Silicon Wafer Manufacturing: A CEP Cer Fica On Course

Slllcon wafer manufacLurlng
Anll kouanLharayll
ll1 8ombay
1
A CL Cerucauon Course:
SemlconducLor 1echnology and ManufacLurlng
Anll kouanLharayll, ll1 8ombay 20Lh november 2012
Anll kouanLharayll, ll1 8ombay 20Lh november 2012 2
Crysta|s
- A mater|a| that exh|b|ts perfect per|od|c|ty |n atom|c structure
naCl crysLal
CourLesy: MlnnesoLa unlverslLy
CrysLalllne
(mono crysLalllne)
olycrysLalllne
(mulu crysLalllne)
amorphous
- Crysta| can be dehned |n terms of a symmetr|c array of po|nts |n space ca||ed
|amce
1he S|||con Crysta| structure
2-u pro[ecuon
ln Lhe [100] on
Lhe (100) plane
1wo lnLerpeneLraung face cenLered cublc lamces dlsplaced by a/4, a/4, a/4
8adlus of Sl aLom: 1.18
Lamce consLanL: 3.43
SmallesL spaclng beLween aLoms: 2.33
Pard sphere packlng denslLy: 34
CreaLed uslng 8alls & Sucks
Monocrysta|||ne and po|y crysta|||ne S|
CrysLalllne
olycrysLalllne amorphous
C.-P. 1ung, C. 1. 1. Sheng and C.-?. Lu, uLSl SemlconducLor 1echnology ALlas, Wlley lnLersclence, 2003
c-Sl
a-SlC
2

poly-Sl
Crysta| |anes
|anes:
1. uene a CarLeslan coordlnaLe sysLem wlLh Lhe orlgln aL any
lamce polnL and allgn Lhe axes wlLh Lhe edges of Lhe cublc unlL
cell
2. CbLaln Lhe lnLercepLs of Lhe plane wlLh Lhe crysLal axes and
express Lhem as lnLeger muluples of basls vecLors
3. 1ake Lhe reclprocals of Lhe Lhree lnLegers and reduce Lhem Lo
Lhe smallesL seL of lnLegers h, k and l, wlLh Lhe same rauo as Lhe
reclprocals
4. 1he plane ls labeled (hkl) and h, k and l are called Mlller lndlces
3. ln a lamce Lhere are many equlvalenL planes. 1hey are
collecuvely called [hkl} planes
Lxerc|se 1
Idennfy the (100), (110) and (111) p|anes |n the cub|c |amce.
Crysta| D|recnons
D|recnons:
1. A dlrecuon ln a crysLal ls dened ln Lerms of Lhe componenLs of a vecLor
ln LhaL dlrecuon
2. 1he vecLor componenLs belng expressed ln Lhe smallesL lnLeger
muluples of Lhe basls vecLors
3. lor example, Lhe dlrecuon 1a, 1b, 1c ln a cublc lamce ls represenLed as
[111]
4. 1he seL of equlvalenL dlrecuons are placed ln angular brackeLs <>
3. ln a cublc lamce, Lhe dlrecuon [hkl] ls perpendlcular Lo Lhe plane (hkl)
Lxerc|se 2
Idennfy the [100], [110] and [111] d|recnons |n the cub|c |amce.
An|sotropy |n S| |amce
ro[ecuon on (100) ln [100]
ro[ecuon on (111) ln [111] ro[ecuon on (110) ln [110]
CreaLed uslng 8alls & Sucks
Crysta| Defects
Any |nterrupnon from the regu|ar arrangement |n a crysta| |s a
defect.
olnL defecLs: subsuLuuonal, vacancles and lnLersuuals
1u defecLs: dlslocauons
2u defecLs: sLacklng faulLs
3u defecLs: volds (collecuon of vacancles), preclplLaLes of
dopanLs and lmpurlues
o|nt defects
SubsuLuuonal vacancy lnLersuual
Crysta| Defects: L|ements from other groups
uonor level
AccepLor level
S. M. Sze, hyslcs of SemlconducLor uevlces
Sl, 1.12 ev
n|gher order defects: formanon
Stress: lnLernal forces wlLhln a maLerlal ln response Lo exLernal forces and
ls expressed ln force per unlL area (n/m
2
)
Stra|n: measure of Lhe deformauon of Lhe maLerlal ln response Lo sLress

L|asnc ||m|t]y|e|d strength: sLress aL whlch Lhe maLerlal sLarLs Lo deform
plasucally.
|asnc deformanon: lrreverslble deformauon of Lhe maLerlal

Lxample: bendlng a plasuc ruler

Plgher order defecLs relaxes Lhe sLress.

n|gher order defects: formanon (2)
Lxamples from Sl processlng:

1. Plgh concenLrauon of dopanLs wlLh hlgh mlsL facLor

n|gher order defects: formanon (3)
Lxamples from Sl processlng:

2. 1hermal sLresses: 8apld 1hermal rocesslng, crysLal growLh

o ls Lhe Lhermal sLress, o ls Lhe Lhermal expanslon coemclenL, ? ls Lhe ?oung's
modulus and A1 Lhe LemperaLure dlerence.

When Lhermal sLress exceeds yleld sLrengLh, plasuc deformauon can happen
leadlng Lo defecLs.

lor Sl:
?
111
= 1.9 x 10
7
n/cm
2
, ?leld sLrengLh ~ 0.3 x 10
4
n/cm
2
, o = 2.6 x 10
-6
/
o
C

WhaL value of A1 could lead Lo defecL formauon?
!
" = #Y$T
D|s|ocanons
dlslocauon ls a 1u defecL
for example, lnseruon of an exLra llne of aLoms or vacancles lnLo an
oLherwlse perfecL lamce
Lhe lnserLed llne ls Lyplcally Lhe same klnd as Lhe hosL maLerlal, l.e. Sl ln
Sl
Stack|ng fau|ts
A sLacklng faulL can be consldered as a 2u verslon of a dlslocauon
A mlsslng crysLal plane ls called an lnLrlnslc sLacklng faulL
An exLra plane ls called an exLrlnslc sLacklng faulL
A sLacklng faulL LermlnaLes ln a dlslocauon
Lxample from CrysLal Maker soware package
Stack|ng fau|ts
LlecLron mlcroscopy group, ueparLmenL of MaLerlals Sclence
and MeLallurgy, unlverslLy of Cambrldge.
hup://www-hrem.msm.cam.ac.uk/gallery/plcs/ganlarge.[pg
Can
MaLerlal: Slllcon
hup://www.ece.umn.edu/groups/nsfreL/1LMplcs.hLml
rec|p|tates and vo|ds
reclplLaLes are 3u defecLs. Agglomerauon of polnL, llne and 2u defecLs.
1yplcally of forelgn aLoms or molecules ln an oLherwlse crysLalllne
maLerlal.
Can be of large slze ~ mlcro meLers
Local order of Lhe preclplLaLed specles, can be dlerenL from Lhe
crysLal of lnLeresL => bounded by lower order defecLs
reclplLauon of unwanLed lmpurlues ls a Lechnlque Lo keep Lhem
away from devlce reglons
volds are usually noL presenL ln grown crysLals. 8uL we would see
examples ln SCl wafers laLer on.
lmage of oxygen preclplLaLes ln Sl wafer from C. k. Su
(MLMC), ConLrolllng dlslocauons and bulk mlcrodefecLs on
fabrlcaLed wafers Lo prevenL devlce leakage, hup://
www.mlcromagazlne.com/archlve/03/07/su.hLml
S| Wafer Manufactur|ng
uevlce
uevlce

uevlce uevlce
Lxample: vLSl Lxamples: some of Lhe power devlces,
phoLovolLalcs
- Sl - 2
nd
mosL abundanL maLerlal on earLh's cresL (~23)
- 8uL ln Lhe form of SlC
2
- quarLz - sand (SlC
2
+ lmpurlues)
- vLSl grade: lmpurlLy levels Lyplcally ppb or 10
13
cm
-3
(~10
13
cm
-3
C & 10
18
cm
-3

oxygen Ck)
- Slngle crysLal for elecLronlc appllcauons, can be poly crysLalllne for solar cell
appllcauons
- ueslred reslsuvlLy (doplng) and orlenLauon
- 8equlred ln Lhe shape of clrcular wafers for vLSl and square for solar cell
- Mechanlcal properues
- smooLh mlrror nlsh Lop surface (llLhography and lnLerfaces)
- mlnlmal bow and Laper
- Lhlckness of Lhe wafer Lo glve mechanlcal sLrengLh
22
uartz to Meta||urg|ca| Grade S|||con
S|C
2
+ 2 C ! S| + 2CC
quarLzlLe
coke
/coal
MeLallurglcal grade ~ 98 purlLy
~ 2000C & 13 kWh/kg
Impur|nes |n meta||urg|ca| grade S|||con (|n ppm by we|ght)
C:100 - 3000
le: 300 - 3000
Al: 300 - 3000
Ca: 20 - 2000
C: 30 - 1300
Mg: 3 - 200
1l: 100 - 1000
Mn: 10 - 300
v: 1 - 300
8: 3 - 70
: 3 - 100
Cu: 3 - 100
Cr: 3 - 130
nl: 10 - 100
Zr: 3 - 300
Mo: 1 - 10
A. Luque and S. Pegedus, Pandbook of hoLovolLalc Sclence and Lnglneerlng, Wlley, 2011
23
Arc furnace for meta||urg|ca| grade s|||con producnon
2Sl (l) + C
2
(g) ! 2SlC (g)
2SlC (g) + C
2
(g) ! SlC
2
(g)
SlC
2
+ 2 C ! Sl + 2CC
24
Meta||urg|ca| grade to e|ectron|c grade s|||con

S| + nC| ! S|n
4
+ C|
2
! S|n
3
C| + C|
2
! S|n
2
C|
2
! S|nC|
3
+ n
2
! S|C|
4
+ n
2
MCS, powder
Plgh LemperaLure

caLalysLs
S|emens process reacnons

S|nC|
3
+ n
2
! S| + 3nC|

2S|nC|
3
! S|n
2
C|
2
+ S|C|
4
S|n
2
C|
2
! S| + 2nC|

nC| + S|nC|
3
! S|C|
4
+ n
2
23
S|emens process for producnon of L|ectron|c
grade S|||con
26
S|emens process for producnon of e|ectron|c
grade S|||con
90 energy losL Lo Lhe cold
walls
MeLallurglcal grade (MCS) Lo elecLronlc grade (LCS)

SlPCl
3
ls a llquld aL 81 ! purlfy furLher by fracuonal dlsullauon

urled SlPCl
3
ls used for deposluon of poly-Sl on a poly-Sl rod by chemlcal
vapor deposluon (Cvu)

SlPCl
3
(gas) + P
2

(gas) ! Sl (solld) + 3 PCl (gas)

oly-Sl (99.999999999 pure)

- lmpurlLy levels of ppb or 10
13
Lo 10
14
cm
-3

- 8uL we need slngle crysLal wafers for uLSl
- SlPCl
3
or LC poly-Sl can be used as raw maLerlal for solar cell
28
Compar|son of d|erent grades of S|||con
Impur|ty Upgraded
meta||urg|ca| S|
So|ar Grade S|||con L|ectron|c Grade S|
1oLal meLalllc
lmpurlues (ppm)
< 1 < 0.03 < 0.001
uonor/
phosphorous
(ppm)
< 3 < 0.003 < 0.0003
AccepLor/boron
(ppm)
< 3 < 0.0003 < 0.0001
Carbon (ppm) < 30 < 3 < 0.1
Cxygen (ppm) < 100 < 3 < 1
S| Wafer Manufactur|ng for VLSI
- 1wo Lechnlques for fabrlcauon of slngle crysLal Sl lngoLs
- Czochralskl meLhod
- Large lngoL dlameLer posslble
- Plgh Cxygen (~10
18
cm
-3
) and Carbon (~10
13
cm
-3
) conLenL
- MosL wldely used Lechnlque
- lloaL-Zone meLhod
- Smaller lngoLs
- Less lssues wlLh conLamlnauon
- Plgh reslsuvlLy wafers
- ueLecLors (dark currenL ln phoLodlodes)
- ower semlconducLor devlces (breakdown sLrengLh)
- PlghesL emclency solar cell
- urlcauon by concenLrauon change by segregauon durlng Lhe
llquld - solld Lransluon
S| Wafer Manufacture for VLSI (2)
hup://www.processpeclalues.com/slllconp.hLm hup://www.memc.com/co-as-descrlpuon-crysLal-growLh.asp
Czochra|sk| Method
u|| rate |n C2 process
Czochralskl MeLhod
!
v
p max
=
65.14
r
Maxlmum pull raLe ln cm/hr,
8adlus of Lhe lngoL ln cm
Dopant |ncorporanon |n the crysta| |n the C2 process
Segregauon

uue Lo dlerenL solublllLy of Lhe dopanL ln Lhe solld and llquld phases, Lhe
dopanL would segregaLe Lo Lhe phase ln whlch Lhe solublllLy ls hlgher

LeL C
L
be Lhe concenLrauon by welghL of Lhe dopanL ln Lhe melL
C
S
be Lhe concenLrauon by welghL of Lhe dopanL ln Lhe solld

Segregauon coemclenL k ls dened as

usually k < 1
!
K =
C
S
C
L
Dopant |ncorporanon |n the crysta| |n the C2 process (2)
Segregauon coemclenL of common dopanLs & lmpurlues of lnLeresL ln Sl

Impur|ty Segreganon coemc|ent
As 0.3
C 0.07
C 0.3
0.33
Sb 0.023
Al 2.8 x 10
-3

Ca 8 x 10
-3

8 0.8
Au 2.3 x 10
-3

Dopant |ncorporanon |n the crysta| |n the C2 process (S)
Lxerclse: Make slmllar ploL for
8, As, , Al and Au ln Sl
S. k. Chandhl, vLSl labrlcauon rlnclples - Slllcon and Calllum Arsenlde, ohn Wlley and Sons, 1983
Cxygen |ncorporanon |n the crysta| dur|ng the C2 process
ln CZ process, oxygen dlssolves lnLo Lhe melL from Lhe quarLz cruclble
1yplcal concenLrauons are ln Lhe range of 3 x 10
17
- 10
18
cm
-3

1here are Lhree eecLs of oxygen ln slllcon
1. Solld soluuon hardenlng: oxygen lncorporaLed ln lnLersuual slLes ln Sl
forms covalenL bonds wlLh Sl (Sl-C-Sl) and Lhls resulLs ln lmproved yleld
sLrengLh of Sl (upLo 23 lmprovemenL).
2. Cxygen donors:
SlC
4
complexes whlch acL llke donors.
Can lncrease Lhe reslsuvlLy of llghLly p-Lype doped Sl by
compensauon.
lorms ln Lhe LemperaLure range of 400 - 300
0
C and ls unsLable
above 300
0
C
. u. lummer, M. u. ueal, . C. Crlmn, Slllcon vLSl 1echnology, earson Lducauon, 2001
Cxygen |ncorporanon |n the crysta| dur|ng the C2 process (2)
3. reclplLauon ln Lhe form of SlC
2

Solld solublllLy of oxygen ln Sl aL 1417
0
C ls ~ 10
18
cm
-3
whereas aL
1000
0
C, lL ls ~ 10
17
cm
-3

When Sl ls oxldlzed Lo form SlC
2
, Lhe volume expands by 120 over
LhaL of Lhe Sl used ln Lhe formauon. LxLra space ls requlred => SlC
2

forms by absorpuon of vacancles and creauon of lnLersuuals
(1 + 2) Sl + 2C
l
+ 2 v "! SlC
2
+ 2 l + sLress
Slnce a slgnlcanL local sLress can be developed, preclplLauon ls noL
favored aL all LemperaLures => compeung reacuons of SlC
2
formauon
and dlssoclauon can happen.
reclplLaLes are seen Lo nucleaLe or coalesce for process condluons aL
~ 700
0
C
Cnce small preclplLaLes are formed furLher expanslon can happen aL
1000
0
C
Cxygen |ncorporanon |n the crysta| dur|ng the C2 process (3)
1yplcal oxygen preclplLauon process
CZ wafer ls annealed aL 1100 - 1200
0
C for several hours Lo ouL
dluse Lhe oxygen from Lhe wafer surface => process should be
carrled ouL ln an oxygen free amblenL
A surface reglon wlLh oxygen concenLrauon below Lhe crlucal value
for preclplLauon can be obLalned
PeaL Lhe samples for several hours aL 700
0
C for nucleauon of Lhe
preclplLaLes => nucleauon happens below Lhe surface reglon
reclplLauon sLep aL 1000
0
C for several hours
. u. lummer, M. u. ueal, . C. Crlmn, Slllcon vLSl 1echnology,
earson Lducauon, 2001
lmage of oxygen preclplLaLes ln Sl wafer from C. k. Su (MLMC),
ConLrolllng dlslocauons and bulk mlcrodefecLs on fabrlcaLed wafers
Lo prevenL devlce leakage, hup://www.mlcromagazlne.com/archlve/
03/07/su.hLml
Carbon |ncorporanon |n the crysta| dur|ng the C2 process (4)
ln CZ process, oxygen dlssolves lnLo Lhe melL from Lhe quarLz cruclble and
some of Lhe oxygen would form SlC whlch ls Lhen evaporaLed from Lhe
surface of Lhe melL
SlC reacLs wlLh Lhe graphlLe parLs Lo form CC whlch geLs dlssolved ln Lhe
melL and geLs lncorporaLed ln Lhe crysLal
1yplcal concenLrauons are ln Lhe range of 10
16
1he followlng C relaLed eecLs are posslble ln Sl
1. C ls a group 4 aLom and hence can occupy a subsuLuuonal slLe wlLhouL
any harm
2. C ls smaller Lhan Sl so Lhere ls a local conLracuon aL Lhe slLe. Cxygen
preclplLauon resulLs ln local expanslon.
So Lhe preclplLauon of C and SlC
2
can go hand ln hand
lL would be dlmculL Lo creaLe oxygen free reglons ln Lhe wafer whlch
has large C concenLrauon
S| Wafer Manufactur|ng for VLSI (4)
I|oat-2one Method
hup://www.Lopsll.com/410
S| crysta| Seed
kI co||s
Mo|ten S|
o|y-S|
- LGS (po|y-S|) rods
- No cruc|b|es
- neanng by Lddy currents
- Low contam|nanon
Impur|ty segreganon |n the crysta| dur|ng the I2 process
1he lnlual rod ls llkely Lo have a unlform lmpurlLy prole
As Lhe zone melung sLarLs from Lhe bouom, lmpurlues from Lhe solld
segregaLes Lo Lhe llquld.
As Lhe zone moves up, Lhe llquld would conunue Lo collecL Lhe lmpurlues
1he lmpurlLy concenLrauon ln Lhe crysLal would lncrease as zone moves up
lloaL zone
Impur|ty segreganon |n the crysta| dur|ng the I2 process (2)
An analysls slmllar Lo LhaL ln CZ process can
be carrled ouL => exerclse.

1he rod can be sub[ecLed Lo more Lhan one
zone renlng pass whlch resulL ln hlghly pure
maLerlal aL one end of Lhe rode
8easonably unlform doplng of Lhe crysLal can
be obLalned by a reverse pass aer Lhe lnlual
pass for crysLalllzauon
k = 0.1
Dop|ng of the I2 |ngots
lf Lhe lnlual poly-Sl rod has a unlform doplng, reasonably unlform doplng of Lhe
crysLal can be obLalned by a reverse pass aer Lhe lnlual pass for crysLalllzauon
Carrylng ouL Lhe process ln a amblenL conLalnlng dlluLed gaseous compounds of
Lhe dopanLs llke P
3
, 8
2
P
6
can used for doplng of Lhe crysLal
neuLron LransmuLauon doplng: Sl conLalns nauve
30
Sl lsoLope (~ 3), parL of
whlch can be converLed Lo
31
Sl by neuLron radlauon.
31
Sl decays Lo
31
wlLh a half
llfe of 2.62 hrs. 3 - 10 cm doplng can be achleved.
S| Wafer Manufactur|ng for VLSI (S)
Gr|nd|ng the |ngot Wafer s||c|ng Ldge proh||ng
hup://www.memc.com/lndex.php?vlew=rocess-Anlmauons-
I|ats are ground
on the |ngot
S| Wafer Manufactur|ng for VLSI (6)
Wafer |app|ng
A|
2
C
3
+ water + g|ycer|ne
kemoves bow & taper
I|at wafer
Wafer po||sh
NaCn + S|C
2
CM
M|rror hn|sh
Lp|taxy
n|gh qua||ty S|
on top for dev|ces
S| etch
nNC
3
+ nI +
acenc ac|d
kemoves
mechan|ca|
damage
hup://www.memc.com/lndex.php?vlew=rocess-Anlmauons-
S|||con on |nsu|ator (SCI) wafers
Sl
8urled SlC
2

Sl
SlMC process: Separauon by lMplanLed Cygen
a raLher old Lechnology
Cxygen lmplanLauon, ~ 1.8 x 10
18
cm
-2

Anneallng
~ 1300 C
S|||con on |nsu|ator (SCI) wafers (2)
SmarL-cuL
P. van meer, h. u. Lhesls, ku Leuven, 2002
o|y-S| growth for So|ar Ce||s
ulrecuonal solldlcauon: 1ravelllng heaLer meLhod.
Arafune eL al., ournal of CrysLal CrowLh, 308 (2007) pp. 3.
o|y-S| growth for So|ar Ce||s (2)
1ravelllng heaLer meLhod.
o|y-S| growth for So|ar Ce||s (3)
hup://www.q[solar.com/producLengp.asp
hup://pveducauon.org/pvcdrom/manufacLurlng/mulucrysLalllne-slllcon
oly or mulu crysLalllne Sl block and wafer
Mono crysLalllne Sl wafer
Mono-||ke s|||con
8|b||ography
C.-P. 1ung, C. 1. 1. Sheng and C.-?. Lu, uLSl SemlconducLor 1echnology ALlas, Wlley
lnLersclence, 2003
M. ?ang eL al., erformance dependence of CMCS on slllcon subsLraLe orlenLauon for
ulLraLhln oxynlLrlde and PfC2 gaLe dlelecLrlcs, lLLL LlecLron uevlce Leuers, 2003, pp. 339
Soware for 3u lmage and anlmauon of crysLal sLrucLures, hup://www.LoycraLe.org/bs/
A. Luque and S. Pegedus, Pandbook of hoLovolLalc Sclence and Lnglneerlng, Wlley,
2011
ean-lerre Collnge, Slllcon-on-lnsulaLor Lechnology, MaLerlals Lo vLSl, 2nd edluon,
kluwer Academlc ubllshers, 1997.
ames 8. kuo and ker-Wel Su, CMCS vLSl Lnglneerlng Slllcon-on-lnsuaLor (SCl), kluwer
Academlc ubllshers, 1998.
Sorln CrlsLoloveanu and Sheng Ll, LlecLrlcal CharacLerlzauon of Slllcon-on-lnsulaLor
MaLerlals and uevlces, Sprlnger lnLernauonal Serles ln Lnglneerlng and CompuLer
Sclence, 1993.
Arafune eL al., ulrecuonal solldlcauon of polycrysLalllne slllcon lngoLs by successlve
relaxauon of supercoollng meLhod, ournal of CrysLal CrowLh, vol. 308, pp. 3-9, 2007.

Silicon Wafer Manufacturing: A CEP Cer Fica On Course

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