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SEMILAB Semiconductor Physics Laboratory Co. Ltd.

Semiconductor Physics Laboratory Co. Ltd.

Metrology for Thin Film Applications

Semiconductor Physics Laboratory Co. Ltd.

CIS/CIGS Absorber layers a-Si, !c-Si CdTe

Minority carriers lifetime Surface photovoltage Minority carriers lifetime Surface photovoltage Minority carriers lifetime Surface Photovoltage Layer Thickness Sheet Resistance Haze Layer Roughness Optical Transmission Layer Thickness Quantum efficiency Reflectance Diffusion Length Electro-luminescence

Epi !-PCD SPV Epi !-PCD SPV Epi !-PCD SPV Ellipsometer Eddy Current Haze Reflection Ellipsometer Ellipsometer Ellipsometer LBIC LBIC LBIC IR Camera 3 3

TCO layers

ITO AZO FTO etc

Solar cells

CIS/CIGS a-Si, !c-Si CdTe

Semiconductor Physics Laboratory Co. Ltd.

! Tools for different purposes:

! Laboratory tools ! Process control tools


! At line ! In-line ! Roll to roll

WT-2000 PVN offline and lab tool

Production control for large panels

Roll to roll ellipsometer

GES5E ellipsometer for R&D

Semiconductor Physics Laboratory Co. Ltd.

Minority charge carrier lifetime: effective parameter to characterize the purity of semiconductor material -PCD method: simple, robust, powerful technique for lifetime monitoring Different laser wavelengths can be used to accomodate different layer thickness and material composition

!diff
Excitation (generatio n of excess charge carriers) diffusion of carriers to the surface Redistribution of carriers

!surface
surface recombination Thermal equilibriu m

!bulk
bulk recombination

!meas: measured lifetime !surface: surface recombination lifetime !diff: characteristic time for diffusion to the surface from the bulk"" !bulk: bulk recombination lifetime

D: diffusion constant of minority carriers d: wafer thickness S: Surface recombination velocity

Semiconductor Physics Laboratory Co. Ltd.

! ! !

355nm UV light for charge carrier generation: penetration depth is smaller than conventional IR Measurements on thin layers, SOI, even on SiC Special MW antenna With new, fast transient recorder card, short lifetimes can be measured precisely

Semiconductor Physics Laboratory Co. Ltd.

! ! ! ! ! ! ! !

LBIC and Reflectance Multiple wavelength laser capability: 405 1015nm Up to 200x200mm area mapping High resolution: 100!m Adjustable light intensity Reflectance measurement for Internal Quantum Efficiency determination Separated direct and scattered reflection measurement Reflected light is detected up to an angle of 60o

IQE Measurements made on the same CIS cell with a 980nm and a 405nm laser

IQE Measurement on CIGS cell

Semiconductor Physics Laboratory Co. Ltd.

!"#$%&

'($&%)*+&,&%)&-*.(/0)*-&)&%)"$1

'(2#3&*.(/0)

Textured Zno

Semiconductor Physics Laboratory Co. Ltd.

! A pulsed LED or laser (wavelength 470 nm) creates electron-hole pairs ! Carriers are diffusing to surface and depletion region is charged ! Surface potential change is sensed at the transparent electrode by lock-in technique ! Different frequencies can be used for mapping surface photovoltage (default 1kHz) ! Change in surface photovoltage reflects change in charge state of surface or at layer interface.

Semiconductor Physics Laboratory Co. Ltd.

! SPV frequency scan allows determination of

! SPV Spectroscopybased composition indicatior (due to change in bandgap)


!

! Shunt Resistance RSH ! Junction capacitance CD ! junction lifetime "S= RSH *CD

4 '*

Rshunt
!

*High frequency Vspv ~ 1/CD CD2 ~ NA in absorber Low frequency Vspv ~ RSH

Semiconductor Physics Laboratory Co. Ltd.

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! Principle of non-contact I-V (suns-Voc); Voc is measured as function of light intensity. ! Measurements of Voc done with SPV or CPD (Contact Potential Difference) probe also known as Kelvin probe. ! Measurements of Voc as a function of light intensity are converted to I-V curves. ! Current is normalized to Isc. ! Values of n, FF and Voc are obtained. ! To get absolute values of Isc, calibration to final cell required.
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Junction Photo-Voltage Sheet Resistance Measurement


! ! ! ! ! ! ! e- and hole generation by chopped LED light This causes change in junction voltage Change spreads laterally, and the attenuation depends on sheet resistance Change of the potential is picked up by capacitive sensors Rs, Cd and Jleak are calculated by fitting the theoretical JPV signal Evaluation of p/n junctions in Thin Films Evaluation of laserseparation quality of active layers (laser 2)

Emitter sheet resistance map on a multi-crystalline silicon cell

JPV Sheet Resistance Measurements on CIGS cell

Semiconductor Physics Laboratory Co. Ltd.

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Resistivity measurement with Eddy current An AC current flows in a coil in close proximity to a conducting material. The magnetic field of the coil induces circulating (eddy) currents in the sample. The eddy current measurement is actually the measurement of the electrical loss in the material, which depends on the resistivity. Capacitive thickness measurement The capacitance depends on the distance between the probe and the sample:

Eddy current resistivity measurement

where d is the probe-sample distance. From the measured capacitance the distance can be calculated, and the distances from both sides of the sample makes the thickness determination possible.

Capacitive thickness measurement

Semiconductor Physics Laboratory Co. Ltd.

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! Si CCD camera cooled to -75 C ! 1024 x 1024 array of 13 !m square pixels ! Captures photons emitted during radiative recombination in the NIR range (900-1100nm ) ! Distribution is determined by local excitation level ! Imaging capabilities for
! ! ! ! ! ! Minority carrier lifetime (diffusion length) Micro cracks Lateral Series Resistance Shunt Resistance Defects and impurities in the semiconductor Relative efficiency
Semiconductor Physics Laboratory Co. Ltd.

! Calibration is needed to absolute methods


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! ! ! ! !

Spectroscopic Ellipsometers to meet requirements of emerging technologies / materials, R&D and process control Measures complex reflectance ratio Parameters: Spectral range:
!

Unique combination with further techniques:


! ! !

from 190 nm to 2.5 !m high resolution and/or fast measurement mode Grazing X-Ray Reflectance FT Infra-Red Spectroscopic Ellipsometry up to 33 !m Adsorption, EPA: Ellipsometric Porosimeter (EP) at atmospheric pressure

Wavelength

Semiconductor Physics Laboratory Co. Ltd.

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Metrology for Thin Film Applications

Semiconductor Physics Laboratory Co. Ltd.

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! a_Si, !c-Si, TCO: Thickness measurement by SE ! Crystallinity of !c_Si by Raman ! !c_Si, a_Si Resistivity by 4PP ! TCO Sheet Resistance by Eddy Current ! Haze control of Textured TCO ! Carrier lifetime by !PCD
Semiconductor Physics Laboratory Co. Ltd. 17

! CIGS , CdS, TCO & Dielectric thickness measurement by Optical techniques & SE ! TCO sheet resistance by Eddy Current ! CIGS crystallinity and composition measurement ! Carrier lifeTime by !PCD ! Sheet Resistance of CIGS by JPV ! LBIC , IQE ! PhotoLuminescence and Electroluminescence imaging

Semiconductor Physics Laboratory Co. Ltd.

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! CdTe , CdS and TCO thickness measurement by SE ! TCO sheet resistance by Eddy current ! CdTe Carrier lifetime by !PCD

4/22/10

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! Measurements for panels from Gen 1 to Gen 10 ! Ellipsometry, capacitive gauging and sheet resistance measurement can be integrated ! Manual or automatic loading ! Compatible with conveyor ! Offline or inline application

Semiconductor Physics Laboratory Co. Ltd.

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Roughness !Si

10.4 0.3 nm 774.6 0.5 nm

Glass

Total thickness : 785 nm


!Si is a mixture of 89.2 % of Polysilicon and 10.8 % of a_Si.

Measured and fitted curves Semiconductor Physics Laboratory Co. Ltd. 21

! 195 points in less than 10 minutes ! Panel size: 1.1 * 1.3 m


Semiconductor Physics Laboratory Co. Ltd. 22

Roughness Top ZnO Main ZnO

22.0 0.5 nm 188.4 1 nm 955.0 1 nm

Glass

Total thickness: 1165nm

Measured and fitted curves Semiconductor Physics Laboratory Co. Ltd. 23


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Semiconductor Physics Laboratory Co. Ltd.

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non textured

textured

Semiconductor Physics Laboratory Co. Ltd.

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Top CIGS 0.346 0.008 !m CIGS 2.1 0.02 !m Mo Total thickness = 2.446 !m

! ! ! ! !
Measurement and model fit

Measurement and analysis from 1.6 to 17 !m (580 6000 cm-1) CIGS is becoming quite fully transparent. Determination of thickness and refractive index is much easier The roughness becomes small compare to the wavelength and does not disturb measurement.
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Semiconductor Physics Laboratory Co. Ltd.

1!m, !c-Si on ceramic: 68ns

0.5!m !c-Si on glass : 87ns

! Measurement parameters:
! ! ! !

Excitation laser wavelength: 350 nm Spatial resolution 0.5 mm Lifetime variation 49ns 168ns Sample size: 1.5*3cm
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8!m CdTe layer on glass after CdCl2 treatment (10x10 cm)

Sample Transient ! Measurement parameters:


! Excitation laser wavelength: 535 nm ! Spatial resolution 1 mm ! Lifetime variation 23ns 50ns

Semiconductor Physics Laboratory Co. Ltd.

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CIGS: 30.3ns

CIGS/CdS:59.2 ns

CIGS/CdS/TCO:110.8 ns

CIGS solar cell structure

Luifetime results on different CIGS structure on steel foil (2x3 cm)

! Different lifetimes after different process steps ! Tendency is in good agreement with theory expectations ! Combining results between different manufacturing stages enables absorber layer quality & process control
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Lifetime map of CIGS Cell (1x2 cm)

LBIC IQE map of same CIGS Cell (1x2 cm)

! Carrier lifetime and Internal quantum efficiency map comparison on CIGS/CdS/TCO structure on steel substrate ! Strong correlation can be seen between minority carrier lifetime and internal quantum efficiency
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Measured lifetime values of two series 1X2 inch sized CIGS/CdS/TCO samples what are in different manufacturing stages. On the series A&B different processes were performed. Semiconductor Physics Laboratory Co. Ltd.
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Sample structure: Thin ~1!m TCO layer on 4 mm glass substrate Measurement raster: 0.5mm Edge exclusion: 7mm necessary
Transparent layer

TCO SnO2

DOPANT Sb,F,As,Nb,Ta Al, Ga,B,In,Y,Sc,F,V,Si,Ge,Ti,Zr,Hf,Mg,A s,H Sn,Mo,Ta,W,Zr,F,Ge,Nb,Hf,Mg In,Sn

Measurement range: 0.02 "/sq - 250 "/ sq On TCO layers a linear correlation between 4pp and Eddy current can be observed Repeatability <1%

ZnO In2O3 CdO Ta2O GaInO3 CdSb2O 3

Sn,Ge Y

Semiconductor Physics Laboratory Co. Ltd.

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! CIGS Cell with TCO layer on metal sheet (5X2cm) ! Hamamatsu CCD Camera 512x256 pix ! < 1sec integration time ! 1-1.5 V and 0.6-0.8A BIAS ! 20% QE at 1!m wavelength ! Contrast enhanced by software
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Electroluminescence pictures comparison with Internal Quantum Efficiency map measured with LBIC head 6x3 cm CIGS Cell on steel foil
El. Picture* Dark spots like this are shunts* El. Picture with reverse bias shows shining shunts * IQE map*

Ring shaped bright object*

Ring shaped bright object shows higher IQE value*

Semiconductor Physics Laboratory Co. Ltd.

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Electroluminescence picture: 19V; 46mA; 3sec exp. time

Electroluminescence picture: 15V; 6mA; 60sec exp. time

Internal Quantum Efficiency map

Bright regions marked with red circles show extra current (shunts) and locally increased temperature.

With smaller current density it can be seen that shunts effect the whole cells.

The IQE map with same pattern as electroluminescence picture

10x11 inch sized integrally interconnected CIS panel (25x28cm)


Semiconductor Physics Laboratory Co. Ltd. 35

1-2 !m thick CdS layer on glass (12x12cm)

CIS solar cell Structure (6x28cm)

1-2 !m thick CIGS/CdS/TCO structure on steel sheet (2.5x8cm)

Average SPV signal: 0.75mV

1x3 sized cm 1-2 !m thick CIGS/CdS structure on steel sheet (2.5x8cm) Average SPV signal: 0.65mV

Average SPV signal: 20mV

Average SPV signal: 5.42mV

! Topography correlates to layer interface charge density distribution ! SPV mapping helps in electric field engineering
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405nm

980nm

Internal Quantum Efficiency


40.2% 40.3%

Reflectance

11.2%

9.4% 37

Semiconductor Physics Laboratory Co. Ltd.

Comparison of 3 CIGS samples


Semiconductor Physics Laboratory Co. Ltd. 38

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