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Title: The effect of Na on Cu-K-In-Se thin film growth

Abstract

Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ~ 0.85 and K/(K + Cu) ~ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu1-xKxInSe2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe2 + KInSe2 mixed-phase films. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe2 content,more » or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S)2 absorbers to optimize both initial and long-term photovoltaic power generation.« less

Authors:
 [1];  [2];  [3]
  1. Univ. of Florida, Gainesville, FL (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Florida, Gainesville, FL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Florida, Gainesville, FL (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), Renewable Power Office. Solar Energy Technologies Office
OSTI Identifier:
1427350
Report Number(s):
NREL/JA-5K00-71039
Journal ID: ISSN 0022-0248
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Crystal Growth
Additional Journal Information:
Journal Volume: 488; Journal Issue: C; Journal ID: ISSN 0022-0248
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; crystal morphology; segregation; solid solutions; physical vapor deposition processes; alloys; semiconducting materials

Citation Formats

Muzzillo, Christopher P., Tong, Ho Ming, and Anderson, Timothy J. The effect of Na on Cu-K-In-Se thin film growth. United States: N. p., 2018. Web. doi:10.1016/j.jcrysgro.2018.02.035.
Muzzillo, Christopher P., Tong, Ho Ming, & Anderson, Timothy J. The effect of Na on Cu-K-In-Se thin film growth. United States. https://doi.org/10.1016/j.jcrysgro.2018.02.035
Muzzillo, Christopher P., Tong, Ho Ming, and Anderson, Timothy J. Tue . "The effect of Na on Cu-K-In-Se thin film growth". United States. https://doi.org/10.1016/j.jcrysgro.2018.02.035. https://www.osti.gov/servlets/purl/1427350.
@article{osti_1427350,
title = {The effect of Na on Cu-K-In-Se thin film growth},
author = {Muzzillo, Christopher P. and Tong, Ho Ming and Anderson, Timothy J.},
abstractNote = {Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ~ 0.85 and K/(K + Cu) ~ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu1-xKxInSe2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe2 + KInSe2 mixed-phase films. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S)2 absorbers to optimize both initial and long-term photovoltaic power generation.},
doi = {10.1016/j.jcrysgro.2018.02.035},
journal = {Journal of Crystal Growth},
number = C,
volume = 488,
place = {United States},
year = {2018},
month = {2}
}

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Cited by: 4 works
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Figures / Tables:

Fig. 1 Fig. 1: Plan view (top) and cross-sectional (bottom) SEM micrographs of CuInSe2 (CKIS with K/(K+Cu), or x ~ 0) films on Mo (left) and SLG (right) substrates.

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Works referenced in this record:

Potassium-induced surface modification of Cu(In,Ga)Se2 thin films for high-efficiency solar cells
journal, November 2013

  • Chirilă, Adrian; Reinhard, Patrick; Pianezzi, Fabian
  • Nature Materials, Vol. 12, Issue 12
  • DOI: 10.1038/nmat3789

Improved Photocurrent in Cu(In,Ga)Se 2 Solar Cells: From 20.8% to 21.7% Efficiency with CdS Buffer and 21.0% Cd-Free
journal, September 2015

  • Friedlmeier, Theresa Magorian; Jackson, Philip; Bauer, Andreas
  • IEEE Journal of Photovoltaics, Vol. 5, Issue 5
  • DOI: 10.1109/JPHOTOV.2015.2458039

Compositional investigation of potassium doped Cu(In,Ga)Se 2 solar cells with efficiencies up to 20.8% : Compositional investigation of potassium doped Cu(In,Ga)Se
journal, February 2014

  • Jackson, Philip; Hariskos, Dimitrios; Wuerz, Roland
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 8, Issue 3
  • DOI: 10.1002/pssr.201409040

Efficiency enhancement of Cu(In,Ga)Se 2 thin-film solar cells by a post-deposition treatment with potassium fluoride : Efficiency enhancement of Cu(In,Ga)Se
journal, July 2013

  • Laemmle, Anke; Wuerz, Roland; Powalla, Michael
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 7, Issue 9
  • DOI: 10.1002/pssr.201307238

Investigation of the effect of potassium on Cu(In,Ga)Se 2 layers and solar cells
journal, May 2015


Unveiling the effects of post-deposition treatment with different alkaline elements on the electronic properties of CIGS thin film solar cells
journal, January 2014

  • Pianezzi, Fabian; Reinhard, Patrick; Chirilă, Adrian
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 19
  • DOI: 10.1039/c4cp00614c

Defect formation in Cu(In,Ga)Se 2 thin films due to the presence of potassium during growth by low temperature co-evaporation process
journal, November 2013

  • Pianezzi, F.; Reinhard, P.; Chirilă, A.
  • Journal of Applied Physics, Vol. 114, Issue 19
  • DOI: 10.1063/1.4832781

Features of KF and NaF Postdeposition Treatments of Cu(In,Ga)Se 2 Absorbers for High Efficiency Thin Film Solar Cells
journal, August 2015


Effects of Sodium and Potassium on the Photovoltaic Performance of CIGS Solar Cells
journal, January 2017

  • Raguse, John M.; Muzzillo, Christopher P.; Sites, James R.
  • IEEE Journal of Photovoltaics, Vol. 7, Issue 1
  • DOI: 10.1109/JPHOTOV.2016.2621343

On the role of Na and modifications to Cu(In,Ga)Se/sub 2/ absorber materials using thin-MF (M=Na, K, Cs) precursor layers [solar cells]
conference, January 1997

  • Contreras, M. A.; Egaas, B.; Dippo, P.
  • Conference Record of the Twenty Sixth IEEE Photovoltaic Specialists Conference - 1997
  • DOI: 10.1109/PVSC.1997.654102

CIGS thin-film solar cells and modules on enamelled steel substrates
journal, May 2012


First-principles study on alkali-metal effect of Li, Na, and K in CuInSe 2 and CuGaSe 2
journal, July 2015

  • Maeda, Tsuyoshi; Kawabata, Atsuhito; Wada, Takahiro
  • Japanese Journal of Applied Physics, Vol. 54, Issue 8S1
  • DOI: 10.7567/JJAP.54.08KC20

Investigation of the potassium fluoride post deposition treatment on the CIGSe/CdS interface using hard X-ray photoemission spectroscopy – a comparative study
journal, January 2016

  • Ümsür, Bünyamin; Calvet, Wolfram; Steigert, Alexander
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 20
  • DOI: 10.1039/C6CP00260A

Experimental indication for band gap widening of chalcopyrite solar cell absorbers after potassium fluoride treatment
journal, August 2014

  • Pistor, P.; Greiner, D.; Kaufmann, C. A.
  • Applied Physics Letters, Vol. 105, Issue 6
  • DOI: 10.1063/1.4892882

Potassium Postdeposition Treatment-Induced Band Gap Widening at Cu(In,Ga)Se 2 Surfaces – Reason for Performance Leap?
journal, December 2015

  • Handick, Evelyn; Reinhard, Patrick; Alsmeier, Jan-Hendrik
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 49
  • DOI: 10.1021/acsami.5b09231

Alkali-Templated Surface Nanopatterning of Chalcogenide Thin Films: A Novel Approach Toward Solar Cells with Enhanced Efficiency
journal, April 2015


Cu(In,Ga)Se$_{\bf 2}$ Thin-Film Solar Cells and Modules—A Boost in Efficiency Due to Potassium
journal, March 2015


Influence of post-deposition selenium supply on Cu(In,Ga)Se 2 -based solar cell properties
journal, May 2015


Surface modification of CIGS film by annealing and its effect on the band structure and photovoltaic properties of CIGS solar cells
journal, January 2015


The impact of alkali elements on the degradation of CIGS solar cells: Degradation of CIGS solar cells
journal, April 2015

  • Theelen, Mirjam; Hans, Vincent; Barreau, Nicolas
  • Progress in Photovoltaics: Research and Applications, Vol. 23, Issue 5
  • DOI: 10.1002/pip.2610

Properties of Cu1−x K x InSe2 alloys
journal, April 2016

  • Muzzillo, Christopher P.; Mansfield, Lorelle M.; Ramanathan, Kannan
  • Journal of Materials Science, Vol. 51, Issue 14
  • DOI: 10.1007/s10853-016-9969-5

The effect of Ga content on the selenization of co-evaporated CuGa/In films and their photovoltaic performance
conference, June 2014

  • Muzzillo, Christopher P.; Mansfield, Lorelle M.; DeHart, Clay
  • 2014 IEEE 40th Photovoltaic Specialists Conference (PVSC), 2014 IEEE 40th Photovoltaic Specialist Conference (PVSC)
  • DOI: 10.1109/PVSC.2014.6925236

Differences between CuGa/In and Cu/Ga/In films for selenization
conference, June 2015

  • Muzzillo, Christopher P.; Mansfield, Lorelle M.; DeHart, Clay
  • 2015 IEEE 42nd Photovoltaic Specialists Conference (PVSC), 2015 IEEE 42nd Photovoltaic Specialist Conference (PVSC)
  • DOI: 10.1109/PVSC.2015.7356374

Na-induced variations in the structural, optical, and electrical properties of Cu(In,Ga)Se2 thin films
journal, August 2009

  • Ishizuka, Shogo; Yamada, Akimasa; Islam, Muhammad Monirul
  • Journal of Applied Physics, Vol. 106, Issue 3
  • DOI: 10.1063/1.3190528

Diffusion of indium and gallium in Cu(In,Ga)Se2 thin film solar cells
journal, September 2003


Fiber-fed time-resolved photoluminescence for reduced process feedback time on thin-film photovoltaics
journal, January 2015

  • Repins, I. L.; Egaas, B.; Mansfield, L. M.
  • Review of Scientific Instruments, Vol. 86, Issue 1
  • DOI: 10.1063/1.4905535

Photovoltaic properties of selenized CuGa/In films with varied compositions
conference, June 2016

  • Muzzillo, Christopher P.; Mansfield, Lorelle M.; Ramanathan, Kannan
  • 2016 IEEE 43rd Photovoltaic Specialists Conference (PVSC)
  • DOI: 10.1109/PVSC.2016.7750033

Effect of Alkali Metal Atom Doping on the CuInSe 2 -Based Solar Cell Absorber
journal, July 2017

  • Malitckaya, M.; Komsa, H. -P.; Havu, V.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 29
  • DOI: 10.1021/acs.jpcc.7b03083

KF post deposition treatment in co-evaporated Cu(In,Ga)Se 2 thin film solar cells: Beneficial or detrimental effect induced by the absorber characteristics
journal, July 2017

  • Lepetit, Thomas; Harel, Sylvie; Arzel, Ludovic
  • Progress in Photovoltaics: Research and Applications, Vol. 25, Issue 12
  • DOI: 10.1002/pip.2924

Surface and bulk effects of K in highly efficient Cu1-xKxInSe2 solar cells
journal, October 2018

  • Muzzillo, Christopher P.; Li, Jian V.; Mansfield, Lorelle M.
  • Solar Energy Materials and Solar Cells, Vol. 185
  • DOI: 10.1016/j.solmat.2018.05.013

Review of grain interior, grain boundary, and interface effects of K in CIGS solar cells: Mechanisms for performance enhancement
journal, December 2017


Works referencing / citing this record:

Revealing the beneficial role of K in grain interiors, grain boundaries, and at the buffer interface for highly efficient CuInSe 2 solar cells
journal, June 2018

  • Muzzillo, Christopher P.; Poplawsky, Jonathan D.; Tong, Ho Ming
  • Progress in Photovoltaics: Research and Applications, Vol. 26, Issue 10
  • DOI: 10.1002/pip.3022