WO2009143921A1 - Procédé permettant de déterminer une propriété optique d'une couche optique - Google Patents

Procédé permettant de déterminer une propriété optique d'une couche optique Download PDF

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Publication number
WO2009143921A1
WO2009143921A1 PCT/EP2009/001800 EP2009001800W WO2009143921A1 WO 2009143921 A1 WO2009143921 A1 WO 2009143921A1 EP 2009001800 W EP2009001800 W EP 2009001800W WO 2009143921 A1 WO2009143921 A1 WO 2009143921A1
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WO
WIPO (PCT)
Prior art keywords
reflection
transmission
value
spectrum
optical
Prior art date
Application number
PCT/EP2009/001800
Other languages
English (en)
Inventor
Jürgen Schröder
Original Assignee
Applied Materials, Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP08009845A external-priority patent/EP2128603A1/fr
Priority claimed from US12/129,143 external-priority patent/US20090296100A1/en
Application filed by Applied Materials, Inc filed Critical Applied Materials, Inc
Publication of WO2009143921A1 publication Critical patent/WO2009143921A1/fr

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00Measuring arrangements characterised by the use of optical techniques
    • G01B11/02Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0616Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating
    • G01B11/0625Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating with measurement of absorption or reflection
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/59Transmissivity
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • G01N21/8422Investigating thin films, e.g. matrix isolation method
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N2021/558Measuring reflectivity and transmission
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • G01N21/8422Investigating thin films, e.g. matrix isolation method
    • G01N2021/8427Coatings

Definitions

  • the present invention relates to determining the thickness and optical properties of optical layers.
  • Current solar cells are comprised of one or plural optical layers, whose optical properties significantly influence the possible energy generation.
  • One of the optical layers is the absorption layer, which is often made of silicon (Si).
  • Si silicon
  • the energy band gap, or its position is a substantial parameter, since it determines which spectral ranges of the sunlight are absorbed, and which are not absorbed. In order to assure the required quality of large surface solar cells, the energy band gap and other absorption properties therefore have to comply with particular requirements with respect to the absorption spectra.
  • the position of the energy of the band gap can be influenced e.g. by performing the coating process, which is used for forming the absorption layer, in a suitable manner. Said energy position particularly depends on the crystal structure of the silicon used, so that e.g. for thin layer solar cells, a mix ratio between an amorphous silicon and a microcrystalline silicon can be adjusted by means of one or plural coating process parameters, so that the energy position of the optical band gap corresponds to a target value.
  • the mix ratio of amorphous and microcrystalline silicon can e.g. be determined by Raman-Spectroscopy.
  • the spectral distribution of the refractory index n( ⁇ ) and of the extinction coefficient k( ⁇ ) can be determined e.g. from an optical measurement with an ellipsometer, wherein ⁇ characterizes the wavelength.
  • the present invention is based on the finding that the optical models of the optical layers, which are used in the context of the known method for determining the energy band gap, like e.g. Tauc-Lorentz Model, can also be used for determining the energy band gap based on a spectral photometric measurement.
  • the position of the energy band gap can e.g. be determined based on a measurement of a spectral transmission value T( ⁇ ) and of a spectral reflection value R( ⁇ ) using an optical model of an optical layer. If the model of the optical layer can e.g. parameterized thus by a change of one or several parameters e.g.
  • the respective energy band gap can be determined, which can be associated with the respective transmission and/or reflection value and which most closely corresponds to the detected values.
  • the optical property can e.g. be determined based on a minimization task using the model of the optical layer.
  • a measuring system which measures in two dimension can be used to prove the optical homogeneity of large area coatings with a surface area of e.g. more than 1 m 2 .
  • a measurement system of this type can e.g. determine the spectral transmission T( ⁇ ) and the spectral reflection R( ⁇ ) as well as additional layer properties, like e.g. the color spectrum or the energy position of transmission- and reflection-maxima and -minima.
  • a measurement system of said type can also be used for determining the optical energy band gap, so that the measurements neither have to be performed with an ellipsometer, nor the transmission measurement has to be performed under the Brewster-angle.
  • a spectral photometer is used for measuring the transmission T( ⁇ ) and the reflection R( ⁇ ).
  • the measurement data can be stored e.g. for any location that is being measured wherein e.g. a computer program reads in the spectral data for each location and feeds it to a suitable optical model, based on which e.g. the layer thickness d, the spectral distribution n( ⁇ ), the spectral distribution K( ⁇ ) and the optical energy band gap or its position are determined as optical properties.
  • the detection of the optical property based on the optical model of the optical layer can e.g. be performed by means of a fit-software.
  • the method according to the invention can e.g. be implemented through an expansion of a system, which measures in two dimensions for proofing the optical homogeneity of large area coatings, with a location resolved determination of the optical energy band gap as an additional parameter
  • ellipsometers For determining the optical properties e.g. of solar absorption layers which are deposited on a large area, ellipsometers with large scanning tables can be used. However, it is disadvantageous that a measurement with an ellipsometer requires more time than a measurement with a spectral photometer. Furthermore, ellipsometers are more expensive than spectral photometers and they require a higher precision when adjusting a sample, which is time consuming and error prone.
  • the invention relates to a method for determining an optical property of an optical layer including the detection of a transmission value or a transmission spectrum, and a reflection value or a reflection spectrum of the optical layer and for determining the optical property based on the transmission value or the transmission spectrum, the reflection value or the reflection spectrum and a model of the optical layer.
  • the optical property is an energy band gap, or its position, or an absorption coefficient, or an extinction coefficient, or a refractory index, or a layer thickness.
  • the transmission value or the transmission spectrum and/or the reflection value, or the reflection spectrum can be detected by a spectral-photometric measurement.
  • the transmission value or the transmission spectrum and /or the reflection value or the reflection spectrum can be detected in a predetermined range of the optical layer.
  • the transmission value or the transmission spectrum and the reflection value or the reflection spectrum can be detected in a predetermined portion of the optical layer, wherein an additional transmission value or an additional transmission spectrum an additional reflection value or an additional reflection spectrum are detected in an additional predetermined portion of the optical layer, wherein a distribution, in particular a local distribution of the optical property is determined based on the transmission values or the transmission spectra and the reflection values or the reflection spectra.
  • the optical layer is a solar absorption layer.
  • an optimization method is used for determining the optical property, in particular a non linear optimization method using the model of the optical layer.
  • a theoretical reflection value or a theoretical reflection spectrum and a theoretical transmission value or a theoretical transmission spectrum are determined, wherein for determining the optical property a minimum of an evaluation function is determined, which is related to the model of the optical layer, using the theoretical reflection value or the theoretical reflection spectrum, the theoretical transmission value or the theoretical transmission spectrum, the detected reflection value or the detected reflection spectrum and the detected transmission value or the detected transmission spectrum.
  • the model of the optical layer is a parameterizable optical model or an Urbach-model or a Tauc-model or a Tauc-Lorentz-model or a Foroui-Bloomer-model or a Dasgupta-model or an O'Leary-model or a Cody-Lorentz-model.
  • the invention furthermore relates to a device for determining and optical property of an optical layer by a detection means, in particular a spectral photometer for detecting a transmission value or a transmission spectrum or reflection value or refraction spectrum of the optical layer and a processor for determining the optical property based on the transmission value or the transmission spectrum, the reflection value or a reflection spectrum and a model of the optical layer.
  • a detection means in particular a spectral photometer for detecting a transmission value or a transmission spectrum or reflection value or refraction spectrum of the optical layer and a processor for determining the optical property based on the transmission value or the transmission spectrum, the reflection value or a reflection spectrum and a model of the optical layer.
  • the program of the processor is configured to perform the method according to the invention.
  • the method furthermore relates to a computer program for performing the method according to the invention, when the computer program is executed on a computer.
  • the invention furthermore relates to a program driven device, which is configured to execute the computer program for performing the method according to the invention.
  • Fig. 1 a flow chart of a method for determining an optical property
  • Fig. 2 an assembly for determining an optical property
  • Fig. 3 a distribution of an extinction coefficient as a function of energy
  • Fig. 4 a measurement pattern.
  • a transmission and a reflection of the optical layer are detected in step 101 , wherein said detection can be performed in parallel or in series.
  • the optical property e.g. an energy band gap and/or an extinction coefficient and/or a refractory index and/or a layer thickness are determined based on the transmission, the reflection and on a model of the optical layer.
  • the model of the optical layer is preferably an optical model, which can e.g. be characterized by an evaluation function, so that the optical property can be determined e.g. by the minimizing the evaluation function.
  • the mathematical non linear optimization methods or optimization algorithms can be used, like e.g. the Simplex-method of Nelder and Mead, the Powell Algorithm or an optimization by a genetic algorithm.
  • the non linear optimization is based on finding a minimum for an evaluation function, which is determined e.g. by the sum of deviation squares between measured refraction- and/or transmission values and e.g. theoretically computed reflection- and/or transmission values.
  • the theoretical reflection and/or transmission values can be illustrated e.g. as a function of the absorption coefficient, the refractory index, the layer thickness, or e.g. the energy band gap.
  • the absorption coefficient the refractory index
  • the layer thickness or e.g. the energy band gap.
  • the energy band gap Preferably e.g.
  • a target layer thickness can be selected for the optimization method using non linear optimization algorithms e.g. a target layer thickness, or a start value or an initial value can be predetermined, wherein the initial values can be e.g. 80, 100, 120, 180 and 200 nm.
  • Fig 2 shows an assembly for determining an optical property of an optical layer 201 using a measurement computer 203, which comprises a local data memory 203 and an analysis computer 207.
  • the analysis computer 207 can be a separate computer and can be different computer from the measurement computer 203. According to an embodiment, however the functionality according to the invention of the measurement computer 203 and of the analysis computer 207 can be implemented in a singly computer.
  • the optical layer 201 is fed e.g. to a spectral photometer 209, which comprises a transmission port 211 and a reflection port 213.
  • the measurement computer 203 is provided to control the measurement process and to store the measured spectral transmission values (T ⁇ ) and the reflection values R ( ⁇ ), e.g. while using the local data memory 205.
  • the local data memory 205 can e.g. be installed in the hardware of the measurement computer 203. According to an embodiment the local data memory 205, however, can be portable and can be connected to the analysis computer 207. Furthermore the measurement computer 203 and the analysis computer 207 can e.g. communicate amongst each other using a network. For detecting the optical property, the analysis computer 207 retrieves the measured spectral values T ( ⁇ ) and R( ⁇ ) and computes the optical property based thereon using an optical model , wherein said property is e.g. the layer thickness, the spectral distribution of the refractory index n( ⁇ ), the spectral distribution of the absorption index K( ⁇ ), and the optical band gap (OBG). The analysis computer 207 is provided e.g. to execute a software, which is configured for determining the spectral distributions n( ⁇ ), k( ⁇ ) and the optical energy band gap E g .
  • a software which is configured for determining the spectral distributions n( ⁇ ), k
  • the measurement of the optical property will preferably be performed based on an optical model of the optical layer, e.g. based on the Tauc-Lorentz-Model, which is described in the publication by F. Jellison and Modene: "Parameterization of the optical functions of amorphous materials in the inter band region", Applied Physics Letters 69 (3), July 15, 1996 and Applied Physics Letters, September 13, 1996.
  • the Tauc-Lorentz-model is mathematically defined as follows:
  • ⁇ ta (E 2 -E 2 )E 2 +(E g 2 C 2 )-E 0 2 (E 0 2 +3E g 2 )
  • ⁇ i(E) and S 2 (E) designate the real part and imaginary part of a dielectric constant
  • E is the energy of the electromagnetic wave
  • E [eV] 1240/ ⁇ [nm]
  • designates the real part of the dielectric function for large wave lengths with ⁇ ⁇ ⁇
  • A is the amplitude of a Tauc-Lorentz-oscillator
  • C is the width of the Tauc-Lorentz- oscillator
  • E 0 designates a coefficient of the Tauc-Lorentz oscillator, which comprises a ratio of the mean wavelength to the mean energy.
  • Fig. 3 emphasizes the absorption distribution ⁇ 2 depending on the energy E, wherein the position of the energy band gap E g is indicated by an arrow. Based on the distribution illustrated in Fig. 3, the position of the energy band gap and its displacement can e.g. be considered depending on optionally selectable parameters of the optical model.
  • Fig. 4 emphasizes predetermined measuring points for detecting T( ⁇ ) and R( ⁇ ) on a glass pane (401 ), whose dimensions are e.g. 1 100 x 1300 mm.
  • the measuring points simultaneously determine a measuring pattern, comprising e.g. 441 data points, which are e.g. offset by 63 mm in the direction of the Y-axis illustrated in Fig. 4, and offset by 53 mm in the direction of the X-axis.
  • the exterior measurement points are offset e.g. by 20 mm from the edge of the glass pane.
  • the measuring time can e.g. be 15 min.
  • the measurement or control computer 203 illustrated in Fig. 2 can initially determine e.g. the measurement points illustrated in Fig. 4 for the large area measurement system, which is being used. Furthermore, additional measurement parameters can be defined for transmission and reflection measurements, like e.g. a particular scan speed or a particular scan precision.
  • the analysis- or processing computer 207 which is used for OGB determination, there while is e.g. in a standby condition.
  • a relevant spectral range can furthermore be predetermined at the processing computer 207, wherein the processing can e.g. be performed using the previously mentioned fit-software.
  • the result thus obtained is subjected to an evaluation, in order to determine, if the theoretically calculated spectral distribution or spectral value differs from the measurement result, and what size the difference may be.
  • differences which are e.g. smaller than 0.5%, can become negligible. It may be possible to improve the measurement concept by effectuating a change, which causes a smaller difference between the theoretically computed spectral value and the measurement result. Furthermore, the spectral value can be changed.
  • an additional measurement T( ⁇ ) and R( ⁇ ) can be manually performed, e.g. by means of the measurement computer 203, in another area of interest, wherein processing of the measurement results is performed at the analysis computer 207 for the additional location(s), using the fit-software, wherein each result is described as mentioned above.
  • an automatic measurement can be initiated e.g. by means of a measurement computer 203, wherein the previously programmed measurement points are sequentially approached, and wherein T( ⁇ ) and R( ⁇ ) are measured at predetermined locations.
  • the analysis computer 207 can begin automatic processing, thus it is being initially monitored, if e.g. an expected spectral pair T( ⁇ ) is present for a measurement point, e.g. for a first measurement point. If the result of the test is positive, T( ⁇ ) and R( ⁇ ) can be loaded, wherein the processing is performed according to a measurement concept. Thus, e.g. the layer thickness and/or the energy band gap E g can be determined for said point.
  • ⁇ ⁇ , A, C, and E 0 can be computed. Subsequently, it can be monitored, if a next expected spectral pair T( ⁇ ) and R( ⁇ ) is present, wherein the above described method is continued until the last predetermined measurement point has been considered.
  • the results of the processing can e.g. be stored in the analysis computer 207. Finally, the measurement computer 203 and the analysis computer 207 can be put into a standby mode until another sample is being measured.
  • the method according to the invention can e.g. be used to determine the optical band gap at solar absorption layers, deposited on a large area.
  • the exemplary large area measurement system illustrated in Fig. 2 can e.g. be used for determining the spectral transmission T( ⁇ ) and the reflection R( ⁇ ), which measures said values in predetermined portions of the optical layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Mathematical Physics (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Length Measuring Devices By Optical Means (AREA)

Abstract

La présente invention concerne un procédé permettant de déterminer une propriété optique d'une couche optique. Ledit procédé comprend la détection (101) d'une valeur de transmission ou d'un spectre de transmission et d'une valeur de réflexion ou d'un spectre de réflexion de la couche optique, puis la détermination (103) de la propriété optique sur la base de la valeur de transmission ou du spectre de transmission, de la valeur de réflexion ou du spectre de réflexion et d'un modèle de la couche optique.
PCT/EP2009/001800 2008-05-29 2009-03-12 Procédé permettant de déterminer une propriété optique d'une couche optique WO2009143921A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08009845.2 2008-05-29
EP08009845A EP2128603A1 (fr) 2008-05-29 2008-05-29 Procédé pour déterminer une propriété optique d'une couche optique
US12/129,143 US20090296100A1 (en) 2008-05-29 2008-05-29 Method for determining an optical property of an optical layer
US12/129,143 2008-05-29

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Publication Number Publication Date
WO2009143921A1 true WO2009143921A1 (fr) 2009-12-03

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012012795A1 (fr) * 2010-07-23 2012-01-26 First Solar, Inc Système et procédé de métrologie en ligne
WO2014105555A1 (fr) * 2012-12-27 2014-07-03 First Solar, Inc. Procédé et système de calcul en temps réel et en ligne d'épaisseurs de couche de semi-conducteur
US9245808B2 (en) 2012-12-27 2016-01-26 First Solar, Inc. Method and system for in-line real-time measurements of layers of multilayered front contacts of photovoltaic devices and calculation of opto-electronic properties and layer thicknesses thereof
KR20180011146A (ko) * 2015-05-21 2018-01-31 케이엘에이-텐코 코포레이션 광 분산의 다중 발진기, 연속 코디 로렌츠 모델
CN110651353A (zh) * 2017-05-22 2020-01-03 梭莱先进镀膜工业有限公司 反馈系统

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FERLAUTO A S ET AL: "Analytical model for the optical functions of amorphous semiconductors from the near-infrared to ultraviolet: Applications in thin film photovoltaics", JOURNAL OF APPLIED PHYSICS, AMERICAN INSTITUTE OF PHYSICS. NEW YORK, US, vol. 92, no. 5, 1 September 2002 (2002-09-01), pages 2424 - 2436, XP012057136, ISSN: 0021-8979 *
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012012795A1 (fr) * 2010-07-23 2012-01-26 First Solar, Inc Système et procédé de métrologie en ligne
CN103119704A (zh) * 2010-07-23 2013-05-22 第一太阳能有限公司 在线计量系统及方法
US8603839B2 (en) 2010-07-23 2013-12-10 First Solar, Inc. In-line metrology system
US9123584B2 (en) 2010-07-23 2015-09-01 First Solar, Inc In-line metrology system
WO2014105555A1 (fr) * 2012-12-27 2014-07-03 First Solar, Inc. Procédé et système de calcul en temps réel et en ligne d'épaisseurs de couche de semi-conducteur
US9245808B2 (en) 2012-12-27 2016-01-26 First Solar, Inc. Method and system for in-line real-time measurements of layers of multilayered front contacts of photovoltaic devices and calculation of opto-electronic properties and layer thicknesses thereof
KR20180011146A (ko) * 2015-05-21 2018-01-31 케이엘에이-텐코 코포레이션 광 분산의 다중 발진기, 연속 코디 로렌츠 모델
KR102324045B1 (ko) 2015-05-21 2021-11-08 케이엘에이 코포레이션 광 분산의 다중 발진기, 연속 코디 로렌츠 모델
CN110651353A (zh) * 2017-05-22 2020-01-03 梭莱先进镀膜工业有限公司 反馈系统
CN110651353B (zh) * 2017-05-22 2022-06-03 梭莱先进镀膜工业有限公司 反馈系统
US11875979B2 (en) 2017-05-22 2024-01-16 Soleras Advanced Coatings Bv Feedback system

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