temperatura la care materialul sufer tranziia din
faza tetragonal feroelectric n faza cubic
paraelectric. T emperatura la care are loc tranziia
tetragonal-cubic pentru BaT iO3 este de regul n
jurul valorii de 120C, dar poate fi reglat cu
ajutorul elementelor de aliere.
Domeniul de aplicare al acestor materiale este
industria electronic i electrotehnic, telecomunicaiile, automatizrile, industria de automobile.

be observed an essential change of the electric


conductivity characterized by a positive temperature
coefficient of resistivity. So, at a certain
temperature which is closely connected with the
nature of doping elements and level of doping, it
can be produced a very steep rise of resistivity
(PT CR effect). This effect is produced at
temperature at which the material allows the
transition from ferro-electric tetragonal phase to
paraelectric cubic phase. T he right temperature for
tetragonal-cubic transition of BaT iO3 is usually
about 120C, but it can be regulated by helping of
doping elements.
The range of application of these materials is:
electronic and electrotechnical industry, telecommunication, automatiszation, automobile industry.

2. Prepararea probelor

2. Preparation of samples

n acest studiu s-au preparat 12 compoziii care


au fost procesate dup cum urmeaz: cntrirea
componenilor, mcinarea cu bile a oxizilor i
carbonailor de nalt puritate, calcinarea amestecului
uscat, mcinarea cu bile a produsului calcinat pentru
a reduce dimensiunile particulelor, adugarea unui
liant organic corespunztor i formarea de discuri
prin presare, sinterizarea pieselor formate i, n final,
depunerea contactelor electrice i realizarea
msurtorilor electrice.
Compoziiile elaborate sunt prezentate n
tabelul 1.
1) Cntrirea materiilor prime. Materiile prime
utilizate, de provenien autohton i din import,
au fost de puritate P.A. Puritatea materiilor prime
este un factor care are o influen decisiv asupra
proprietilor finale ale materialului i a supra
reproductibilitii lui. T itanatul de bariu a fost
impurificat controlat cu Pb, Ca, Co, Se i Zr n
scopul obinerii proprietilor semiconductoare.
Materiile prime au fost dozate n proporii bine
stabilite conform compoziiilor prezentate mai sus.
2) Mcinarea. Materiile prime dozate au fost
mcinate umed n ap distilat, n moar planetar,
timp de ase ore. Scopul operaiei a fost obinerea
uniformizrii distribuiei componenilor n masa
materialului i a unei granulometrii definite.
3)Uscarea. S-a fcut n etuv de uscare ventilat la
temperatura de 120C.
4)Calcinarea. Materialele mcinate i uscate au fost
calcinate n cuptor electric camer, n intervalul de
temperatur 900C 1100C, meninndu-se cinci
ore. Calcinarea asigur obinerea omogenitii
compoziiei i a densitii materialului.

In this study 12 compositions of powders have


been prepared as follows: weighing the
components, milling with balls of high purity oxides
and carbonates, calcination of dry mixture, milling
with balls of calcined product for reduction the
dimensions of particles, adding a proper organic
binder and forming disks by pressing, sintering of
formed pellets and, finally, coated electric contacts
and achievement electric measurements.
The elaborated compositions are presented in
table1.
1) Weighing of raw materials. T he used raw
materials, autochthonous and imported, were of
analytical purity. The purity of raw materials is a
factor which exercise a decisive influence over
final property of the material and over its
reproducible. T he barium titanate was controlled
doped with Pb, Ca, Co, Se and Zr in order to
obtain semi conducting properties. Raw materials
were dosed in right established proportion
according to compositions above mentioned.
2) Milling. The dosed raw materials were wet
milled in distilled water, in planetary mill during
six hours. The purpose of the operation was to
obtain an uniform distribution of the components
into the mass of the material and obtaining a
definite granulometry.
3) Drying. It was made in ventilated drying oven at
temperature 120C.
4) Calcination. Milled and dried materials were
calcined in the range of temperatures 900C
1100C in chamber electric furnace, during five
hours. Calcination ensures obtaining the
homogeneousness of the composition and the
density of the material.

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Semiconductoare pe baz de titanat de bariu impurificat controlat (Partea I-a)


5) Mcinarea materialelor calcinate. Materialele
calcinate au fost remcinate n vederea reducerii
dimensiunilor particulelor. Operaia a fost
executat utiliznd ca mediu de mcinare apa
distilat, n moar planetar, timp de opt ore.
6) Granularea. Pulberile mcinate i uscate au fost
amestecate cu un liant de tip alcool polivinilic tip
30/98, obinndu-se un amestec de granule ce pot
fi uor presate.
7) Presarea. Pulberile granulate au fost presate n
matrie din otel, sub form de discuri cu diametrul
= 12 mm i grosimea g = 2,5 mm, cu ajutorul
unei prese rotative automate.
8) Sinterizarea. Discurile presate au fost sinterizate
n cuptor electric camer nclzit cu elemente
superkanthal, n cuptor electric industrial tunel tip
Riedhammer i n cuptor electric tubular nclzit
cu elemente de crusilit, n intervalul de
temperatur 1220C 1370C. n tabelul 2 sunt
prezentate calcinrile i sinterizrile care au fost
efectuate pentru compoziiile 112.
9) Depunerea contactelor electrice. Cele dou fee
ale discurilor sinterizate au fost acoperite cu
electrozi din past de argint (78%Ag), prin
tehnica serigrafiei.
10) Msurtori electrice. Msurarea rezistenei /
capacitii la temperatura camerei a fost fcut pe
discuri c u contacte ohmice. Pentru msurarea
rezistenei s-a utilizat un aparat multimetru
numeric E0302, iar pentru msurarea capacitii
electrice s-a utilizat o punte T esla BM 595
RLCG.

5) Milling of calcined materials. The calcined


materials were milled again in order to reduce the
dimensions of the particles. The operation was
executed using as medium of milling distilled
water, in planetary mill, during eight hours.
6) Granulation. T he milled and dried powders were
mixed with a binder such us polyvinyl alcohol
30/98 type, obtaining a mixture of grains which
can be easily pressed.
7) Pressing. The granulated powders were pressed
in steel dies into disks with = 12 mm diameter
and g = 2.5 mm thickness using an automatic
rotary printing press.
8) Sintering. The pressed disks were sintered in
chamber electric furnace heated with superkanthal
elements, in tunnel industrial electric furnace
Riedhammer type and in tubular electric furnace
heated with crusilit elements, in range of
temperature 1220C 1370C. In table 2 are
presented the calcinations and sinterings which
were made for compositions 112.
9) Coated with electrodes. The two faces of sintered
disks were coated with silver paste (78%Ag)
electrodes by printing technique.
10) Electrical measurements. The measured of
resistance/capacity at room temperature was made
on disks with ohmmic contacts. For measure the
resistance it was used an apparatus numerical
multimeter E0302 (0.2 k 2 M) and for
measure the electric capacity it was use d a small
bridge T esla BM595 RLCG.

Tabelul 1. Compoziiile elaborate


Table 1. The elaborated compositions

No. comp.
1
2
3
4
5
6
7
8
9
10
11
12

130

The elabotated compositions


BaT iO3 43.5%, PbCO3 6.5%
BaT iO3 37%, PbCO3 13%
BaT iO3 30.5%, PbCO3 19.5%
BaT iO3 24%, PbCO3 26%
BaT iO3 17.5%, PbCO3 32.5%
BaCO3 87.26%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%
BaCO3 87.0421%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%, Co 3 O4 0.2179%
BaCO3 87.041%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%, Co3 O4 0.2179%,
Se 0.001%
BaCO3 87.0321%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%, Co 3 O4 0.2179%,
Se 0.010%
BaCO3 86.9421%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%, Co 3 O4 0.2179%,
Se 0.100%
BaCO3 86.9421%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%, Co 3 O4 0.2179%,
ZrO2 0.100%
BaCO3 87.0321%, T iO2 29.05%, PbCO3 25.02%, CaCO3 6.6%, Co 3 O4 0.2179%,
ZrO2 0.010%
RECENT, Vol. 8, nr. 2 (20), Iulie, 2007

Semiconductors Based on Controlled Doped Barium Titanate (1st Part)


Tabelul 2. Tabelul tratamentelor termice (calcinri, sinterizri)
Table 2. The table of thermic treatments (cal cinations, sinterings)

1
2
3
4
5
6

Calcinations
T(C)
chamber fu rnace
1000C
1000C
1000C
1000C
1000C
900C

950C

1000C

1050C

1100C

1000C

1000C

1000C

10

1000C

11

1000C

12

1000C

No.
comp.

Sinterings T(C) tunnel furn ace, chamb er furnace, tubular furnace


1300 C tunnel furnace, 1330C chamber furnace, 1370C chamber furnace
1300 C tunnel furnace, 1330C chamber furnace, 1370C chamber furnace
1300 C tunnel furnace, 1330C chamber furnace, 1370C chamber furnace
1300 C tunnel furnace, 1330C chamber furnace, 1370C chamber furnace
1300 C tunnel furnace, 1330C chamber furnace, 1370C chamber furnace
1220C tunnel furn ace, 1300C chamber fu rnace, 1320C chamber furnace,
chamber fu rnace
1220C tunnel furn ace, 1300C chamber fu rnace, 1320C chamber furnace,
chamber fu rnace
1220C tunnel furn ace, 1300C chamber fu rnace, 1320C chamber furnace,
chamber fu rnace
1220C tunnel furn ace, 1300C chamber fu rnace, 1320C chamber furnace,
chamber fu rnace
1220C tunnel furn ace, 1300C chamber fu rnace, 1320C chamber furnace,
chamber fu rnace
1250C tunnel furn ace, 1300C chamber fu rnace, 1330C chamber furnace,
chamber fu rnace
1250C tunnel furn ace, 1300C chamber fu rnace, 1330C chamber furnace,
chamber fu rnace
1250C tunnel furn ace, 1300C chamber fu rnace, 1330C chamber furnace,
chamber fu rnace
1250C tunnel furn ace, 1300C chamber fu rnace, 1330C chamber furnace,
chamber fu rnace
1250C tunnel furn ace, 1300C chamber fu rnace, 1330C chamber furnace,
chamber fu rnace
1250C tunnel furn ace, 1300C chamber fu rnace, 1330C chamber furnace,
chamber fu rnace

1370C
1370C
1370C
1370C
1370C
1350C
1350C
1350C
1350C
1350C
1350C

3. Caracterizarea microstructural prin


difracie de raze X a materialelor obinute
n urma tratamentelor termice

3. Microstructural characterization by
X-Ray diffractometry of obtained
materials by thermic treatments

Materialele calcinate si discurile sinterizate la


diferite temperaturi au fost analizate prin difracie
de raze X.
Pentru probele din materialele cu compoziiile
7, 10, 11, 12, calcinate la 1000C i sinterizate la
1330C pe cuptor tunel, sunt prezentate spectrele de
difracie n figura 1.

The calcined materials and sintered disks at


different temperatures were analysed by X-Ray
diffractometry.
For samples of materials with compositions 7,
10, 11, 12 calcined at 1000C and sintered at
1330C in tunnel furnace are presented diffraction
spectrums in figure 1.

4. Proprieti electrice

4. Electrical properties

Discurile cu contacte electrice din cele 12


compoziii au fost msurate electric.
Pentru discurile sinterizate cu contacte ohmice
din pasta de argint (78%Ag) a fost msurat
rezistena electric la temperatura camerei, n curent
continuu i n curent alternativ, folosind un
multimetru numeric E0302.
Capacitatea C i tangenta unghiului de pierdere,
tg, au fost msurate tot pe discuri cu contacte
ohmice, utiliznd o punte Tesla BM 595 RLCG.

The disks with electric contacts from 12


compositions were electric measured.
For disks sintered, with ohmmic contacts of
silver paste (78%Ag), it was measured the electrical
resistance at room temperature in continuous
current and alternative current using a numerical
multimeter E0302.
The capacity C and tangent of loss angle tg
were also measured for disks with ohmmic contacts
using a small bridge T esla BM 595 RLCG.

RECENT, Vol. 8, no. 2 (20), July, 2007

131

Semiconductoare pe baz de titanat de bariu impurificat controlat (Partea I-a)


Rezultatele msurtorilor sunt prezentate n
fiele de msurtori 1, 2, 3.

The results of measurements are presented in


the lists of measurements 1, 2, 3.

a)

b)

c)

d)

Figura 1. Spectrele de difracie ale probelor din compoziiile 7, 10, 11, 12 calcinate la 1000C i sinterizate la 1330C
pe cuptor tunel: a) compoziia 7; b) compoziia 10; c) compoziia 11; d) compoziia 12
Figure1. Diffraction spectrums of 7, 10, 11, 12 samples calcined at 1000C and sintered at 1330C in tunnel furnace:
a) composition no. 7; b) composition no. 10; c) composition no. 11; d) composition no. 12
Fia de msurtori nr. 1
The list of measurements no. 1

No.comp.
1.
2.
3.
4.
5.
1.
2.
3.
4.
5.
1.
2.
3.
4.
5.
132

T calcinationC
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C
1000 C

T sintering C
1300C tunnel furnace
1300C tunnel furnace
1300C tunnel furnace
1300C tunnel furnace
1300C tunnel furnace
1330C chamber furnace
1330C chamber furnace
1330C chamber furnace
1330C chamber furnace
1330C chamber furnace
1370C chamber furnace
1370C chamber furnace
1370C chamber furnace
1370C chamber furnace
1370C chamber furnace

Rc.c.
>20 M
>20 M
>20 M
>20 M
>20 M
3.80 M
>20 M
>20 M
>20 M
>20 M
3.02 M
14.72 M
>20 M
>20 M
>20 M

RECENT, Vol. 8, nr. 2 (20), Iulie, 2007

Rc.a.
49.6 k
49.8 k
50.1 k
49.8 k
50.3 k
43.3 k
48.9 k
60.1 k
48.9 k
53.5 k
48.5 k
46.9 k
72.3 k
113.2 k
112.0 k

C(nf)
5.30
4.90
5.72
6.30
5.20
2.50
4.18
3.90
4.29
4.30
4.03
3.80
4.89
4.52
4.67

Semiconductors Based on Controlled Doped Barium Titanate (1st Part)


Fia de msurtori nr. 2
The list of measurements no. 2
T
calcination
(C)
900C
950C
1000C
1050C
1100C
900C
950C
1000C
1050C
1100C
900C
950C
1000C
1050C
1100C
900C
950C

T
sintering
(C)
1300C
1300C
1300C
1300C
1300C
1320C
1320C
1320C
1320C
1320C
1370C
1370C
1370C
1370C
1370C
1220C
1220C

No.
R(k)

7
807

No.
R(k)

7
861

R
c.c.
100 M
90 M
12 M
30 M
40 M
35 M
17 M
10 M
340 M
150 M
20 M
450 M
40 M
60 M
5000 M
6000 M

tg104

C
c.a.
3.4 M
6.7 M
2.25 M
6.2 M
3.68 M
2 M
6.4 M
2.2 M
6.3 M
2.9 M
1.2 M
3.6 M
1.7 M
3.4 M
1.6 M
19 M
21 M

250
311
279
311
228
347
312
299
305
228
377
360
278
362
316
355
443

pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF
pF

Fia de msurtori nr. 3


The list of measurements no. 3
Tubular furnace T= 1250C
8
9
10
3.26
2.18
3.12
Tubular furnace T= 1350C
8
9
10
31.2
4.23
25.8

2011
1072
3246
1216
2286
4200
965
3323
1158
3130
4650
1527
4035
2064
4335
346
216

f
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz
kHz

11
1.52

12
2.10

11
4.77

12
4.52

5. Concluzii

5. Conclusions

Toate rezultatele experimentale au demonstrat


c exist o corelaie ntre proprietile electrice,
compoziia pulberilor i microstructura probelor.
Msurtorile efectuate asupra compoziiilor
112 elaborate au demonstrat urmtoarele:
a) Pentru compoziiile 1, 2, 3, 4, 5, 6 msurtorile
electrice au evideniat caracterul capacitiv i
faptul c ele pot fi folosite drept condensatoare;
b) Compoziiile 7, 8, 9, 10, 11, 12 au o rezistivitate
electric n intervalul [4103 310 6 ] cm,
aa nct ele sunt semiconductoare.

The whole experimental results demonstrated that


there was a correlation between electrical properties,
powders composition and samples microstructure.
The measurements effected over elaborated
compositions 112 demonstrated following:
a) For compositions 1, 2, 3, 4, 5, 6 electrical measurements pointed out the capacitance character and the
real fact that they can be used as condensers.
b) Compositions 7, 8, 9, 10, 11, 12 have an electrical
resistivity in the range [410 3 310 6] cm,
so, they are semiconductors.

Refe rences
1. Blanchart, P ., Balestrieri, D., Weber, F., Abelard, P .: Influence of Calcium Addition on the Microstructure and the Electrical
Properties at Room Temperature of BaTiO 3 for PTC Thermistors. Silicates Industriels, Vol. 1, no. 2, 1994, p. 47-52
2. Gissibi, B., Wilhelm, D., Herring, H.: Electron microscopy of nanocrystalline BaTiO 3. NanoStructured Materials, Vol. 9, 1997,
p. 619-622
3. Beek, H.P ., Muller, F., Haberkorn, R., Wilhelm, D.: Synthesis of perovkite type compounds via different routes and their X-Ray
characterization. NanoStructured Materials, Vol. 6, 1995, p. 659-662
4. Brzozowski, E., Castro, M.S.: Conduction mechanism of barium titanate ceramics. Ceramics International, 26, 2000, p. 265-269
5. Tuan, W.H., Lin, S.K.: The microstructure-mechanical properties relationship of BaTiO 3. Ceramics International, 25, 1999, p. 35-40

Lucrare primit n Mai, 2007


(i n form revizuit n Iunie, 2007)

Received in May, 2007


(and revised form in June, 2007)

RECENT, Vol. 8, no. 2 (20), July, 2007

133