The spray-ILGAR (R) (ion layer gas reaction) method for the deposition of thin semiconductor layers: Process and applications for thin film solar cells

[摘要]：The spray Ion Layer Gas Reaction (ILGAR) process starts with ultrasonic nebulisation of the precursor solution, e.g. InCl(3)/ethanol for our successful buffer material In(2)S(3). In an aerosol assisted chemical vapour deposition (AACVD) type reaction an In(O,OH,Cl) film is deposited on a heated substrate and is subsequently converted to In(2)S(3) by H(2)S gas. The cycle of these steps is repeated until the required layer thickness is obtained. The robust and reproducible process allows a wide control of composition and morphology. Results of this "spray-ILGAR" method with respect to process, material properties and its application depositing the buffer layer in chalcopyrite solar cells are reviewed. New aspects such as the investigation of the complex chemical mechanism by mass spectrometry, the process acceleration by the addition of H(2)S gas to the aerosol, the controlled deposition of ZnS nano-dot films and finally the latest achievements in process up-scaling are also included. Solar cells based on industrial Cu(In,Ga)(S,Se)(2) absorbers (Avancis GmbH) with a Spray-ILGAR In(2)S(3) buffer reached 14.7% efficiency (certified) and 15.3% with a ZnS/In(2)S(3) bi-layer buffer comparable to reference cells using standard CdS buffer layers deposited by chemical bath deposition (CBD). The quasi-dry, vacuum-free ILGAR method for In(2)S(3) buffer layers is well suited for industrial in-line production and is capable of not only replacing the standard buffer material (the toxic CdS) but also the often slow CBD process. A tape coater for 10 cm wide steel tape was constructed. It was shown that In(2)S(3) layers could be produced with an indium yield better than 30% and a linear production speed of 1 m/min. A roll-to-roll pilot production line for electrochemically deposited Cu(In,Ga)Se(2) with ILGAR buffer is running in industry (CIS-Solartechnik, Hamburg). A 30x30 cm(2) prototype of an ILGAR in-line coater developed by Singulus and Helmholtz Zentrum Berlin is currently being optimised. First 30 x 30 cm(2) encapsulated modules achieved efficiencies up to 13.0% (CdS buffered reference 13.3%). (C) 2010 Elsevier B.V. All rights reserved.

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