C-Si Industrial Cell Process: Whole Value Chain

c-Si industrial cell process: Whole value chain
Today’s c-Si cell process

Behind photovoltaics 57
Industrial process – MG-Si
- Elkem produced ca. 49% of the

world volume 200 000 t per year
for
- Aluminium-Industry
- Chemistry (Silicone)
- Semiconductor-Industry
- PV requiered 2008 ca. 50000 t

per year
- SiO2 (s)+ 2C(s) Si(l) + 2CO
- Purity: 99%
Firma Elkem, Norwegen
Today’s c-Si industrial cell process: Whole value
chain
chain
Required purities:
- for Elektronic-Industry: 98 % 10-13 %

- for Photovoltaic: 98 % 10-9 %
Process:
- 1. Destillation of SiHCl3
- 2. Deposition of Si from gas phase
1. Si(s) + 3HCl(g) SiHCl3(g)+ H2 (g) + heat

2. SiHCl3(g) + H2(g) Si(s) + 3HCl(g)
chain
Crystallisation
Industrial process: Crystallization
Boron doped Si
Oxygen
Metal impurities e.g. Fei
Mono crystalline Multicrystalline
Industrial process : crystallization
240 kg
chain
Industrial process: sawing
Industrial process: Slicing
- Max. Drahtgeschwindigkeit: 15 m/s Industrielle Maschine

- Drahtdurchmesser: 0,14 mm,
- Länge: 800 km
chain
How is the costs division for material, cell and

module?
Today’s c-Si industrial cell process
Properties
- P-type Si bulk (ca. 0.5 - 3 Ωcm and 200 µm)
- Texture (KOH+IPA or isotexture)
Ag
- Homogeneous P- emitter (40-60 Ω/sq)
n+
p-type Si - Al-BSF (depth 5 -10 µm)
p+ - Front side PECVD SiNx ARC (73 nm/n=2.1)
Al
AgAl
- Screen printed front Ag-contact
Typical c-Si industrial
- Full Al rear contact + AgAl pads
solar cell
Texture and wafer cleaning
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing
Edge isolation
220 µm
p-type mc-Si (ca. 1 Ωcm)
Texture and wafer cleaning mc-Si: acidic texture

Cz-Si: alkaline texture
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing
Edge isolation p 210 µm
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing
n+
Edge isolation p 55 Ω/sq. on both sides
POCl3-diffusion
PECVD SiNx one sided 70 nm
Screen printing
Co-firing
n+
p
Edge isolation
POCl3-diffusion
PECVD SiNx
Screen printing
Ag
Co-firing
n+
p Ag on front
Edge isolation
Al on rear side
Al
AgAl
Texture and wafer cleaning metal belt furnace
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing Ag
n+
Edge isolation p
p+
AgAl Al
POCl3-diffusion
− Laser
PECVD SiNx − Wet chemical
treatment
Screen printing
− Dicing saw
Co-firing Ag
n+
Edge isolation p
p+
AgAl Al
Single processes
Texture, saw damage etch
Texture and wafer cleaning mc-Si: acidic texture

Cz-Si: alkaline texture
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing
Edge isolation p 210 µm
Three ways to remove saw damage at ISC?
Alkaline etching (NaOH, KOH)
50
NaOH-etch - 36.0%
40
Reflectance, %
30
20
10
0
Actec etching and cleaning bench 400 500 600 700 800 900 1000 1100
Wavelength, nm
Isotexture (HF, HNO3, H2O)
50 NaOH-etch - 36.0%
acidic etching - 25,4%
40
Reflectance, %
30
20
10
Is KOH+IPA even more effective?
RENA inline acidic texturing tool 0
400 500 600 700 800 900 1000 1100
Wavelength, nm
reflectance curves of wafers after etching. Large

reductions due to texturing.
HNO3: oxidises the surface

HF: etches the oxide
only on as-cut surfaces!!!
SEM picture of an isotropic textured
surface with a screen printed finger standard texture takes ca. 5µm Si from each side
Alkaline texture (KOH+IPA)
- Reduces the reflection on (100) Si- surfaces

Licht
from 36% to 11% (400-1100 nm);
- Simple and cost effective texturisation with

NaOH-IPA or KOH-IPA on (100) surfaces only
but ...
- The reproducibility of the results often not satisfactory

- IPA is expensive and organic
- Texture quite slow to be in-line compatible >>>
70
60
50
Reflexion [%]
40
30
20
10
0
300 400 500 600 700 800 900 1000 1100 1200
Wellenlänge [nm]
keine Textur UKONx-Textur-2 KOH-IPA
How can you reduce the reflection even

more? What other texturisation do you know?
- Mechanical abrasion + damage etch!!
- Masking, photolithography, etching
- Remote Plasma Source (RPS) etch
- Reactive Ion Etching (RIE)
Diffusion
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing
n+
Edge isolation p
55 Ω/sq. on both sides
BBr3-diffusion
ECV measurements of different B-
B-emitter profiles (BBr3-diffusion)
emitters
2 step oxidation (90 Ohm/sq)
in-situ oxidation (90 Ohm/sq)
20
10
carrier concentration p [cm ]

-3
19
10
4BBr3+ 3O2 → 2B2O3 + 6Br2
2B2O3 + 3Si → 4B + 3 SiO2

18
10
principle of BBr3 diffusion and a loaded quartz boat
What other possibilities for diffusion do you

N(x,t)=Ns erfc(x/2sqtr(Dt)) 10 know? 17
0,0 0,2 0,4 0,6

depth [µm]
>> standard 60Ohm/sq diffusion is done at 940°

°C for 40min (2h 38 minutes total time)
BBr3-diffusion: other methods
Precursor deposition by: screen printing,

roller, spin-on, spray on, APCVD…
+
Diffusion in: in-line furnace, tube furnace…
POCl3-diffusion
Why is the P-profile so different from B-

profile?
N2, O2,
POCl3
ECV measurements of different P-

emitters processed at different
temperatures and times
Principle of POCl3 diffusion and a loaded quartz boat
>> standard 55Ohm/sq diffusion is done at 850°

°C for 20 minutes (1h 40 minutes total
time)
PECVD SiNx-deposition
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing n+
p one sided 70 nm
Edge isolation
NH3
Schematic drawing of PECVD SiNx reactor
50 NaOH-etch - 36.0%
acidic etching - 25,4%
45
Graphite boat for PECVD SiNx deposition NaOH-etch with SiNx - 9,8%
40 isotexture witch SiNx - 6.8%
35
Reflectance, %
What is SiNx doing to increase the 30
efficiency? 25
20
15
10
Standard SiNx is about 70nm 5
thick resulting in blue colour 0

400 500 600 700 800 900 1000 1100
Wavelength, nm
Anti Reflection Coating (ARC)
surface Ref. [%]
NaOH-etched 36*
NaOH+SiNx 9.8
isotexture 25.4
Iso+SiNx 6.8
KOH+IPA 11
KOH+IPA+SiNx 4
*reflectance between 400 and 1100nm
Screen printing
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing Ag
n+
Edge isolation p Ag on front
Al Al on rear side
AgAl
Screen printing
Baccini screen printer with improved camera system principle of screen printing
To ensure good fillfactors:

- Geometry of standard screen printed finger:
- Height: 20 µm
- Width110-140 µm
- Amount of paste ~ 150 mg for 156x156
mm2 wafers
How can the shadowing be reduced? standard screen printed finger
Screen printing: other metallisation
Standard screen Fine-line screen Angledcontact

Buried Buried(BC)
Contact
printing printing (ABC)
SiNx
ARC
Front contact
P-emitter
Si
+ easy contact formation + easy contact formation ++NO

veryshading losseslosses
low shading
+ good fill factors (78%) + low shading losses ++very
verygood
good fill
fillfactors
factors
(>80%)
(>80%)
- high shading losses - poor fill factors

--additional
additional process
process steps
steps
- stability problems
Screen printing: other metallisation
Roller-printing technique
for finger Material: mc-Si (Baysix), as-cut thickness 330 µm
metallisation
Solar cell size: 10x10 cm2
texture printing Voc Jsc FF η
[mV] [mA/cm2] [%] [%]
V-textured screen 614 34.2 76.2 16.0
V-textured roller 612 35.4 75.4 16.3
Solar cell size: 12.5x12.5 cm2

Buried-contact cell concept texture hydrogen Voc Jsc FF η
silicon nitride 2
passivation [mV] [mA/cm ] [%] [%]
alkaline no 593 31.0 77.2 14.2

+ plated
n + +
Ni/Cu
n alkaline yes 602 32.1 77.4 15.0
p
+ V-textured yes 628 36.3 76.8 17.5*
p
plated Ni/Cu * POLIX wafer; independently confirmed by FhG-ISE, Freiburg, Germany
M. McCann, B. Raabe, W. Jooss, R. Kopecek and P. Fath, 18.1% Efficiency for a Large Area, Multi-Crystalline Silicon Solar Cell, IEEE 4th World
Conference on Photovoltaic Energy Conversion, Hawaii, USA (2006)
Belt-furnace firing
POCl3-diffusion
PECVD SiNx Metal belt furnace

Screen printing
Ag
Co-firing
n+
p
Edge isolation p+
AgAl Al
Belt-furnace firing
Placement of solar cell on belt

6 zone belt furnace for fast firing
What contains the Ag-metal paste?

How does the front contact look after
firing?
Temperature on the cell during process Firing temperature dependent on

area and thickness of solar cell
Belt-furnace firing: Front
contact
Belt-furnace firing: front
contact
Ag
glass
Ag crystals tunneling
Cross section of a simple metal/Si interface (top) and a more
realistic picture of glass frit containing metal Ag paste/Si
interface for an industrial solar cell (bottom).
− Separation of Ag-crystals by glass layer

− Contact of Ag to emitter only through few points
− Tunneling of carriers through glass
− Contact resistance?
How does the BSF look after firing?
Edge isolation
How can the edges be isolated?
POCl3-diffusion
PECVD SiNx
Screen printing
Co-firing Ag
n+
Edge isolation p
p+
AgAl Al
− Laser
− Wet chemical treatment
− Dicing saw
Edge isolation
dicing saw:
slow but very good isolation
laser:
fast and good, used in the
industry
sand paper: these methods are used the

good isolation, low yield if not most at isc
done properly
fill factors exceeding 79%
were already processed
wet chemical:
fast and good, used in the industry
!has to be done directly after P-diffusion!
What is behind a solar cell?, June 2013 99

What are we talking about? c-Si solar cells
Semiconductor device consisting of a p-n junction and

metalized regions that directly converts sunlight into electricity.
area 15.6x15.6 cm2
thickness 180 µm area 90x160 cm2
Ag, Al contacts 60 cells in series
17-20 % efficiency 250-300 Wp
4-5 Wp
5/20
Processing
Reflexion:
Texture and wafer cleaning Reduced to 11%
(400 nm–1100 nm)
p-n junction formation (diffusion)
Plasma enhanced chemical

vapour deposition (passivation)
Elkem (1904)
Norway
Metallization
(screen printing)
Firing
Laser edge isolation
6/20
Cell efficiency
FFJ scVoc J max PPVmax PP
Cell efficiency η= where FF =
Pin J scVoc
FF: fill factor (measure of quadrature of JV curve)
JmaxPP and VmaxPP: maximum power point values
Jsc and Voc: short circuit current density and open circuit voltage
8/20
Loss mechanisms
Drawing from: H. Mäckel, 2004

Optical
Reflexion, shading
Transmission
Electrical: (1) recombination, (2) ohmic

(1) Radiative, Auger & Rec. via traps
Surfaces, emitter, bulk & space charge region
(2) Resistance of bulk metals (Ag fingers, Al area), Si

Contact resistance: metal to Si (Ag-Si, Al-Si)
9/20
Resulting contact
Ag finger (Ag bulk)
Ag bulk
Ag crystallites, glass, nano particles
11/20
Trend in PV technology

Thinner wafers
400 - 400 µm in 1990, 180 µm in 2007
wafer thickness [µm]
- aim: 150 µm in 2010

300
Larger wafers
- 1990: 100 cm2
200
- today: 225 cm2
?
100
Use of SoG-Si
0 - chemical purification
2002 2004 2006 2008 2010
- metallurgical purification
What happens with the efficiency when <d?

industrial solar cell
Ag
n+
p-type Si
p+
Al cells
Thinner and larger solar
16.5
standard process
16.0 improved rear side passivation
solar cell efficiency
15.5
15.0
14.5
Main losses on the rear side
14.0
250 200 150 100 50
Improved passivation: +25-30 mV / ca.+2
solar cell thickness [µm]
mA/cm2

bow
open
relaxation
passivation
rear contact

front junction bifacial device with BSF
main advantages
- elimination of bow
- improved rear side passivation
- less paste and printing steps used
- increased power output
- applicable for p and n-type Si
- simplified module interconnection
What is the advantage of bi-facial

modules??
Outdoors measurement on roof of PV lab at UKON
(southern Germany)
1,0
80
70
Conditions
0,8
in P [%]units]
- module
60 embedded in black frame (1x0.5) m2
[arbitrary 0,6
- placed
50
on white board
- inclined by 30° and facing to the South
gain
0,4
Pmpp
40
- measured in average gain
andinmonofacial
bifacialbifacial P of 33% (rear side
0,2
30 monofacial
30° covered) arrangement
0,0
20
white board 10 12 14 16 18
timeduring
time duringone
oneday
dayininAugust
August[h][h]
What efficiency can be reached with both sided contacted cells?
Why other processes? - selective emitter
20 - B-BSF rear side
19
- selective emitter
18
- standard rear
efficiency [%]
17
16 - standard cell
15
Do you know other trends?
14 Efficiencies >19% possible with
both sided contacted cells
13
1 10 100 1000
minority carrier lifetime [µs] To exceed 20% rear contact solar
cells needed
improvement of standard process

- Selective emitters Thin film solar cells
- Rear passivated cells - Thin Si absorbers
- CdTe, CIGS, GaAs
rear contact solar cells

- MWT, MWA, EWT, IBC
n-type solar cells
- Al-rear emitter
- B-front emitter

Improvement of standard
carrier concentration n [cm ]

-3
profile of selective emitter
20 30 nm SiNx
10
process: front with barrier (80 Ω/sq)
lasered regions (19 Ω/sq)
- Selective emitters
19
- Improved passivation 10
- Innovative metallisation
18
10
0,0 0,2 0,4 0,6
Improvement of standard
What selective emitter methods do you
process: rear know?
- Selective BSF
- Open rear contact
- Improved
passivation
- Innovative
metallisation
n-type solar cells
Rear Al-emitter solar cell Front B-emitter solar cell
n+ (phosphorous-FSF) p+ (boron-emitter)
n n
p+ (Al-emitter) n+ (phosphorous-BSF)
mc-Si: 15.0% mc-Si: 16.4%

FZ-Si: 17.4% Cz-Si: 18.5%
☺ Similar to p-type solar cell process ☺ Low quality material acceptable
☺ Easy implementation into existing ☺ Bifacial character
process lines What kind of rear contact cells do you
know? Passivation of p+ surfaces?
High quality, lowly doped material B-diffusion with mc-Si?
needed
Isofoton BOSCH

Rear contact solar cells
Metallisation Metallisation Emitter

Wrap Around (MWA) Wrap Through (MWT) Wrap Through (EWT)
+ +
+
n
+ + +
+ +
n n
+
+ n + +
n
+
n +
n
p p p
MWA MWA MWT EWT

Voc[mV] 611 614 612 591
Jsc[mA/cm2] 37.2 35.9 37.2 37.4
FF [%] 77.2 75.5 75.8 75.1
h [%] 17.5 16.6 17.2 16.6
Area [cm2] 5x5 10x10 5x5 5x5
What is the large area cell with highest efficiency?

Rear contact solar cells:

IBC cell
Efficiency of 23% was reached!!

HIT solar cell
Efficiency of 22% was

reached
What thin film technologies do you know?

Thin film solar cells:
- CdTe (First Solar)

- CIS, CIGS (Würth)
- a-Si
- micromorph Si
- crystalline Si
UMG - substrate

ISC building
Behind photovoltaics
120
ISC building
121
Well known research institutes
Well known research institutes
technlogy transfer highest efficiency
ZEBRA cell: history and roadmap
2012 EU project moderN-type: Eurotron modules ZEBRA gen2
24 2013 BMU project MetalTopp: p+ metallisation
pilot line and 2013 EU project HERCULES: ion-implantation
technology 23.5%
23 ZEBRA gen1 ion-implantation
transfer screen printed
22.5%
contacts
22 diffusions 330Wp 60 cell
screen printed contacts modules
21% 315Wp 60 cell modules
21 diffusions
screen printed contacts
300Wp 60 cell modules
20
19.7%
19
18
17.6%
17
2010 2011 2012 2013 2014 2015 2016
CoO of Module Technologies
High efficiency
Low cost
ZEBRA-IBC Module High efficiency
(expected CoO)
Module
ZEBRA (e.g. Sunpower IBC,
Panasonic HIT, ..)
High efficiency
High cost
Standard efficiency
MWT Module
avg. estimated CoO

2013 Standard Module sales price range (Q1/2013)
Low cost
Data from: Pvinsights, Photon, ITRPV 2013, Eurotron,

own calculations

C-Si Industrial Cell Process: Whole Value Chain

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c-Si industrial cell process: Whole value chain

Today’s c-Si cell process

- Elkem produced ca. 49% of the

- PV requiered 2008 ca. 50000 t

- SiO2 (s)+ 2C(s) Si(l) + 2CO

Firma Elkem, Norwegen

- for Elektronic-Industry: 98 % 10-13 %

1. Si(s) + 3HCl(g) SiHCl3(g)+ H2 (g) + heat

- Max. Drahtgeschwindigkeit: 15 m/s Industrielle Maschine

How is the costs division for material, cell and

- Texture (KOH+IPA or isotexture)

Texture and wafer cleaning

Texture and wafer cleaning mc-Si: acidic texture

Edge isolation p 210 µm

Texture and wafer cleaning

Texture and wafer cleaning

PECVD SiNx one sided 70 nm

Texture and wafer cleaning

Texture and wafer cleaning metal belt furnace

Texture and wafer cleaning

Texture and wafer cleaning mc-Si: acidic texture

Edge isolation p 210 µm

Three ways to remove saw damage at ISC?

reflectance curves of wafers after etching. Large

HNO3: oxidises the surface

- Reduces the reflection on (100) Si- surfaces

- Simple and cost effective texturisation with

- The reproducibility of the results often not satisfactory

keine Textur UKONx-Textur-2 KOH-IPA

How can you reduce the reflection even

- Mechanical abrasion + damage etch!!

- Masking, photolithography, etching

- Remote Plasma Source (RPS) etch

- Reactive Ion Etching (RIE)

Texture and wafer cleaning

55 Ω/sq. on both sides

carrier concentration p [cm ]

4BBr3+ 3O2 → 2B2O3 + 6Br2

2B2O3 + 3Si → 4B + 3 SiO2

principle of BBr3 diffusion and a loaded quartz boat

What other possibilities for diffusion do you

0,0 0,2 0,4 0,6

>> standard 60Ohm/sq diffusion is done at 940°

Precursor deposition by: screen printing,

Why is the P-profile so different from B-

ECV measurements of different P-

>> standard 55Ohm/sq diffusion is done at 850°

Texture and wafer cleaning

Schematic drawing of PECVD SiNx reactor

thick resulting in blue colour 0

Anti Reflection Coating (ARC)

surface Ref. [%]

*reflectance between 400 and 1100nm

Texture and wafer cleaning

To ensure good fillfactors:

Standard screen Fine-line screen Angledcontact

+ easy contact formation + easy contact formation ++NO

- high shading losses - poor fill factors

Solar cell size: 12.5x12.5 cm2

alkaline no 593 31.0 77.2 14.2

plated Ni/Cu * POLIX wafer; independently confirmed by FhG-ISE, Freiburg, Germany

Texture and wafer cleaning