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AN INFLUENCE OF DOPING ON THE KINETICS OF BPSG DEPOSITION PROCESS AND THE
PROPERTIES OF THE DEPOSITED LAYER
P. Grabiec, S. Pietruszko
To cite this version:
P. Grabiec, S. Pietruszko. AN INFLUENCE OF DOPING ON THE KINETICS OF BPSG DEPO-
SITION PROCESS AND THE PROPERTIES OF THE DEPOSITED LAYER. Journal de Physique
Colloques, 1989, 50 (C5), pp.C5-585-C5-593. �10.1051/jphyscol:1989569�. �jpa-00229601�
JOURNAL DE PHYSIQUE
Colloque C5, supplbment au n 0 5 , Tome 50, mai 1989
AN INFLUENCE O F DOPING O N THE KINETICS OF BPSG DEPOSITION PROCESS AND THE PROPERTIES O F THE DEPOSITED LAYER
P.B. GRABIEC and S.M. PIETRUSZKO*
Inst. of Electron Technol., al. Lotnikow 32-46, 02-668 Warsaw, Poland
* I M I O , Warsaw Technical University, ul. Koszykowa 75, 00-662 Wdzwiw, Pol and
FIikwm6 Parmi les differentes m6thodes de planarisation, le dewt chimique de BPSG suivi de recuit a 6te largement reconnu pour les applications des circuits a tr& haute int6gration. On pesente dans cette communication une analyse de I'influence du dopage sur la cinetique de d6p6t de BPSG sous pression atmosph6rique. Quelques proprietes de couches sont e v o q u k . Le but de cette 6tude est I'optimisation ulterieure du prookie. A partir de I1&ude p w e m m e n t publib sur Si02, I'influence du dopage a & consideke. En conclusion, le pmc6de de dep6t de BPSG devrait @tm effectue a relativement basse temperature avec un rapport 02ISiH4 eleve.
Coptimisation de I8uniformit6 du flux gazeux a une grande importance.
A b s t r a c t
-
From among different p l a n a r l z a t i o n methods, BPSG deposition and r e f l o w has been w l d e l y a c c e p t e d I n t h e case of s h a l l o w j u n c t i o n VLSI technology. I n t h i s p a p e r a n a n a l y s i s of i n f l u e n c e of doping on t h e k i n e t i c s of atmo*pneric p r e s s u r e BPSG deposition p r o c e s s and some p r o p e r t i e s of t h e d e p o s i t e d l a y e r i s p r e s e n t e d . The a i m of t h i s s t u d y i s t o o p t i m i z e t h e p r o c e s s from t h e p o i n t of view of subsequent proces- s i n g r e s u l t s and y i e l d . S t a r t i n g t h e s t u d y w i t h t h e model of S i 0 2 de- p o s i t i o n d e s c r i b e d e l s e w h e r e , t h e i n f l u e n c e of doping w a s considered.A s a r e s u l t , it w a s conclude& t h a t t h e BPSG d e p o s i t i o n p r o c e s s should be performed a t r a t h e r low temperature and h i g h oxygen t o s i l a n e r a t i o . B e s i d e s , o p t i m l z a t l o n of gas flow uniformity il of g r e a t importance.
INTRODUCTION
h e of t h e most s e n s i t i v e p o i n t s of modern I C p r o d u c t i o n p r o c e s s , s e r i o u s l y i n f l u e n c i n g o r even d e t e r m i n i n g t h e y l e l d , 1s c r e a t l o n of c o n t a c t s and i n t e r - c o n n e c t i o n s . The c o n t i n u i t y and u n i f o m l t y of m e t a l i n t e r c o n n e c t s o v e r s t e p s and d r y e t c h e d v e r t i c a l w a l l s i n i n s u l a t o r l a y e r s must be i n s u r e d , r e g a r d l e s s of s u b s t r a t e topography. The w i d e l y adopted s t r a t e g y f o r a c c o m p l i s h i n g t h i s t a s k i s d e p o s i t i o n and s u b s e q u e n t h i g h t e m p e r a t u r e flow o f p h o s p h o s i l i c a t e g l a s s (PSG) l a y e r
[I].
A s d e v i c e geometry s h r i n k and low t e m p e r a t u r e pro- c e s s i n g becomes more and more i m p o r t a n t , PSG i s r e p l a c e d w i t h t e r n a r y , boro- p h o s p h o s i l i c a t e g l a s s (BPSG),
which f l o w t e m p e r a t u r e i s c o n s i d e r a b l y lower [2].I n t h l s p a p e r a n a n a l y s l s of influence o f BPSG d e p o s i t i o n p r o c e s s c o n d i t i o n s on t h e k i n e t i c s and some p r o p e r t i e s of t h e deposited l a y e r w i l l be p r e s e n t e d . Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1989569
C5-586 JOURNAL DE PHYSIQUE
The a i m of t h i s s t u d y w a s t o optimize d e p o s i t i o n process from t h e p o i n t of view of s u b s e q u e n t p r o c e s s i n g r e s u l t s and f i n a l l y , of y i e l d .
The c r i t e r i a
Now, t h e q u e s t i o n a r i s e which p r o p e r t i e s of t h e d e p o s i t e d l a y e r should be adopted as a c r i t e r i a . ~ t ' s o u r e x p e r i e n c e , t h a t t h e most i w p o r t a n t f o r subsequent p r o c e s s i n g i s good u n i f o r m i t y of b o t h , p l a n a r i z a t i o n ( i . e . f l o w ) and e t c h r a t e of t h e BPSG l a y e r . B e s i d e s , low p a r t i c u l a t e l e v e l is of g r e a t importance f o r h i g h y i e l d of VLSI d e v i c e s . I t s h o u l d be n o t e d h e r e , t h a t both, flow and e t c h r a t e u n l f o r m i t l e s a r e determined mainly by uniformity of boron concentration I n t h e d e p o s i t e d l a y e r .
According t o t h e d a t a p u b l i s h e d by W.Kern e t a l . [ 2 ] t h e one p e r c e n t i n c r e a s e of boron c o n c e n t r a t i o n w i t h phosphorous c o n c e n t r a t i o n f i x e d c a u s e 1 0 0 ~ ~ drop of t h e g l a s s flow t e m p e r a t u r e and a p p r . 50% d e c r e a s e of e t c h r a t e i n 1:6 b u f f e r e d HF s o l u t i o n . Our r e s u l t s f o r l a y e r d e p o s i t e d i n s t a n d a r d VAPOX b e l t t y p e APCVD r e a c t o r a t 3 7 5 O ~ a r e p r e s e n t e d on f i g . 1.
t
3PS6 as depositedI C
4 2 9 4 5 6
B o r o n c o n c e n t r a t i o f i , dt Z
Fig.1. BPSG e t c h r a t e i n 1:6 BHF, as d e p o s i t e d , as a f u n c t i o n of boron c o n c e n t r a t i o n , phosphorous c o n c e n t r a t i o n f i x e d a t appr. 4 W t % Both, PSG and BPSG l a y e r s may be d e p o s i t e d by means of CVD method i n t h e v a r i e t y of r e a c t o r t y p e s and u s i n g d i f f e r e n t t y p e s of c h e m i s t r y . Well known s i l a n e o x i d a t i o p a t atmospheric p r e s s u r e i n t h e presence of phosphine and d i b o r a n e seems t o b e , however, t h e method a c c e p t e d and w e l l e s t a b l i s h e d i n thb i n d u s t r y .
There a r e t h r e e main r e a s o n s of t h i s :
-
t h e equipment neeeessary i s s i m p l e and i n e x p e n s i v e ,-
t h e method i s s i m p l e and w e l l c o n t r o l l e d ,-
t h i c k n e s s and, what i s most i m p o r t a n t , dopant c o n t e n t u n i f o r m i t i e s a r e good, u s u a l l y b e t t e r t h a n i n t h e c a s e o f o t h e r methods 153.I n g e n e r a l opinion, t h e weak p o i n t of t h i s method i s h i g h d e n s i t y of p a r t i - c l e s d e p o s i t e d on t h e w a f e r s u r f a c e . P r o p e r d e s i g n of r e a c t o r geometry however, l e a d s t o s u b s t a n t i a l improvement of t h e p r o c e s s c l e a n l i n e s s [7,4]
N e v e r t h e l e s s , p r o p e r s e l e c t i o n of t h e p r o c e s s c o n d i t i o n s i s v e r y i m p o r t a n t t o r e d u c e t h e g e n e r a t i o n of p a r t i c l e s .
l o summarize t h i s p a r t of t h e s t u d y it may be s t a t e d t h a t ,
-
d e s p i t e of numerous new methods of d e p o s i t i o n , APCVD method is s t i l l w i d e l y u t i l i z e d i n m i c r o e l e c t r o n i c s f o r BPSG l a y e r d e p o s i t i o n ,-
conditions of t h e d e p o s l t l o n s h o u l d be optimized t o a c h i e v e good d o p a n t , e s p e c i a l l y boron, c o n t e n t u n i f o r m i t y and low p a r t i c u l a t e d e n s i t y .EXPERIMENTAL
BPSG l a y e r s were d e p o s i t e d on 3" s i l i c o n w a f e r s i n s t a n d a r d , b e l t t y p e APCVD r e a c t o r , u s i n g 5% SiH4-N2
,
5% pHg-N2,
2% B2H6 -N2 and oxygen a s t h e r e a c t a n t s . P r o c e s s t e m p e r a t u r e was changed from 325 -ho 4 2 5 ' ~ . Thickness of t h e d e p o s i t e d l a y e r s were measured u s i n g e l l i p s o m e t e r . Dopant c o n c e n t r a t i o n w a s measured by means of wet chemical a n a l y s i s . P a r t i c l e d e n s i t y measurements were done by means of v a r i e t y of l a s e r based t e c h n i q u e s , among o t h e r s u s i n g S u r f s c a n (Tencor) and WIS 150 (EsTEC-~eronca) d e v i c e s .PROCESS KINETICS
C o n s i d e r i n g t h e i n f l u e n c e of p r o c e s s c o n d i t i o n s on ~ t s k i n e t i c s and f i n a l l y on t h e p r o p e r t i e s of t h e d e p o s i t e d l a y e r , we may s t a r t t h e s t u d y from t h e mo- d e l of t h e d e p o s i t i o n p r o y z s developed f o r SiOa d e p o s i t i o n [ 6 , 7 , 8 ) .
It w a s demonstrated [8,9] <ay be proved t h e o r e t i c a l l y
fi01,
t h a t t h e kind of r a t e c o n t r o l ( k i n e t i c o r d i f f u s i v e ) depends on t h e p o s i t i o n of t h e p r o c e s s o p e r a t i n g p o i n t a t t h e r = F ( n ) p l o t , where n denotes oxygen t o h y d r i d e r a t i o Cfi8.2).Table I. The dependence of r a t e c o n t r o l on t h e p o s i t i o n of o p e r a t i n g p o i n t on r = f ( n ) graph.
The meaning of v a l u e s A3 and A4 i s d e s c r i b e d by e x p r e s i o n s :
"
/lrZ4)* (k15 k13/k14)-1A3 = (2k25 27 r o l l i n g s t e p d i f f u s i o n of SiH4 d i f f u s i o n of O2 a d s o r p . , d e s o r p . d i s s o c i a t i o n
I
+
I1
+
t I - I V
-+
c
IV-A4
+
111-11
+ + +
R4
i t
+
A 4 - I I T
-I-
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O x s q e n t o k y d r ; d e rrrtr'o m o l / m o L ( n ) Fig.2. The t h e o r e t i c a l dependence of t h e S i 0 2 d e p o s i t i o n r a t e on t h e
oxygen t o s i l a n e r a t i o ( n ) a t 3 7 5 ' ~ and f i x e d v a l u e s of s i l a n e c o n c e n t r a t i o n (mol/mol) 5x1 0-4, 1 X I
o-'
and 2x1om3
( c u r v e s l a b e l l e d r l , r 2 , and r 3 r e s p e c t i v e l y ) . Curves I , 11, 111 and I V s e p a r a t e t h e a r e a w i t h d i f f e r e n t kind of r a t e c o n t r o l , a c c o r d i n g t o t h e t a b l e I.where :
kl 3
-
oxygen a d s o r p t i o n r a t e c o n s t a n t , k I 4-
oxygen d e s o r p t i o n r a t e c o n s t a n t , k1 5-
oxygen d i s s o c i a t i o n r a t e c o n s t a n t , k2 3-
s i l a n e a d s o r p t i o n r a t e c o n s t a n t , k24-
s i l a n e d e s o r p t i o n r a t e c o n s t a n t , k2 5-
s i l a n e d i s s o c i a t i o n r a t e c o n s t a n t .It f o l l o w s from t h e model [ 8 ] , t h a t i n c r e a s e of t h e p r o c e s s t e m p e r a t u r e r e s u l t s i n r a i s e of A and A v a l u e s and s h i f t of t h e whole p l o t t o t h e hig-
3 4
h e r v a l u e s of oxygen t o s i l a n e r a t i o ( f i g . 3 ) .
c u r v e s 1-1, 11-1 and r-1 a r e p l o t t e d f o r t e m p e r a t u r e TI
n
o r y q e n 40 ~ i L ~ n t 2 ra60
F i g . 3. The i n f l u e n c e of t e m p e r a t u r e on t h e p r o c e s s k i n e t i c s , t h e meaning of curves 1,II and r a c c o r d i n g t o f i g . 2 .
F o r oxygen t o s i l a n e r a t i o n p r o c e s s c o n t r o l i s k i n e t i c a t tempera- t u r e T, and d i f f u s i v e o r mixed a t temperature T2.
INFLUENCE OF DOPANTS
P r e s e n c e of dopants i n gas phase s u b s t a n t i a l l y i n f l u e n c e s g l a s s d e p o s i t i o n k i n e t i c s . According t o d a t a p u b l i s h e d by Kern e t a l , 1 2 1 , a d d i t i o n of 9,6%
of d i b o r a n e r e s u l t s i n 50% d e c r e a s e of d e p o s i t i o n r a t e . Phosphine doping a f f e c t s d e p o s i t i o n r a t e s l i g h t l y o n l y [ l l ] . Our r e s u l t s f o r l a y e r s d e p o s i - t e d i n APCVD b e l t t y p e r e a c t o r a r e p r e s e n t e d a t f i g . 4.
C o n s i d e r i n g t h e i n f l u e n c e of boron and phosphorous doping on t h e k i n e t i c s of t h e d e p o s i t i o n p r o c e s s we have t o d e c i d e , a t t h e f i r s t , what i s the-me- chanism of t h i s i n f l u e n c e
-
h e t e r o g e n e o u s o r homogeneous.I n o u r opinion, t h e r e a s o n i n g proposed by Meyerson eta@
4
m a y be a d o p t e d i n t h i s c a s e a l s o . C o n c e n t r a t i o n of B H 2 6 i n t h e gas phase i s i n s u f f i c i e n t t oY
f too
".-I
0
Q 9,
I
2 4 6 8 ~ 0
mole Ye B z H s
0 P? c o n c e n t r a t i o n 8 mole%
PH c o n c e n t r a t i o n 3' mole%, 3
Fig.4. An i n f l u e n c e of doping on t h e BPSG d e p o s i t i o n r a t e , T= 3 7 5 O ~
.,
C5-590 JOURNAL DE PHYSIQUE
e x p l a i n observed i n h i b i t i o n by consumption of s i l a n e as a r e s u l t of gas phase r e g c t i o n w i t h d i b o r a n e . B e s i d e s , gas phase t e m p e r a t u r e i s r e l a t i v e l y low ( 100
-
2 0 0 ' ~ ). T h e r e f o r e , t h e i n f l u e n c e of doping on t h e d e p o s i t i o n r a t e i s most p r o b a b l y due t o heterogeneous r e a c t i o n .C o n s i d e r i n g now t h e atomic and e l e c t r o n c o n f i g u r a t i o n of s u r f a c e [6] and r e a c t a n t m o l e c u l e s , we have t o n o t e , t h a t d i b o r a n e molecule i s e l e c t r o n d e f i c i e n t and e a s i l y r e a c t s w i t h Lewis bases. T h e r e f o r e we may suppose, t h a t a d s o r p t i o n of B2H6 p r o c e e d s on n e g a t i v e l y charged oxygen atoms a t t h e s u b s t r a t e s u r f a c e . S i m i l a r p r o c e s s of PH a d s o r p t i o n i s n o t l i k e l y , s i n c e i t proceeds through a n i n t e r a c t i o n of PH 3 f r e e e l e c t r o n p a i r w i t h t h e s u r f a c e a c t i v e c e n t e r . It may be supposed t h e n , t h a t t h e f i r s t s t e p of t h i s 3 p r o c e s s i s interaction of PH molecule w i t h p o s i t i v e l y charged " s i l i c o n "
s u r f a c e a c t i v e c e n t e r and i n second s t e p phosphorous atom i s bonded t o 3 oxygen 1133.
C o n s i d e r i n g s u r f a c e a d s o r p t i o n mechanism we have t o r e a l i z e , t h a t t h r e e d i f f e r e n t s p e c i e s compete t o a d s o r b a t lloxygenn s u r f a c e a c t i v e c e n t e r s , namely SiH3 [6], PA3 and B2H6 r a d i c a l s and molecules. I f we compare now t h e e n t h a l p y of oxide f o r m a t i o n p e r mole 0 2 , which could be a measure of bonding s t r e n g h t , f o r P (456IC~/mol O2 )
,
f o r S i (574 k ~ / m o l 02) and f o r B (632 k ~ / m o l 03)1141
it's n o t s u p r i s i n g t h a t boron behaves as p o i s o n of S i 0 2 and P205 d e p o s i t i o n , whereas analogous i n f l u e n c e of phosphorous i s n e g l i g i b l e . On t h e o t h e r hand boron a c t s as a s h a l l o w a c c e p t o r i namorphous SiO while t h e b e h a v i o u r of phosphorous atoms i s n o t s o c l e a r
n3
Therefore, l o o k i n g once more a t t h e mechanism of s u r f a c e r e a c t i o n proposed 2 i n [6] we may n o t e , t h a t h o l e s c r e a t e d by boron atoms w i l l enhahce s i l a n e a d s o r p t i o n a t p o s i t i v e l y charged u s i l i c o n u a c t i v e c e n t e r s . S i m i l a r pheno- menon w a s r e p o r t e d i n t h e c a s e of s i l i c o n d e p o s i t i o n [16,17]. A s a r e s u l t
of t h i s , i n c r e a s i n g boron c o n c e n t r a t i o n wil$ause i n c r e a s e of A3 v a l u e (eq. 2)' and f i n a l l y , t h e change of r a t e c o n t r o l i n t o d i r e c t i o n of more d i f f u s i v e t y p e ( f i g . 5 ) .
The i m p o r t a n t c o n c l u s i o n which may be drawn a t t h i s p o i n t i s , t h a t i n t h e c a s e of BPSG d e p o s i t i o n t h e p r o c e s s u n i f o r m i t y w i l l be l e s s dependent on t e m p e r a t u r e and more on qas f l o w u n i f o r m i t y t h a n i n t h e c a s e of SiO 2'
curves 1-1, 11-1 and r-I p l o t t e d f o r boron conc.
curves 1-2, 11-2 and 32-2 p l o t t e d f o r boron conc.
b
" 9
h3- 4
t
As- 2 Owy gen +o hydrrde vat.&
a r e C ~ l a r e ' ~ 2
Fig.5. The i n f l u e n c e of boron c o n c e n t r a t i o n on t h e process k i n e t i c s , t h e meaning of curves I , I1 and r, a c c o r d i n g t o fig.2.
For oxygen t o s i l a n e r a t i o n , process c o n t r o l is k i n e t i c a t boron c o n c e n t r a t i o n CB, and d i f f u s i v e o r mixed a t boron c o n c e n t r a t i o n CBp.
PARTICLES
A s i t was mentioned e a r l i e r , a p a r t from u n i f o r m i t y , low p a r t i c l e l e v e l is of g r e a t importance i n VLSI technology. Considering t h i s problem we have t o n o t e , t h a t i n t h e case of cold w a l l r e a c t o r system, gas phase temperature
i s considerably lower than t h a t of s u b s t r a t e s u r f a c e . Such s i t u a t i o n i s i d e n t i c a l a s p r e s e n t e d s c h e m a t i c a l l y i n fig.3. Curves 1-1, 11-1 and r-I d e s c r i b e t h e p r o c e s s k i n e t i c s a t t h e p a r t i c l e s u r f a c e (lower temperature) whereas curves 1-2, 11-2 and r-2 d e s c r i b e t h e l a y e r growth ( h i g h e r tempera- t u r e ) . We may s e e now, t h a t t o s u p r e s s p a r t i c l e growth, we have t o c a r r y out t h e process a t high oxygen t o s i l a n e ( h y d r i d e ) r a t i o , s o t h a t t h e l a y e r d e p o s i t i o n r a t e w i l l be high enough, while p a r t i c l e growth w i l l be i n h i b i t e d . T h e o r e t i c a l e s t i m a t i o n taken from such curves p l o t t e d f o r v a r i o u s process temperature as w e l l a s experimental r e s u l t s measured with S u r f s c a n
(Tencor) instrument (0.25 um2 c r o s s s e c t i o n range) and v e r i f i e d by means of WIS 150 (ESIEC) device (0.5 pm range) a r e p r e s e n t e d i n f i g . 6.
JOURNAL DE PHYSIQUE
Fig.6. D e n s i t y o f p a r t i c l e s d e p o s i t e d on wafers as a f u n c t i o n of r e c i p r o c a l of t e m p e r a t u r e , f o r two oxygen t o h y d r i d e r a t i o n=30 and n=40.
d C 0.6
J
0.5 Q
0.4
2 ao-
A a, 0.2
Y 0
t' 0.4
2
B e s i d e s , i t s h o u l d be noted f u r t h e r , t h a t f o r h i g h oxygen t o h y d r i d e r a t i o ( n ) , t h e p a r t i c l e growth i s k i n e t i c a l l y c o n t r o l l e d , whereas l a y e r growth c o n t r o l i s mixed. T h e r e f o r e , a p p a r e n t a c t i v a t i o n energy of t h e l a y e r growth i s lower t h a n t h a t of t h e p a r t i c l e growth. I n o t h e r words, t h e p a r t i c l e growth s t r o n g l y depends on t h e t e m p e r a t u r e , w h i l e t h e t e m p e r a t u r e dependen- c e of t h e l a y e r growth i s r e l a t i v e l y weak. The p r a c t i c a l c o n c l u s i o n from t h i s s i m p l e r e a s o n i n g i s t h a t low t e m p e r a t u r e i s recommended f o r BPSG d e p o s i t i o n .
4
1. e x p e r i m e n t a l c u r v e , n=40-
2.. e x p e r i m e n t a l c u r v e , n = 3 63. t h e o r e t i c a l e s t i m a t i o n
- - -
-
b
To optimize 3PSG d e p o s i t i o n c o n d i t i o n s t h e a n a l y s i s of p r o c e s s k i n e t i c s w a s e r f o r m e d . The c o n c l u s i o n s were drawn t h a t t o a c h i e v e good u n i f o r m i t y and ].ow p a r t i c l e l e v e l , t h e p r o c e s s s h o u l d be c a r r i e d out a t low temperatu- r e (350
-
3 8 0 ' ~ ) and h i g h oxygen t o s i l a n e r a t i o( 3
40). I t w a s concluded a l s o , t h a t t h e u n i f o r m i t y of t h e d e p o s i t e d l a y e r ( t h i c k n e s s and dopaht c o n t e n t ) depends mainly on t h e g a s flow u n i f o r m i t y . T h e r e f o r e r e a c t o r geometry s h o u l d be c a r e f u l l y optimized.T h i s work w a s s u p p o r t e d by t h e program CPBP 01.08.
WFERENCES
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(1986)2199, Grabiec, P.B., Proc. of the Fifth European Conf. on CVD, IJppsala 1985,161 10. Grabiec, P.B., Electron Technol., to be published
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(1984) 236113. Saxena, A.N., Powell, R.A., in "The lhysics of Si02 and its Interfacesu, Ed. S.T.Pantelides, Pergamon 1978,p.195
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