skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Predicting Ga and Cu Profiles in Co-Evaporated Cu(In,Ga)Se 2 Using Modified Diffusion Equations and a Spreadsheet

Abstract

Cu(In,Ga)Se 2(CIGS) photovoltaic absorbers frequently develop Ga gradients during growth. These gradients vary as a function of growth recipe, and are important to device performance. Prediction of Ga profiles using classic diffusion equations is not possible because In and Ga atoms occupy the same lattice sites and thus diffuse interdependently, and there is not yet a detailed experimental knowledge of the chemical potential as a function of composition that describes this interaction. Here, we show how diffusion equations can be modified to account for site sharing between In and Ga atoms. The analysis has been implemented in an Excel spreadsheet, and outputs predicted Cu, In, and Ga profiles for entered deposition recipes. A single set of diffusion coefficients and activation energies are chosen, such that simulated elemental profiles track with published data and those from this study. Extent and limits of agreement between elemental profiles predicted from the growth recipes and the spreadsheet tool are demonstrated.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Solar Energy Technologies Office (EE-4S)
OSTI Identifier:
1407468
Report Number(s):
NREL/JA-5J00-68144
Journal ID: ISSN 2059-8521; applab
Grant/Contract Number:
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
MRS Advances
Additional Journal Information:
Journal Volume: 2; Journal Issue: 53; Journal ID: ISSN 2059-8521
Publisher:
Materials Research Society (MRS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; cigs; gallium profile; diffusion; simulation; thin film

Citation Formats

Repins, Ingrid L., Harvey, Steve, Bowers, Karen, Glynn, Stephen, and Mansfield, Lorelle M. Predicting Ga and Cu Profiles in Co-Evaporated Cu(In,Ga)Se2 Using Modified Diffusion Equations and a Spreadsheet. United States: N. p., 2017. Web. doi:10.1557/adv.2017.350.
Repins, Ingrid L., Harvey, Steve, Bowers, Karen, Glynn, Stephen, & Mansfield, Lorelle M. Predicting Ga and Cu Profiles in Co-Evaporated Cu(In,Ga)Se2 Using Modified Diffusion Equations and a Spreadsheet. United States. doi:10.1557/adv.2017.350.
Repins, Ingrid L., Harvey, Steve, Bowers, Karen, Glynn, Stephen, and Mansfield, Lorelle M. Mon . "Predicting Ga and Cu Profiles in Co-Evaporated Cu(In,Ga)Se2 Using Modified Diffusion Equations and a Spreadsheet". United States. doi:10.1557/adv.2017.350. https://www.osti.gov/servlets/purl/1407468.
@article{osti_1407468,
title = {Predicting Ga and Cu Profiles in Co-Evaporated Cu(In,Ga)Se2 Using Modified Diffusion Equations and a Spreadsheet},
author = {Repins, Ingrid L. and Harvey, Steve and Bowers, Karen and Glynn, Stephen and Mansfield, Lorelle M.},
abstractNote = {Cu(In,Ga)Se2(CIGS) photovoltaic absorbers frequently develop Ga gradients during growth. These gradients vary as a function of growth recipe, and are important to device performance. Prediction of Ga profiles using classic diffusion equations is not possible because In and Ga atoms occupy the same lattice sites and thus diffuse interdependently, and there is not yet a detailed experimental knowledge of the chemical potential as a function of composition that describes this interaction. Here, we show how diffusion equations can be modified to account for site sharing between In and Ga atoms. The analysis has been implemented in an Excel spreadsheet, and outputs predicted Cu, In, and Ga profiles for entered deposition recipes. A single set of diffusion coefficients and activation energies are chosen, such that simulated elemental profiles track with published data and those from this study. Extent and limits of agreement between elemental profiles predicted from the growth recipes and the spreadsheet tool are demonstrated.},
doi = {10.1557/adv.2017.350},
journal = {MRS Advances},
number = 53,
volume = 2,
place = {United States},
year = {Mon May 15 00:00:00 EDT 2017},
month = {Mon May 15 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:
  • Cadmium diffusion experiments were performed on polished copper indium gallium diselenide (Cu(In,Ga)Se{sub 2} or CIGS) samples with resulting cadmium diffusion profiles measured by time-of-flight secondary ion mass spectroscopy. Experiments done in the annealing temperature range between 275 °C and 425 °C reveal two-stage cadmium diffusion profiles which may be indicative of multiple diffusion mechanisms. Each stage can be described by the standard solutions of Fick's second law. The slower cadmium diffusion in the first stage can be described by the Arrhenius equation D{sub 1} = 3 × 10{sup −4} exp (− 1.53 eV/k{sub B}T) cm{sup 2} s{sup −1}, possibly representing vacancy-meditated diffusion. The faster second-stage diffusion coefficients determined in these experiments matchmore » the previously reported cadmium diffusion Arrhenius equation of D{sub 2} = 4.8 × 10{sup −4} exp (−1.04 eV/k{sub B}T) cm{sup 2} s{sup −1}, suggesting an interstitial-based mechanism.« less
  • In{sub 2}S{sub 3} layers were deposited by flash evaporation technique with varying flash rates. The optical constants of layers based on Tauc-Lorentz model dielectric function were extracted from spectroscopic ellipsometry measurements. X-ray photoelectron spectroscopic investigation revealed the presence of oxygen impurity in as-deposited and air-annealed layers with traces of Na inclusion in the layer grown at high flash rate. The enhancement in crystalline arrangement of as-deposited layer after air annealing was confirmed by Raman spectroscopy. Rutherford backscattering measurements revealed the growth of off-stoichiometric layers at all flash rates. An analytical layer growth model has been proposed supporting the results obtainedmore » by various layer characterization techniques. The solar cells were prepared with flash evaporated In{sub 2}S{sub 3} buffer layers and their performances were compared with CdS reference solar cell. A significant gain in short-circuit current was obtained after air annealing of the complete device at 200 deg. C for 20 min. A maximum conversion efficiency of 12.6% was delivered by a high flash rate In{sub 2}S{sub 3} buffered cell with open-circuit voltage close to that of CdS reference cell. The improvement in device performance after air annealing treatment is explained by thermally enhanced Cu and oxygen diffusion from Cu(In,Ga)Se{sub 2} and i-ZnO to In{sub 2}S{sub 3} layer, respectively.« less
  • Structures of compounds in the Cu{sub 2}Se-In{sub 2}Se{sub 3}-Ga{sub 2}Se{sub 3} system have been investigated through X-ray diffraction. Single crystal structure studies for the so-called stoichiometric compounds Cu(In,Ga)Se{sub 2} (CIGSe) confirm that the chalcopyrite structure (space group I4-bar 2d) is very flexible and can adapt itself to the substitution of Ga for In. On the other hand a structure modification is evidenced in the Cu{sub 1-z}(In{sub 0.5}Ga{sub 0.5}){sub 1+z/3}Se{sub 2} series when the copper vacancy ratio (z) increases; the chalcopyrite structure turns to a modified-stannite structure (I4-bar 2m) when z{>=}0.26. There is a continuous evolution of the structure from Cu{submore » 0.74}(In{sub 0.5}Ga{sub 0.5}){sub 1.09}Se{sub 2} to Cu{sub 0.25}(In{sub 0.5}Ga{sub 0.5}){sub 1.25}Se{sub 2} ((i.e. Cu(In{sub 0.5}Ga{sub 0.5}){sub 5}Se{sub 8}), including Cu{sub 0.4}(In{sub 0.5}Ga{sub 0.5}){sub 1.2}Se{sub 2} (i.e. Cu(In{sub 0.5}Ga{sub 0.5}){sub 3}Se{sub 5}). From this single crystal structural investigation, it is definitively clear that no ordered vacancy compound exists in that series. X-ray photoemission spectroscopy study shows for the first time that the surface of powdered Cu{sub 1-z}(In{sub 0.5}Ga{sub 0.5}){sub 1+z/3}Se{sub 2} compounds (z{ne}0) is more copper-poor than the bulk. The same result has often been observed on CIGSe thin films material for photovoltaic applications. In addition, optical band gaps of these non-stoichiometric compounds increase from 1.2 to 1.4 eV when z varies from 0 to 0.75. - Abstract: Pseudo-ternary diagram in the Cu{sub 2}Se-In{sub 2}Se{sub 3}-Ga{sub 2}Se{sub 3} system showing the composition of all the synthesized compounds. The crystal structure of the compounds corresponding to red circles are presented in this study.« less
  • We investigate point defects in CdS buffer layers that may arise from intermixing with Cu(In,Ga)Se{sub 2} (CIGSe) or Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe) absorber layers in thin-film photovoltaics (PV). Using hybrid functional calculations, we characterize the migration barriers of Cu, In, Ga, Se, Sn, Zn, Na, and K impurities and assess the activation energies necessary for their diffusion into the bulk of the buffer. We find that Cu, In, and Ga are the most mobile defects in CIGS-derived impurities, with diffusion expected to proceed into the buffer via interstitial-hopping and cadmium vacancy-assisted mechanisms at temperatures ∼400 °C. Cu is predicted to stronglymore » favor migration paths within the basal plane of the wurtzite CdS lattice, which may facilitate defect clustering and ultimately the formation of Cu-rich interfacial phases as observed by energy dispersive x-ray spectroscopic elemental maps in real PV devices. Se, Zn, and Sn defects are found to exhibit much larger activation energies and are not expected to diffuse within the CdS bulk at temperatures compatible with typical PV processing temperatures. Lastly, we find that Na interstitials are expected to exhibit slightly lower activation energies than K interstitials despite having a larger migration barrier. Still, we find both alkali species are expected to diffuse via an interstitially mediated mechanism at slightly higher temperatures than enable In, Ga, and Cu diffusion in the bulk. Our results indicate that processing temperatures in excess of ∼400 °C will lead to more interfacial intermixing with CdS buffer layers in CIGSe devices, and less so for CZTSSe absorbers where only Cu is expected to significantly diffuse into the buffer.« less
  • Development of highly efficient thin film solar cells involves band gap engineering by tuning their elemental composition with depth. Here we show that grazing incidence X-ray fluorescence (GIXRF) analysis using monochromatic synchrotron radiation and well-characterized instrumentation is suitable for a non-destructive and reference-free analysis of compositional depth profiles in thin films. Variation of the incidence angle provides quantitative access to the in-depth distribution of the elements, which are retrieved from measured fluorescence intensities by modeling parameterized gradients and fitting calculated to measured fluorescence intensities. Our results show that double Ga gradients in Cu(In{sub 1−x},Ga{sub x})Se{sub 2} can be resolved bymore » GIXRF.« less