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STUDY OF SOME OPTICAL AND ELECTRICAL
PROPERTIES OF HEAVILY DOPED SILICON
LAYERS
A. Slaoui, E. Fogarassy, J. Muller, P. Siffert
To cite this version:
A. Slaoui, E. Fogarassy, J. Muller, P. Siffert.
STUDY OF SOME OPTICAL AND
ELEC-TRICAL PROPERTIES OF HEAVILY DOPED SILICON LAYERS. Laser-Solid Interactions
and Transient Thermal Processing of Materials, 1983, Strasbourg, France.
pp.C5-65-C5-71,
JOURNAL DE PHYSIQUE
Colloque C5, supplkment au nO1O, Tome 44, octobre 1983 page C5-65
STUDY OF SOME OPTICAL AND ELECTRICAL PROPERTIES OF HEAVILY DOPED S I L I C O N LAYERS
A. Slaoui, E. Fogarassy, J.C. Muller and P. Siffert
Centre de Recherches Nucllaires, Laboratoire PHASE, 67037 Strasbourg Cedex,
France
Resume
-
On e t u d i e c e r t a i n e s p r o p r i e t e s optiques de couches de s i l i c i u m dopees au-dela de l a s o l u b i l i t 6 maximale 1 l ' e q u i l i b r e p a r un procede d ' i m - p l a n t a t i o n s u i v i d'une f u s i o n l a s e r .Des p l a q u e t t e s de s i l i c i u m de type P sont implantees 1 des doses a l l a n t j u s q u t l 1017 cmm3 par des i o n s a r s e n i c (80 KeV), puis l e s dopants s o n t incorpores au reseau p a r une f u s i o n l a s e r i n d u i t e par un l a s e r pulse au
-
YAG 1 des energies a l l a n t j u s q u ' 1 2,5 ~ / c m ~ pour des durees d ' i m p u l s i o n s de 25 e t 100 ns, respectivement.La r e f l e c t i v i t e des couches e n t r e 250 e t 500 nm a i n s i que des mesures e l l i p s o m 6 t r i q u e s o n t
e t e
e f f e c t u e e s en f o n c t i o n des c o n d i t i o n s experimen- t a l e s . Aux f o r t e s doses l e s d e f a u t s j o u e n t un r61e non n 6 g l i g e a b l e s u r ces p r o p r i e t e s optiques.A b s t r a c t
-
I t i s w e l l known t h a t t h e s o l u b i l i t y o f most dopants can be n o t i - c e a b l y n c r e a s e d i n s i l i c o n by pulsed l a s e r annealing o f t h e imp1 antedl a y e r s . Here, we have i n v e s t i g a t e d the e v o l u t i o n o f some o p t i c a l and e l e c - t r i c a l p r o p e r t i e s o f such h e a v i l y doped l a y e r s as a f u n c t i o n o f implanted dose, t r y i n g t o separate e f f e c t s due t o t h e h i g h doping from those r e s u l t i n g from d e f e c t s o r p r e c i p i t a t e s
.
P-type s i l i c o n wafers have been implanted w i t h 80 KeV a r s e n i c ions a t doses
- -
-
o f up t o 10'' cm-' and annealed by a pulsed ruby and YAG l a s e r , g i v i n g pulses o f 20 and 100 ns d u r a t i o n , r e s p e c t i v e l y and d e p o s i t i n g energies up t oU.V. and v i s i b l e l i g h t (250 and 500 nm) r e f l e c t a n c e , as w e l l as e l l i p s o m e t r y (632.8 nm) measurements have been performed as w e l l as dark I
-
V and C-
Vc h a r a c t e r i s t i c s .
These i n v e s t i g a t i o n s i n d i c a t e t h a t by i n c r e a s i n g t h e implanted dose, t h e doping l e v e l f i r s t increases u n t i l near s u r f a c e d e f e c t s and p r e c i p i t a t e s modify t h e o p t i c a l as w e l l as t h e e l e c t r i c a l p r o p e r t i e s o f t h e h e a v i l y doped l a y e r s . The generation o f these d e f e c t s has been f o l l o w e d by RBS i n random and c h a n n e l l i n g c o n d i t i o n s .
INTRODUCTION
I n t h e f a b r i c a t i o n o f s o p h i s t i c a t e d devices such as t h e b i p o l a r r a n s i s t o r used i n
$
modern s i l i c o n i n t e g r a t e d c i r c u i t s , i n t e g r a t e d i n j e c t i o n l o g i c ( I L ) and s o l a r c e l l s , t h e use o f h i g h-
dose i o n-
implanted l a s e r-
annealed s i n g l e-
c r y s t a l s i l i c o n allowed ( 1 ) f o r m a t i o n o f b o t h h i g h l y doped shallow'
N
and P+ l a y e r s .C5-66 JOURNAL DE PHYSIQUE
A h i g h
-
power l a s e r i r r a d i a t i o n can anneal t h e i o n-
implanted damage r e g i o n i n s i n g l e-
c r y s t a l semi-conductors. Rapid s u r f a c e m e l t i n g and subsequent l i q u i d phast e p i t a x i a l regrowth i n nanosecond pulse annealing make i t p o s s i b l e t o dope s i l i c o n w i t h e l e c t r i c a l l y a c t i v e i m p u r i t i e s we1 1 above t h e thermal equi 1 ib r i u m s o l i d s o l u - b i l i t y l i m i t (2), and t o completely anneal implanted regions w i t h o u t any macrosco- p i c a l l y extented defects, such as d i s l o c a t i o n s , s t a c k i n g f a c e t s o r p r e c i p i t a t i o n s( 3 ) . Three techniques are used t o analyze e l e c t r i c a l and s t r u c t u r a l p r o p e r t i e s o f l a s e r
-
annealed damage : e l e c t r o n microscopy, He+ b a c k s c a t t e r i n g ( 3 ) and o p t i c a spectroscopy (4,5) m a i n l y i n t h e UV and v i s i b l e range. Indeed, f o r photon energies s m a l l e r than Eo, t h a t i s f o r edge absorption, t h e semi-conductor i s more o r l e s s t r a n s p a r e n t ( f r e e absorption); f o r energies l a r g e r than Eo, i t i s opaque (band t o band absorption). The former gives i n f o r m a t i o n about various l a t t i c e imperfec- t i o n (e.g. i m p u r i t i e s , defects, phonons, e t c....
The l a t t e r i s m a i n l y r e l a t e d t o t h e band s t r u c t u r e and c o n t r i b u t e s e s s e n t i a l l y t o a d e t a i l e d understanding o f the e l e c t r o n i c s t r u c t u r e o f t h e semi-conductor (6). Pankove ( 7 ) has s t u d i e d e x t e n s i v e l y t h e o p t i c a l p r o p e r t i e s o f h e a v i l y doped germanium and has shown t h e m o d i f i c a t i o n i n band s t r u c t u r e and i t s consequence on e l e c t r i c a l p r o p e r t i e s o f P-
N j u n c t i o n s .I n t h i s paper, we attempt t o c h a r a c t e r i z e h e a v i l y doped s i l i c o n l a y e r s by UV and v i s i b l e r e f l e c t i v i t y experiments and by e l e c t r i c a l measurements f o r v e r y l a r g e doping concentrations.
EXPERIMENTS
Several P-type (100) S i wafers, o f 1
-
5 R.cm r e s i s t i v i t i e s , were implanted w i t hAS' (80 KeV) i o n s . The doses ranged between 1015 and 1017 cm-'. This
o p e r a t i o n was f o l l o w e d by Q
-
switched p u l s e YAG o r r u b y l a s e r treatment. The parameters o f t h e l a s e r s a r e r e s p e c t i v e l y : X = 0.532 and 0.690 nm, d u r a t i o n time = 100 and 20 ns, pulse energy = 2.5 and 1.4 ~ / c m 2 . A f t e r l a s e r annealing, almost a l l implanted i m p u r i t i e s were l o c a t e d i n s u b s t i t u t i o n a l p o s i t i o n s , as confirmed by RBS. The maximum c a r r i e r concentrations i n t h e c r y s t a l s were between 8 x 2 0 ' ~ and 4.3 x 10" ( F i g . 1, Table 1) f o r an implanted dose o f 1016 t o 5 x 1 0 l 6 cm-2.F i g . 1
-
RBS spectra f o r both S i and As Table 1-
The samples a r e annealed by a f t e r l a s e r annealing. The ma- l a s e r YAG ( A = 0.53 um) a tThe o p t i c a l r e f l e c t i v i t y spectra were performed o by u s i n g a Beckmann double beam spectrophotometer over t h e range 2500
-
5000A.
An evaporated aluminium m i r r o r , whose r e f l e c t a n c e was assumed t o be 108%. provided t h e reference spectrum. The e l l i p s o m e t r y measurements a t X = 6328 A (He-
Ne) were performed on YAG annealed m-p l e s a t doses 1016 t o 5 x 1016 ~ m - ~ . J u s t p r i o r t o b o t h types o f measurements above the samples were cleaned by f l u o r i d r i c s o l u t i o n t o remove any oxide l a y e r . For e l e c t r i c a l measurements, t h e f r o n t c o n t a c t was r e a l i z e d w i t h Ag evaporation on small nesas and back c o n t a c t was performed w i t h evaporated gold. The s h e e t - r e s i s - tance data was measured w i t h a f o u r
-
p o i n t probe.RESULTS AND DISCUSSION
1 ) OPTICAL CHARACTERISTICS
The r e f l e c t i v i t y sjjectra o f s;bstrate c r y s t a l Two peaks a t 3650 A and 2750 A are observed, and denoted El, E2 r e s p e c t i v e l y . The El
(3.4 ev) peak, i n i t i a l l y a t t r i b u t e d t o an i n t e r b a n d t r a n s i t i o n
ri5
-
r15,
has been revealed (8) t o be a m i x t u r e o fT'
27
:
y12;L i
-
L1 and-
t r a n s i t i o n s F'ig.
As t o the E3 peak (4.5 ev), i t i s due t o t h e a c c i d e n t a l degeneracy o f an M1 edge due t o the X4-
X1 t r a n s i t i o n and an M2 edge due t o t h e C 4-
x1 t r a n s i t i o n (8) ( F i g . 3). Both peaks were p r a t i c a l l y unaf- f e c t e d when t h e doping dose was l e s s than 1016 cm-2 ( F i g . 3 ) . However, t h e peaks were appreciably degraded as t h e dopingc o n c e n t r a t i o n increased. A t 1017 ~s+/cm' t h e E2 peak n e a r l y desappears. We i n t r o - duce t h e r e f l e c t i v i t y change AR, d e f i n e d as t h e d e v i a t i o n from the c r y s t a l l i n e s u b s t r a t e r e f l e c t i v i t y a t 2750
2\
t o b e t t e r d i s t i n g u i s h t h e change w i t h doping. As p r e v i o u s l y i m p l i e d , R s t a r t s t o increase when dose exceeds 1016 cmu2 ( F i g . 4). T h i s k i n d o f behaviour has been a l r e a d y r e p o r t e d f o r P and As implanted and r u b y l a s e r annealed s i l i c o n ( 9 ) . As has been shown ( 9 ) , t h e cause o f t h e degradation o f t h e E2 peak i s n e i t h e r due t o f r e e c a r r i e r s n o r t o s t r e s s caused by i m p u r i t y atoms, b u t r a t h e r t o supersaturated s o l i d s o l u t i o n s o f a r s e n i c i n t h e s i l i c o n l a t t i c e . It i s c l e a r t h a t t h i s r e f l e c t i v i t y reduc- t i o n i s r e l a t e d t o t h e change i n band s t r u c t u r e due t o the h i g h doping.and doped s i l i c o n a r e shown i n F i g . 2.
r
Ee Y A G . LASER1
JOURNAL DE PHYSIQUE 5 El6 cm2 L : Y a g L a s e r T : Therrn.Annea1 (600 a . 30rnn)
-.,
... ,,~.
.. \ , ,.
....
.. - . L+T...
..
'.. ..>..;..
....,, '- ..._ ...I---.
25 &e-
90 20-
80 iR-
>+
15 I-., > 70 C-( a c a 10 0 W 60 52
W 50 05
LO *2
w w 40 d -74 * 0 0 0 0 0 0 DOSE (crn-2) I~ ~ mO Um J o O v~ Om O A (nrnlFig. 4
-
The r e f l e c t i v i t y change AR (devia- Fin. 5-
Optical r e f l e c t i v i t y tion from the,crystal Si r e f l e c t i - spectra f o r c r y s t a l l i n e vity a t 2750 A ) versus implanted ( - ) and dopeddose. ( 4 . 5 2 lo2' cmU3) ~ i . L designates l a s e r annea- 2 ling (2.5 J/cm ) and T thermal annealing (600° C, 20
mn)
16 2In Fig. 5 shows r e f l e c t i v i t y spectra f o r 5
x
10 /cm doping dose before and a f t e r thermal annealing (600" C , 20 mn). After l a s e r annealing, the highly substitutional arsenic concentration i n s i l i c o n i s metastable. Thermal annealing increases the fraction of i n t e r s t i t i a l atoms and consequently the number of active atoms decreases, as seen by sheet r e s i s t i v i t y measurements. There r e s u l t s , as observed in Fig. 5, the increase of theE2
peak. We can conclude t h a t the r e f l e c t i v i t y reduction i s mainly due to high doping level. Similar behaviour i s observed f o r ruby l a s e r an-,
11 ? 3 6r:
8 M8
3 5,
3 4 nealed samples. 3 15 Several reports in the l i t e r a t u r e (10, 11) inves- Ptigated the e f f e c t s of l a s e r annealing on ion im-
3
planted s i l i c o n layers by using ellipsometry *-
which i s a f a s t and non-destructive method t ocharacterize c r y s t a l damage. From e l 1 ipsometri c
"
,,
measurements, i s i s possible t o calculate refrac- 5
t i v e and extinction indices and absorption coef- f i c i e n t s . Changes i n optical constants can be
k
a t t r i b u t e d t o transformation of the Si band s t r u c - E t u r e a f t e r implantation and annealing.E
=
Fig. 6 shows the r e f r a c t i v e index and absorption
k
c o e f f i c i e n t as a function of implanted dose. The former decreases with increasing dose and satura- tion a t 4x
1016 cmm2, but the second r i s e s t o0
value nearly on order of magnitude higher than
the one f o r pure s i l i c o n . Ostaja e t a7. ( 5 ) fmiP
suggest t h a t the very highly doped layers are F i g . 6
-
Absorptioncoefficient
responsible f o r t h i s increase of the absorption-
and refraction index AS+ c o e f f i c i e n t , giving low diffusion lenghts.F i g . 7
-
Sheet r e s i s t i v i t y versus implanted F i g . 8 - Dark forward and reverse I - V dose. The p u l s e energy f o r YAGand ruby l a y e r s are 2.5 and 1.4 c h a r a c t e r i s t i c s 1=1 (*-1) s nkT J/crn2 r e s p e c t i v e l y . The values
c a l c u l a t e d
t
. - ) gives good agree- where Is i s t h e s a t u r a t i o n ment w i t h experiment (... and--- ) . c u r r e n t , n the qua1 i t y f a c t o rIf is t h e reverse leakage c u r r e n t .
2) ELECTRICAL CHARACTERISTICS
The e l e c t r i c a l a c t i v i t y o f t h e implanted a r s e n i c atoms was proved by sheet r e s i s t a n - ce measurements as shown i n F i g . 7. We observe, f o r YAG and ruby l a s e r treatments, a decrease of R as the dose increases from 1015 t o 5 x 1016 cm-2, f o l l o w e d by an increase f o r doses between 5 x 1016 and 1017 cm-'. The p o s s i b i l i t y was considered t h a t the l a s e r energy d e n s i t y was n o t s u f f i c i e n t t o anneal and a c t i v a t e a l l dopants
2
a t 1017 ~ s + / c m and t h a t p r e c i p i t a t i o n has taken p l a c e due t o the As s o l u b i l i t y 1 i-
m i t ( 6 x
loz1
~ m - ~ ) (12) a f t e r annealing. On t h e same f i g u r e , two o t h e r curves are p l o t t e d : t h e f i r s t ( s o l i d l i n e ) i s t h e Smith e t a l . curve (13) f o r d e v i a t i o nIS S = 250 which has been e x t r a p o l a t e d t o a dose h i g h e r than 1016 ~ r n - ~ . The second curve was d e r i v e d from t h e equation R = (qNs u ) - I where Ns corresponds t o t h e t o t a l number of implanted i o n s per u n i t surface are, and i s the e l e c t r o n m o b i l i t y given by H i l l (14) f o r c a r r i e r c o n c e n t r a t i o n C between
lo2'
and cmb3.P = 7.5 x 10"
c - l l 2 ;
Ns and C were determined by RBS f o r each dose. C a l c u l a t e d va- l u e s were found t o be i n good agreement. For doses i n excess o f 5 x 1015 ~ m - ~ , R (YAG) i s lower than R ( r u b y ) because t h e j u n c t i o n i s deeper f o r t h e YAG l a s e r i r - r a d i a t i o n . This i s due t o t h e d i f f e r e n c e i n t h e p u l s e d u r a t i o n o f YAG ( T = 100 ns) and ruby ( T = 20 ns) l a s e r s i n which t h e l o n g e r p u l s e i n d i c e s a t h i c k e r m e l t i n g zone. The values found are much low ( 2 10/SQ), i m p l y i n g a very good e l e c t r i c a l a c t i v a t i o nWe r e p o r t i n Fig. 8, t h e dark forward and reverse c u r r e n t - v o l t a g e c h a r a c t e r i s t i c s o f t h e l a s e r annealed j u n c t i o n s and o f the thermal d i f f u s e d diode. The forward c u r r e n t recombination f a c t o r nr as d e f i n e d by J = Jor lexp (qV/nrkT)
-
11 was c a l c u l a t e d over the range 0 t o 0.35 v o l t s . Contrary t o d i f f u s e d j u n c t i o n s , t h e devices annea- l e d by YAG o r ruby l a s e r s e x h i b i t e d recombination f a c t o r i n t h e range 1.6 t o 4.2 i m p l y i n g t h e existence of a l a r g e r space charge r e g i o n and surface c o n c e n t r a t i o n of d e f e c t s t h a t a c t as generation-
recombination centers (Table 11). These h i g h va- lues of nr ( > 2) are n o t p r e d i c t e d by t h e Sah-
Noyce and Shockley ( S-
N-
S) theo-C5-70 JOURNAL DE PHYSIQUE
r y ( 1 5 ) , b u t c o u l d be due i n p a r t t o shunt r e s i s t a n c e e f f e c t s and i n p a r t t o m o d i f i - c a t i o n s i n t h e S - N - S theory which account f o r n o n - u n i f o r m i t i e s i n t h e d i s t r i b u - t i o n o f recombination centers ( 1 6 ) . The h i g h l e v e l o f doping makes f o r d i f f u s i o n
Id and recombination Ir s a t u r a t i o n c u r r e n t s t h a t are more than one o r d e r o f magnitu- de h i g h e r than those o f d i f f u s e d diodes, suggesting a change i n d i f f u s i o n constant D, d i f f u s i o n l e n g h t L and i n t r i n s i c c o n c e n t r a t i o n ni composing t h e s a t u r a t i o n c u r r e n t . For h e a v i l y doped l a y e r s , ni i s remplaced by an e f f e c t i v e i n t r i n s i c c o n c e n t r a t i o n
n such t h a t
A
Egi e n i e = n exp
i
(-n)
where A Eg i s t h e shrinkage band gap ( 1 7 ) . Another e l e c t r i c a l c h a r a c t e r i s t i c i s t h e leakage, o r reverse, c u r r e n t ,which we take as Va =
-
1 v o l t . The reverse leakage c u r r e n t ,If,
i s due t o t h r e e mechanisms : c a r r i e r d i f f u s i o n , generation o f c a r r i e r s w i t h i n the d e p l e t i o n regions, and generation o f c a r r i e r s due t o the i n t r o d u c t i o n o f recombination centers a t t h e surface o f t h e p-n j u n c t i o n s . This t h i r d mechanism i s p r e v a l e n t and l a r g e l y exceeds t h e importance o f the o t h e r two (18). As f o r t h e recombination q u a l i t y f a c t o r nr, the increase o f t h e reverse c u r r e n t i n implanted and l a s e r annealed j u n c t i o n s can be due t o surface, and space charge induced defects. Since we have observed s i m i l a r behaviour f o r l a s e r annealed d i f f u s e d j u n c t i o n s (19), we suggest t h a t t h e p r o p e r t i e s o f t h e surface a f t e r l a s e r treatment ( h i g h doping l e v e l , dan- gling-bands, h i g h absorption c o e f f i c i e n t , recombination v e l o c i t y , e t c ...) are m a i n l y r e s p o n s i b l e o f t h e h i g h measured reverse c u r r e n t .Table I 1
-
We assumes,,
I = IoD(expA-
-
n,kT 1)
Table I11
-
$ ( Y ) and $ designate d i f f u - s i o n ~ o t e n t i a l f o r YAG and DOSE lel6cn? O ( Y ) (V) O ( R ) (V)ruby annealed 1 ayers respec- 9 "
+ loR(ex~
-
'1)where K i s a constant depending upon t h e doping c o n c e n t r a t i o n on the p and n sides o f t h e j u n c t i o n , and n i s a constant normally l y i n g between 2 and 3, and i s a measure of the doping p r o f i l e . Here, we found n = 3 i m p l y i n g a l i n e a r l y graded j u n c t i o n . From these measurements, we deduce t h e d i f f u s i o n p o t e n t i a l e
+
presented i n Table 11. The values o f implanted l a s e r annealed j u n c t i o n s are v e r y much lower than those o f d i f f u s e d diodes (0.9 v o l t ) . This d i f f e r e n c e suggest the possi- b i l i t y o f compensating d e f e c t s i n t h e j u n c t i o n r e g i o n (20). As t h e d i f f u s i o n po- t e n t i a l i s d i r e c t l y r e l a t e d t o t h e energy band gap o f t h e semi-conductor, and the @ a r e low, these r e s u l t s c o u l d i n d i c a t e a shrinkage of the energy gap (7) due t o t h e h i g h doping 1 eve1.
CONCLUSION
We have s t u d i e d t h e e l e c t r i c a l and o p t i c a l c h a r a c t e r i s t i c s o f i o n implanted l a s e r annealed s i l i c o n . I n p a r t i c u l a r , t h e decrease o f t h e r e f l e c t i v i t y and t h e i n c r e a - se o f the a b s o r p t i o n c o e f f i c i e n t can be r e l a t e d t o t h e degree o f s u p e r s a t u r a t i o n o f t h e s o l i d s o l u t i o n which r e s u l t s from t h e very h i g h doping l e v e l . There r e s u l t s degraded e l e c t r i c a l c h a r a c t e r i s t i c s ( h i g h recombination q u a l i t y f a c t o r , h i g h satu- r a t i o n and reverse c u r r e n t s ) which c o u l d l i m i t t h e performance o f t h e devices.
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