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

Thin-film photovoltaic devices based on chalcopyrite Cu(In,Ga)Se2 (CIGS) absorber layers show excellent light-to-power conversion efficiencies exceeding 20%. This high performance level requires a small amount of alkaline metals incorporated into the CIGS layer, naturally provided by soda lime glass substrates used for processing of champion devices. The use of flexible substrates requires distinct incorporation of the alkaline metals, and so far mainly Na was believed to be the most favourable element, whereas other alkaline metals have resulted in significantly inferior device performance. Here we present a new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer. The described treatment leads to a significant depletion of Cu and Ga concentrations in the CIGS near-surface region and enables a significant thickness reduction of the CdS buffer layer without the commonly observed losses in photovoltaic parameters. Ion exchange processes, well known in other research areas, are proposed as underlying mechanisms responsible for the changes in chemical composition of the deposited CIGS layer and interface properties of the heterojunction.

[1]  K. Granath,et al.  Growth of Cu(In,Ga)Se2 thin films by coevaporation using alkaline precursors , 2000 .

[2]  H. Schock,et al.  Confined and Chemically Flexible Grain Boundaries in Polycrystalline Compound Semiconductors , 2012 .

[3]  Martin A. Green,et al.  Solar cell efficiency tables (version 41) , 2013 .

[4]  H. Jenny Studies on the Mechanism of Ionic Exchange in Colloidal Aluminum Silicates , 1931 .

[5]  Vasilis Fthenakis,et al.  Photovoltaic manufacturing: Present status, future prospects, and research needs , 2011 .

[6]  T. Nakada,et al.  Direct evidence of Cd diffusion into Cu(In, Ga)Se2 thin films during chemical-bath deposition process of CdS films , 1999 .

[7]  Michael Grätzel,et al.  Photoelectrochemical cells , 2001, Nature.

[8]  J. Bernède,et al.  ORGANIC PHOTOVOLTAIC CELLS: HISTORY, PRINCIPLE AND TECHNIQUES , 2008 .

[9]  Martin E. Nordberg,et al.  Strengthening by Ion Exchange , 1964 .

[10]  C. Felser,et al.  Theoretical Study on the Structure and Energetics of Cd Insertion and Cu Depletion of CuIn5Se8 , 2013 .

[11]  K. Chopra,et al.  The preparation of Cu2S films for solar cells , 1978 .

[12]  Feng Zhao,et al.  Two-step K(+)-Na+ and Ag(+)-Na+ ion-exchanged glass waveguides for C-band applications. , 2002, Applied optics.

[13]  W. Jaegermann,et al.  Fermi level-dependent defect formation at Cu(In,Ga)Se2 interfaces , 2000 .

[14]  D. Abou‐Ras,et al.  Characterization of Grain Boundaries in Cu(In,Ga)Se$_{\bf 2}$ Films Using Atom-Probe Tomography , 2011, IEEE Journal of Photovoltaics.

[15]  M. Grätzel Photoelectrochemical cells : Materials for clean energy , 2001 .

[16]  D. Hariskos,et al.  New world record efficiency for Cu(In,Ga)Se2 thin‐film solar cells beyond 20% , 2011 .

[17]  S. K. Deb Thin-film solar cells: An overview , 1996 .

[18]  F. Kessler,et al.  Technological aspects of flexible CIGS solar cells and modules , 2004 .

[19]  J. Werner,et al.  High quality baseline for high efficiency, Cu(In1−x,Gax)Se2 solar cells , 2007 .

[20]  S. Nishiwaki,et al.  Review of progress toward 20% efficiency flexible CIGS solar cells and manufacturing issues of solar modules , 2012, 2012 IEEE 38th Photovoltaic Specialists Conference (PVSC) PART 2.

[21]  H. Zogg,et al.  Sodium incorporation strategies for CIGS growth at different temperatures , 2005 .

[22]  P. Mahadevan,et al.  An overview , 2007, Journal of Biosciences.

[23]  Shigeru Niki,et al.  Flexible Cu(In,Ga)Se2 solar cells fabricated using alkali-silicate glass thin layers as an alkali source material , 2009 .

[24]  Lei Gao,et al.  History, Principle and Techniques for Waveform Optimization in External Defibrillations , 2012 .

[25]  A. Eicke,et al.  CIGS thin-film solar cells and modules on enamelled steel substrates , 2012 .

[26]  L. Kronik,et al.  Oxygenation and air-annealing effects on the electronic properties of Cu(In,Ga)Se2 films and devices , 1999 .

[27]  Shiro Nishiwaki,et al.  Highly efficient Cu(In,Ga)Se2 solar cells grown on flexible polymer films. , 2011, Nature materials.

[28]  A. Clearfield Role of Ion Exchange in Solid‐State Chemistry , 1988 .

[29]  Rommel Noufi,et al.  Optimization of CBD CdS process in high-efficiency Cu(In, Ga)Se2-based solar cells , 2002 .

[30]  P. Jain,et al.  Cation Exchange on the Nanoscale: An Emerging Technique for New Material Synthesis, Device Fabrication, and Chemical Sensing , 2013 .