Best Polysilicon Technologies

11th China Solar PV Conference and Exhibition

Russ Hamilton
19.Nov.2010
 Best Polysilicon Technologies
•

•WAFER •THIN-FILM CIS-materials •THIN-FILM •THIN-FILM Silicon

•Crystalline Silicon
(CIS/CIGS) •Cadmium Telluride Thin-film transfer
(Multicrystal-Si) (CdTe)
•Only thin-film technique equaling •Today’s commercial products
•Historically high efficiency potential of multi- exhibit 6 – 7% efficiency in
•Lowest manufacturing costs
manufacturing costs crystalline Silicon (20 %) spite of 20 years of
due to economy-of-scale (First optimization
•Substantial need •Modification of material Solar 2010: 1.4 GW)
composition give room for
of high-purity silicon continuous improvement •Severe concerns on various
•High CAPEX per MW
• Highly technical markets regarding
environmental and health impact •10 – 20 % efficiency
production process degradation during first year
of operation

19.5% 16.7%% 11.7% 9.5%

•Maximum efficiencies
achieved on laboratory cells
•Source: Solar efficiency tables, Progress in MultiCr-Si CIS/CIGSe CdTea-Si/µ-Si a-Si
PV, Vol. 18, 346-352 (2010)
 Best Polysilicon Technologies

Commercial PV Cell Efficiencies

Material Efficiency Features
Lengthy production procedure, wafer sawing necessary. Best researched solar cell material -
Monocrystalline Si solar cells 15 - 18 %
highest power/area ratio.

Multicrystalline Si solar cells 13 - 15 % Wafer sawing necessary. Most important production procedure at least for the next ten years.

Lower efficency than monocrystalline solar cells. Attractive solar cells for different BIPV
Polycrystalline transparent Si solar cells 10%
applications.

EFG (Edge Defined Film fed Growth) 14% Limited use of this production procedure Very fast crystal growth, no wafer sawing neccesary

Limited use of this production procedure, no wafer sawing necessary. Decrease in production
Polycrystalline ribbon Si solar cells 12%
costs expected in the future.

Production procedure used only by one producer, no wafer sawing, production in form of band
Apex (polycrystaline Si) solar cells 9,5 %
possible. Significant decrease in production costs expected in the future.

Monocrystaline dendritic web Si solar cells 13% Limited use of this production procedure, no wafer sawing, production in form of band possible.

Amorphous silicon 5-8% Lower efficiency, shorter life span. No sawing necessary, possible production in the form of band.

Module
Cadmium Telluride (CdTe) Poisonous raw materials, significant decrease in production costs expected in the future.
6-9%
Module
Copper-Indium-Diselenide (CIS) Limited Indium supply in nature. Significant decrease in production costs possible in the future.
7.5 – 9.5 %

Organic 1.7% No power warranty.

Source: By Technology, Best Commercial Module Efficiencies, NREL, 03/2010

 Best Polysilicon Technologies

Characteristics of the Best

Low Grade
Polysilicon Technologies:
99.99999999+% Silicon
Silicon Such as Safe and reliable production
MG-Si at the lowest cash cost
and highest quality

Impurities
(Metals, Carbon, P&B)
 Best Polysilicon Technologies

Direct chlorination TCS Non-polysilicon chemicals

(Silicones, Fumed silica)

TCS Siemens CVD Polysilicon

Hydrochlorination TCS

TCS-based silane Siemens CVD Polysilicon

Fluoride-based silane FBR CVD Polysilicon

 Best Polysilicon Technologies

Fluoride Based Silane Process

Al Powder
Li/Na

H2
Metal
Alkyl
Production

CaF2
Si SiF4 Silane Silane Polysilicon
H2SO4 Production Production Purification FBR/Siemens Polysilicon

Na(Li)AlF4 in
Solvent

Na(Li) / Solvent By-product

Al sulfate Recovery Drying

Na(Li)AlF4
 Best Polysilicon Technologies

Fluoride Based Silane Process

• Polysilicon from silicon bearing precursor requires proximity to a phosphate

fertilizer plant for H2SiF6 based process.

• SiF4 produced from H2SiF6 (proven) or from CaF2/NaAlF4 reacted with H2SO4
in a rotary kiln (in development)

• SiF4 reacted with metal (Na/Li) aluminum alkyl to produce Silane gas

• Silane is distilled for purity and polysilicon is produced by thermal decompsition of

silane

• Among the lowest overall power consumption but

• Large recycle streams of dilute sulfuric acid (for H2SiF6 process)
• Development of CaF2/NaAlF4 process
• 5:1 non-hazardous by-product to polysilicon generation (by weight)
 Best Polysilicon Technologies

Direct Chlorination Based TCS Process

HCl

TCS TCS Polysilicon H2

Si Production Purification Siemens Process

TCS STC
STC Storage Polysilicon
HCl Production

Fumed STC
Silica
 Best Polysilicon Technologies

Direct Chlorination Based TCS Process

• Direct Chlorination reactors have been used since at least the 1940s.

• Initially dominant demands were for the production of derivative silanes and
fumed silica.

• Typically HCl and MGSi are reacted in a fluid bed reactor to produce TCS at
approximately 300 deg C and 2 to 4 barg pressure.

• STC recovered from the polysilicon reactors is used for fumed silica production.

• Very energy intensive process.

3HCl + Si  SiHCl3 + H2 + Heat

SiCl4 + H2  SiHCl3 + HCl + Heat

 Best Polysilicon Technologies

Hydrochlorination TCS Based Technology

Chlorides
TCS TCS CVD
Hydrogen Production Purification
Siemens
MG Silicon Hydrochlorination

STC Solar Grade Silicon

TCS, H2
（ Chunk or Rod ）

Waste Gas Recovery

STC, HCl, H2 and Recycle to TCS
(STC, H2, HCl, DCS)

Impurities
Neutral/Safe Solids
 Best Polysilicon Technologies

TCS-Silane based Siemens or FBR CVD

Chlorides

Hydrogen TCS Reactive

TCS CVD
Production Distillation
MG Si Hydrochlorination Purification
(Silane)

STC Solar Grade

Silicon
(Chunk or
Rod)
Waste Gas Recycle
(H2)

Impurities
(Neutral/Safe Solids)
 Best Polysilicon Technologies

PRIMARY REACTIONS

Hydrochlorination (TCS ONLY) Reactive Distillation CVD

Si+3HCl SiHCl3+H2 + Heat 2SiHCl3+H2 Si+SiCl4+2HCl+H2- Heat

SiCl4+H2 SiHCl3+HCl - Heat

Hydrochlorination (SILANE)

SiCl4+H2 SiHCl3+HCl - Heat 4SiHCl3 SiH4 + 3SiCl4 SiH4 Si+2H2 - Heat

(2SiHCl3 SiH2Cl2+ SiCl4) DCS

(2SiH2Cl2 SiHCl3+ SiH3Cl) MCS

(2SiH3Cl SiH2Cl2+ SiH4) SILANE

 Best Polysilicon Technologies

Which Polysilicon Technology is the best?

TCS Silane Silane
  Hydrochlorination/ Hydrochlorination/ Hydrochlorination/
Siemens CVD Siemens CVD FBR CVD
CAPEX BETTER WORSE BEST
MAYBE
HIGHEST QUALITY ELECTRONIC ELECTRONIC
ELECTRONIC
BEST
EASE OF OPERATION VERY GOOD GOOD
(SHOULD BE)

POWER CONSUMPTION BETTER GOOD BEST

(CVD Section) (35-120 kwh/kg) (40-120 kwh/kg) (10-15 kwh/kg)

POWER CONSUMPTION BEST WORSE BEST

(MG Si to E.G POLYSILICON) (70-155 kwh/kg) (90-115 kwh/kg) (70-90 kwh/kg)

O &M STAFF HIGHER HIGHER LOWER

ROBUST PROCESS GOOD GOOD BETTER

R&D REQUIRED NO SOME SOME

RISK LOW HIGHER HIGHER

 Best Polysilicon Technologies

The Best Polysilicon Technology Must:

• Fit your Business Plan;
• Low Operating Cost with Highest Quality; and
• Safe, Environmentally Sound and Reliable Operation; and
• Overall Facility Integrated Processes for Lowest Energy
Consumption and Maximum Waste Recovery; and
• Capable of Under $20/kg Fully Loaded Cost; and
• Have Access to Competitive Raw Materials and Labor; and
• Need Low CAPEX Facility Cost; and
• Remember there are a few best technologies but lots of mistakes
available to select from.
Best Polysilicon Technologies