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Effect of gallium grading in Cu(In,Ga)Se2 solar-cell absorbers produced by multi-stage coevaporation
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics. (Solar Cells)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics. (Solar Cells)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics. (Solar Cells)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Applied Materials Sciences. (Electron Microscopy and Nanoengineering)
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2011 (English)In: Solar Energy Materials and Solar Cells, ISSN 0927-0248, Vol. 95, no 2, 721-726 p.Article in journal (Refereed) Published
Abstract [en]

We investigate Cu(In,Ga)Se2 thin films grown in multi-stage coevaporation processes and solar cells fabricated from such absorbers. Despite some interdiffusion during film growth, Ga/(Ga+In) gradients defined via evaporation-profile variations in the process are to a good part retained in the finished film. This indicates that the bandgap can be engineered in this type of process by varying the evaporation profiles, and consequently also that unintended profile variations should be noted and avoided. With front-side gradients the topmost part of many grains seems to be affected by a higher density of lattice defects due to the strong change of gallium content under copper-poor growth conditions. Electrically, both back-side gradients and moderate front-side gradients are shown to yield an improvement of device efficiency. If a front-side gradient is too wide, though, it causes strong voltage-dependent collection and the fill factor is severely reduced.

Place, publisher, year, edition, pages
2011. Vol. 95, no 2, 721-726 p.
Keyword [en]
CIGS, Coevaporation, Multi-stage process, Three-stage process, Gradients
National Category
Physical Sciences Engineering and Technology
Research subject
Engineering Science with specialization in Electronics; Engineering Science with specialization in Materials Science
Identifiers
URN: urn:nbn:se:uu:diva-132556DOI: 10.1016/j.solmat.2010.10.011ISI: 000287006900048OAI: oai:DiVA.org:uu-132556DiVA: diva2:358290
Available from: 2011-11-23 Created: 2010-10-21 Last updated: 2013-08-30Bibliographically approved
In thesis
1. ZrN Back-Contact Reflectors and Ga Gradients in Cu(In,Ga)Se2 Solar Cells
Open this publication in new window or tab >>ZrN Back-Contact Reflectors and Ga Gradients in Cu(In,Ga)Se2 Solar Cells
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Solar cells constitute the most direct way of converting solar energy to electricity, and thin-film solar-cell technologies have lately been growing in importance, allowing the fabrication of less expensive modules that nonetheless have good power-conversion efficiencies. This thesis focuses on solar cells based on Cu(In,Ga)Se2, which is the thin-film technology that has shown the highest conversion efficiency to date, reaching 20.3 % on the laboratory scale. Solar modules still have some way to go to become entirely competitive with existing energy technologies, and there are two possible paths to this goal: Firstly, reducing their manufacturing costs, for instance by minimizing the material usage per module and/or by increasing the throughput of a given factory; and secondly, increasing the power output per module in other words, the module efficiency. The subject matters of this thesis are related to those two approaches.

The first issue investigated is the possibility for reducing the thickness of the Cu(In,Ga)Se2 layer and compensating for lost absorption by using a ZrN back reflector. ZrN layers are fabricated by reactive sputtering and I present a method for tuning the sputtering parameters so as to obtain a back reflector with good optical, electrical and mechanical properties. The reflector layer cannot be used directly in CIGS devices, but relatively good devices can be achieved with a precursor providing a homogeneous supply of Na, the addition of a very thin sacrificial Mo layer that allows the formation of a film of MoSe2 passivating the back contact, and optionally a Ga gradient that further keeps electrons away from the back contact.

The second field of study concerns the three-stage CIGS coevaporation process, which is widely used in research labs around the world and has yielded small-area cells with highest efficiencies, but has not yet made it to large scale production. My focus lies on the development and the effect of gradients in the [Ga]/[In+Ga] ratio. On the one hand, I investigate 'intrinsic' gradients (ones that form autonomously during the evaporation), and present a formation model based on the differing diffusivity of Ga and In atoms in CIGS and on the development along the quasi-binary tie line between (In,Ga)2Se3 and Cu2Se. On the other hand, I determine how the process should be designed in order to preserve 'extrinsic' gradients due to interdiffusion. Lastly, I examine the electrical effects of Ga-enhancement at the back and at the front of the absorber and of In-enhancement at the front. Over a wide range, In-rich top layers prove to have no or a weakly beneficial effect, while Ga-rich top regions pose a high risk to have a devastating effect on device performance.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2011. 66 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 830
Keyword
Solar cells, CIGS, ZrN, three-stage process, multi-stage process, grading, SIMS, electrical modelling
National Category
Natural Sciences
Research subject
Engineering Science with specialization in Electronics
Identifiers
urn:nbn:se:uu:diva-151402 (URN)978-91-554-8086-8 (ISBN)
Public defence
2011-05-31, room 80101, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2011-05-10 Created: 2011-04-11 Last updated: 2011-07-01Bibliographically approved
2. Microscopic Characterisation of Solar Cells: An Electron Microscopy Study of Cu(In,Ga)Se2 and Cu2ZnSn(S,Se)4 Solar Cells
Open this publication in new window or tab >>Microscopic Characterisation of Solar Cells: An Electron Microscopy Study of Cu(In,Ga)Se2 and Cu2ZnSn(S,Se)4 Solar Cells
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The sun provides us with a surplus of energy convertible to electricity using solar cells. This thesis focuses on solar cells based on chalcopyrite (CIGSe) as well as kesterite (CZTS(e)) absorber layers. These materials yield record efficiencies of 20.4 % and 11.1 %, respectively. Especially for CZTS(e), the absorber layers often do not consist of one single desired phase but can exhibit areas with deviating material properties, referred to as secondary phases. Furthermore, several material layers are required for a working solar cell, each exhibiting interfaces. Even though secondary phases and interfaces represent a very small fraction of the solar cell they can have a profound influence on the over-all electrical solar cell characteristics. As such, it is crucial to understand how secondary phases and interfaces influence the local electrical characteristics.

Characterising secondary phases and interfaces is challenging due to their small sample volume and relatively small differences in composition amongst others. This is where electronmicroscopy, especially transmission electron microscopy, offers valuable insight to material properties on the microscopic scale. The main challenge is, however, to link these material properties to the corresponding electrical characteristics of a solar cell.

This thesis uses electron beam induced current imaging and introduces a new method for JV characterisation of solar cells on the micron scale. Combining microscopic structural and electrical characterisation techniques allowed identifying and characterising local defects found in the absorber layer of CIGS solar cells after thermal treatment. Furthermore, CZTSe solar cells in this thesis exhibited a low photo-current density which is traced to the formation of a current blocking ZnSe secondary phase at the front contact interface. The electron microscopy work has contributed to an understanding of the chemical stability of CZTS and has shown the need for an optimised back contact interface in order to avoid chemical decomposition reactions and formation of detrimental secondary phases. With this additional knowledge, a comprehensive picture of the material properties from the macroscopic down to the microscopic level can be attained throughout all required material layers.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2013. xii + 70 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1053
Keyword
TEM, SEM, FIB, solar cell, CIGS, CZTS, Alternative buffer layers, Gallium gradients, microscopic electrical characterisation, Secondary Phases
National Category
Other Electrical Engineering, Electronic Engineering, Information Engineering Physical Sciences Materials Engineering
Research subject
Engineering Science with specialization in Electronics
Identifiers
urn:nbn:se:uu:diva-199432 (URN)978-91-554-8692-1 (ISBN)
Public defence
2013-09-06, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2013-06-05 Created: 2013-05-04 Last updated: 2013-08-30Bibliographically approved

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Schleussner, SebastianZimmermann, UweWätjen, TimoLeifer, KlausEdoff, Marika
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