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In the confines of Cu(In,Ga)Se2 thin film solar cells with rear surface passivating oxide layers
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics. (Thin film solar cells)ORCID iD: 0000-0003-0741-5068
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The material supply to build renewable energy conversion systems needs to be considered from both a cost and an energy security perspective. For Cu(In,Ga)Se2 (CIGS) thin film solar cells the use of indium in the absorber layer is most problematic. The material input per service unit can be reduced, if the absorber layers are thinned down without a loss in power conversion efficiency.

Thinning down absorber layers can increase the conversion efficiency. However, for real CIGS solar cells absorption losses and recombination rates at the rear surface between the CIGS absorber and the Mo rear contact as well as shunt-like behavior increase. Thus, both rear surface passivation and optical management are essential for maintaining high power conversion efficiencies.

In this work, thin oxide layers, so-called passivation layers, are introduced between the CIGS absorber layer and the Mo contact. They can passivate the CIGS surface, if the CIGS-oxide interface has a lower defect density than the CIGS-Mo interface and/or if they contain a negative fixed oxide charge, which increases the hole concentration and reduces the electron concentration in the CIGS in the vicinity of the oxide.

As these oxides are insulators, electrical conduction through the passivation layer has to be ensured. In this work, nanopoint contacts were etched into ALD-Al2O3 passivation layers in CIGS solar cells. These solar cells had 0.5 -1.5 µm thin absorber layers with a low In content and a high band gap. Ga grading was not used. Although absorber layers with a high Ga content have a short minority carrier diffusion length, a passivation effect could be discerned with the help of external quantum efficiency measurements and current-voltage measurements under varying temperatures in combination with optical and electrical modeling with a two-diode model. Moreover, the possibility of leaving out the additional fabrication step has been explored for ALD-Al2O3 and HfO2 as passivation layers. The results suggest that the passivation layer does not necessarily need to be opened for electrical conduction in an additional fabrication step, if sodium fluoride (NaF) is deposited onto Al2O3 layers prior to CIGS evaporation. In this case solar cells with 215 nm absorber layers and 6 nm thin passivation layers have a power conversion efficiency of 8.6 %, which is 3 % (absolute) higher than the conversion efficiency on a reference. Shunt-like behavior is additionally reduced. For the HfO2 layers photoluminescence data indicate a good passivation effect, but the layers need to be opened up to ensure conduction.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. , p. 118
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1834
Keywords [en]
Alkali, Alumina, Back contact, CIGS, CIGSe, Hafnia, Passivation, Rear contact, Sodium fluoride, Ultra-thin
National Category
Other Electrical Engineering, Electronic Engineering, Information Engineering
Research subject
Engineering Science with specialization in Electronics
Identifiers
URN: urn:nbn:se:uu:diva-390314ISBN: 978-91-513-0713-8 (print)OAI: oai:DiVA.org:uu-390314DiVA, id: diva2:1341337
Public defence
2019-09-30, Room 80101, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2019-09-09 Created: 2019-08-08 Last updated: 2019-09-17
List of papers
1. Thickness and Ga content variations in co-evaporated CIGS solar cells with a flat Ga profile: an electrical characteriyation
Open this publication in new window or tab >>Thickness and Ga content variations in co-evaporated CIGS solar cells with a flat Ga profile: an electrical characteriyation
2014 (English)In: EU PVSEC 2014 Proceedings Papers, Munchen, 2014, p. 1832-1836Conference paper, Published paper (Other academic)
Abstract [en]

In this work an extensive experimental series has been carried out by co-evaporating CIGS layers with varying thickness (0.5, 1.0, 1.5 µm) and varying Ga content (Ga/(Ga+In)=0.15, 0.30, 0.45 and 0.60). In all CIGS layers the Cu concentration has been held constant at Cu/(In+Ga)=0.85. The cells have been characterized with dark and light current voltage measurements, external quantum efficiency measurements and apparent quantum efficiency measurements at negative bias. In agreement with the literature, we observe a distinctively shorter collection length for high Ga concentrations and voltage dependent photo current collection for all cells. Voltage dependent current collection however cannot alone explain our data and the cells need to be described with an illumination dependent diode current or photo current. The generation dependent diode or photo current increase the slope of the light JV curve at negative bias voltage for all solar cells and dominates the slope in cells with 0.5 µm thin absorbers regardless of Ga content. We propose that this behavior is connected to the recombination at the back contact, as it is smaller in the cells with thick absorber layers and since we do not observe the same behavior in back side passivated cells. Keywords: Cu(InGa)Se2, Modelling, Electrical Characterization, Shunting, Ga content, thin absorbers, superposition principle, shifting approximation

Place, publisher, year, edition, pages
Munchen: , 2014
Keywords
CIGS; CIGSe; Thin film solar cells; GGI; Ga content; electrical characterization;
National Category
Condensed Matter Physics
Research subject
Engineering Science with specialization in Electronics
Identifiers
urn:nbn:se:uu:diva-390309 (URN)
Conference
29th European Photovoltaic Solar Energy Conference and Exhibition,22-26 September, 2014, Amsterdam
Available from: 2019-08-08 Created: 2019-08-08 Last updated: 2019-08-29Bibliographically approved
2. Rear Contact Passivation for High Bandgap Cu(In,Ga)Se2 Solar Cells With a Flat Ga profile
Open this publication in new window or tab >>Rear Contact Passivation for High Bandgap Cu(In,Ga)Se2 Solar Cells With a Flat Ga profile
Show others...
2018 (English)In: IEEE Journal of Photovoltaics, ISSN 2156-3381, E-ISSN 2156-3403, Vol. 8, no 3, p. 864-870Article in journal (Refereed) Published
Abstract [en]

In this study, Cu(In, Ga)Se2 solar cells with a high bandgap (1.31 eV) and a flat Ga profile ([Ga]/([Ga]+[In]) ≈ 0.60) were examined. For absorber layer thicknesses varying from 0.60 to 1.45 μm, the Mo rear contact of one set of samples was passivated with an ultrathin (27 nm) Al2O3 layer with point contact openings, and compared with reference samples where the rear contact remained unpassivated. For the passivated samples, mainly large gains in the short-circuit current led to an up to 21% (relative) higher power conversion efficiency compared with unpassivated cells. The differences in temperature-dependent current voltage behavior between the passivated and the unpassivated samples and the thin and the thick samples can be explained by an oppositely poled secondary photodiode at the rear contact.

Place, publisher, year, edition, pages
Institute of Electrical and Electronics Engineers (IEEE), 2018
Keywords
Back contact, CIGS, CIGSe, Cu(In, Ga)Se-2, energy barrier, passivation, rear contact, thin films, two-diode model
National Category
Condensed Matter Physics Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-356073 (URN)10.1109/JPHOTOV.2018.2813259 (DOI)000430718700029 ()
Funder
Swedish Energy AgencyStandUp
Available from: 2018-07-13 Created: 2018-07-13 Last updated: 2022-11-17Bibliographically approved
3. Effect of different Na supply methods on thin Cu(In,Ga)Se2 solar cells with Al2O3 rear passivation layers
Open this publication in new window or tab >>Effect of different Na supply methods on thin Cu(In,Ga)Se2 solar cells with Al2O3 rear passivation layers
Show others...
2018 (English)In: Solar Energy Materials and Solar Cells, ISSN 0927-0248, E-ISSN 1879-3398, Vol. 187, no 1, p. 160-169Article in journal (Refereed) Published
Abstract [en]

In this work, rear-contact passivated Cu(In,Ga)Se2 (CIGS) solar cells were fabricated without any intentional contact openings between the CIGS and Mo layers. The investigated samples were either Na free or one of two Na supply methods was used, i) a NaF precursor on top of the Al2O3 rear passivation layer or ii) an in situ post- deposition treatment with NaF after co-evaporation of the CIGS layer. The thickness of the ALD-Al2O3 passi- vation layer was also varied in order to find an optimal combination of Na supply and passivation layer thickness. Our results from electrical characterization show remarkably different solar cell behavior for different Na supplies. For up to 1nm thick Al2O3 layers an electronically good contact could be confirmed independently of Na deposition method and content. When the Al2O3 thickness exceeded 1 nm, the current was blocked on all samples except on the samples with the NaF precursor. On these samples the current was not blocked up to an Al2O3 layer thickness of about 6 nm, the maximum thickness we could achieve without the CIGS peeling off the Al2O3 layer. Transmission electron microscopy reveals a porous passivation layer for the samples with a NaF precursor. An analysis of the dependence of the open circuit voltage on temperature (JVT) indicates that a thicker NaF precursor layer lowers the height of the hole barrier at the rear contact for the passivated cells. This energy barrier is also lower for the passivated sample, compared to an unpassivated sample, when both samples have been post-deposition treated.

Keywords
Alkali, Back contact, CIGS, Passivation, Thin films, Rear contact, Tunneling
National Category
Electrical Engineering, Electronic Engineering, Information Engineering Energy Systems Other Materials Engineering
Identifiers
urn:nbn:se:uu:diva-357123 (URN)10.1016/j.solmat.2018.07.017 (DOI)000445308300019 ()
Funder
Swedish Research Council, 43523-1StandUpEU, Horizon 2020, 720887
Available from: 2018-08-12 Created: 2018-08-12 Last updated: 2023-10-31Bibliographically approved
4. Effect of NaF pre-cursor on alumina and hafnia rear contact passivation layers in ultra-thin Cu(In,Ga)Se2 solar cells
Open this publication in new window or tab >>Effect of NaF pre-cursor on alumina and hafnia rear contact passivation layers in ultra-thin Cu(In,Ga)Se2 solar cells
Show others...
2019 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 683, p. 156-164Article in journal (Refereed) Published
Abstract [en]

In this work, we evaluate the effect of NaF layers on the properties of Al2O3 and HfO2 rear contact passivation layers in ultra-thin Cu(In,Ga)Se2 solar cells. The 6 nm thin passivation layers were deposited by atomic layer deposition and neither intentionally opened nor nano-patterned in any extra-fabrication step. NaF layers, 7.5 or 15 nm thin, were deposited as precursors prior to CIGS absorber co-evaporation. The 215 nm thick absorbers were co-evaporated with constant evaporation rates for all elements. Directly thereafter, a 70 nm thick cadmium sulfide layer was deposited. Photoluminescence measurements indicate a strongly reduced recombination at the rear contact for all passivated samples compared to an unpassivated reference. Although the sample with Al2O3 passivation and a 15 nm NaF precursor layer luminesces by far the least of the passivated samples, solar cells made from this sample show the highest efficiency (8.6% compared with 5.6% for the reference with no passivation). The current-voltage curves of the solar cells fabricated from the sample with 7.5 nm NaF on top of the Al2O3 layer and both samples with HfO2 exhibit blocking behavior to various degrees, but a high photoluminescence response. We conclude that NaF precursor layers increase conduction through the Al2O3 layer, but also reduce its effectiveness as a passivation layer. In contrast, conduction through the HfO2 passivation layers seem to not be influenced by NaF precursor layers, and thus requires nano-patterning or thinning for conduction.

Keywords
Alkali, Alumina, Copper indium gallium diselenide, Hafnia, Passivation, Sodium fluoride, Ultra-thin
National Category
Condensed Matter Physics Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-387716 (URN)10.1016/j.tsf.2019.05.024 (DOI)000469854700020 ()
Funder
Swedish Energy AgencySwedish Research Council, 621-2014-5599StandUp
Available from: 2019-06-26 Created: 2019-06-26 Last updated: 2020-06-15Bibliographically approved

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