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Window Layer Structures for Chalcopyrite Thin-Film Solar Cells
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solar Cell Technology.ORCID iD: 0000-0002-3162-4292
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis aims to contribute to the development of improved window layer structures for chalcopyrite thin-film solar cells, with an emphasis on the buffer layer, to assist future reductions of the levelized cost of energy. This is realized by exploring the potential of existing materials and deposition processes, as well as developing new buffer layer processes based on atomic layer deposition (ALD).

Ternary compound ALD processes are more complicated to control than when depositing binary compounds and the composition can be significantly different at the absorber interface as compared to the bulk. A method based on in-situ quartz crystal microbalance that can measure these compositional variations is demonstrated in the thesis. Furthermore, the addition of alkali-metal fluoride post-deposition treatments (PDTs) can further complicate ALD of buffer layers, due to residual salts that are formed on the absorber surface during a PDT process. When applying ALD ZnO1-xSx to KF-treated CIGS absorbers, competitive solar cell efficiencies could only be obtained after performing additional wet-chemical treatments prior to ALD processing.

It is shown that the performance of wide-bandgap solar cells can be greatly enhanced by improving the conduction band alignment between the absorber and buffer layers. By applying ALD Zn1-xSnxOy buffer layers in CuGaSe2 solar cells, record efficiency (η = 11.9%) and open-circuit voltage (Voc = 1017 mV) values are demonstrated.

In search of a new buffer layer suitable for a wide range of absorber materials (and surface bandgaps), amorphous tin-gallium oxide grown by ALD is evaluated as a new buffer layer material. This material exhibits a highly variable bandgap (and electron affinity) the absorber/buffer conduction band alignment can be controlled by adjusting the cation composition and deposition temperature. The potential of Sn1-xGaxOy as a buffer layer was studied in combination with low-bandgap (Ag,Cu)(In,Ga)Se2 absorbers (Eg,surface ≈ 1.1 eV). A best cell efficiency of 17.0% was achieved, which was lower than the efficiency of 18.6% obtained for the corresponding CdS reference due to slightly lower Voc and higher series resistance. However, the full potential of Sn1-xGaxOy as a buffer layer remains to be revealed.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2020. , p. 110
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1951
Keywords [en]
CIGS, atomic layer deposition, ALD, thin-film technology, window layer structures, buffer layers, front contacts, metal oxides, ternary compounds
Keywords [sv]
CIGS, tunnfilmssolceller, ALD, tunnfilmsteknik, fönsterlager, buffertlager, framkontakter, metalloxider, ternära föreningar
National Category
Engineering and Technology Other Materials Engineering Other Electrical Engineering, Electronic Engineering, Information Engineering
Research subject
Engineering Science with specialization in Electronics
Identifiers
URN: urn:nbn:se:uu:diva-416751ISBN: 978-91-513-0984-2 (print)OAI: oai:DiVA.org:uu-416751DiVA, id: diva2:1456222
Public defence
2020-09-18, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2020-08-27 Created: 2020-08-03 Last updated: 2020-09-02Bibliographically approved
List of papers
1. Evaluation of different intrinsic ZnO and transparent conducting oxide layer combinations in Cu(In,Ga)Se2 solar cells
Open this publication in new window or tab >>Evaluation of different intrinsic ZnO and transparent conducting oxide layer combinations in Cu(In,Ga)Se2 solar cells
2017 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 633, p. 235-238Article in journal (Refereed) Published
Abstract [en]

We studied the interaction of four different window layer combinations in Cu(In,Ga)Se-2 solar cells. Intrinsic ZnO (i-ZnO) layers were grown on CdS by either chemical vapor deposition (CVD) or magnetron sputtering. These were combined with sputtered ZnO:Al or In2O3:H grown by atomic layer deposition as transparent conducting oxides (TCO). It was found that the thickness of the CVD i-ZnO layer affects the open circuit voltage (V-oc) significantly when using In2O3:H as TCO. The V-oc dropped by roughly 30 mV when the i-ZnO thickness was increased from 20 to 160 nm. This detrimental effect on V-oc was not as prominent when a ZnO:Al TCO was used, where the corresponding decrease was in the range of 5 to 10 my. In addition, the V-oc drop for the CVD i-ZnO/In2O3:H structure was not observed when using the sputtered i-ZnO layer. Furthermore, large fill factor variations were observed when using the In2O3:H TCO without an i-ZnO layer underneath, where already a thin (20 nm) CVD i-ZnO layer mitigated this effect. Device simulations were applied to explain the experimentally observed Voc trends.

Keywords
Copper indium gallium selenide, Transparent conducting oxide, Atomic layer deposition, Zinc oxide, Indium oxide
National Category
Physical Sciences Materials Engineering
Identifiers
urn:nbn:se:uu:diva-330020 (URN)10.1016/j.tsf.2016.09.015 (DOI)000404802300045 ()
Conference
Symposium V on Thin Film Chalcogenide Photovoltaic Materials held at the 13th E-MRS Spring Meeting, MAY 02-06, 2016, Lille, FRANCE
Funder
Swedish Energy Agency, 2012-004591
Note

Evaluation of different intrinsic ZnO and transparent conducting oxide layer combinations in Cu(In,Ga)Se-2 solar cells

Available from: 2017-10-10 Created: 2017-10-10 Last updated: 2020-08-03Bibliographically approved
2. Record 1.0 V open-circuit voltage in wide band gap chalcopyrite solar cells
Open this publication in new window or tab >>Record 1.0 V open-circuit voltage in wide band gap chalcopyrite solar cells
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2017 (English)In: Progress in Photovoltaics, ISSN 1062-7995, E-ISSN 1099-159X, Vol. 25, p. 755-763Article in journal (Refereed) Published
Abstract [en]

Tandem solar cell structures require a high‐performance wide band gap absorber as top cell. Apossible candidate is CuGaSe2, with a fundamental band gap of 1.7 eV. However, a significantopen‐circuit voltage deficit is often reported for wide band gap chalcopyrite solar cells likeCuGaSe2. In this paper, we show that the open‐circuit voltage can be drastically improved in wideband gap p‐Cu(In,Ga)Se2and p‐CuGaSe2devices by improving the conduction band alignment tothe n‐type buffer layer. This is accomplished by using Zn1−xSnxOy, grown by atomic layer deposi-tion, as a buffer layer. In this case, the conduction band level can be adapted to an almost perfectfit to the wide band gap Cu(In,Ga)Se2and CuGaSe2materials. With an improved buffer bandalignment for CuGaSe2absorbers, evaporated in a 3‐stage type process, we show devicesexhibiting open‐circuit voltages up to 1017 mV, and efficiencies up to 11.9%. This is to the bestof our knowledge the highest reported open‐circuit voltage and efficiency for a CuGaSe2device.Temperature‐dependent current‐voltage measurements show that the high open‐circuit voltageis explained by reduced interface recombination, which makes it possible to separate theinfluence of absorber quality from interface recombination in future studies.

National Category
Other Electrical Engineering, Electronic Engineering, Information Engineering
Identifiers
urn:nbn:se:uu:diva-332821 (URN)10.1002/pip.2914 (DOI)000407209800001 ()
Funder
Swedish Energy Agency, 2012-004591
Available from: 2017-11-02 Created: 2017-11-02 Last updated: 2020-08-03Bibliographically approved
3. Atomic layer deposition of Zn(O,S) buffer layers for Cu(In,Ga)Se2 solar cells with KF post-deposition treatment
Open this publication in new window or tab >>Atomic layer deposition of Zn(O,S) buffer layers for Cu(In,Ga)Se2 solar cells with KF post-deposition treatment
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2018 (English)In: Solar Energy Materials and Solar Cells, ISSN 0927-0248, E-ISSN 1879-3398, Vol. 183, p. 8-15Article in journal (Refereed) Published
Abstract [en]

We investigate the possibility to combine Zn(O,S) buffer layers grown by atomic layer deposition (ALD) with KF post-deposition treated Cu(In,Ga)Se-2 (CIGS-KF) in solar cells. It is shown that the beneficial effect on open-circuit voltage from the post-deposition treatment is essentially independent of buffer layer material. However, a wet chemical surface treatment is required prior to ALD in order to achieve competitive fill factor values. A water rinse is sufficient to create an absorber surface similar to the one formed during a conventional CdS chemical bath deposition process. However, it is observed that CIGS-KF/Zn(O,S) devices made with water-rinsed absorbers systematically result in lower fill factor values than for the corresponding CIGS-KF/CdS references. This effect can be mitigated by decreasing the H2S:H2O precursor ratio during ALD initiation, indicating that the fill factor limitation is linked to the initial Zn(O,S) growth on the modified CIGS-KF surface. The best CIGS-KF/Zn (O,S) devices were fabricated by etching away the KF-modified surface layer prior to ALD, followed by a low temperature anneal. The thermal treatment step is needed to increase the open-circuit voltage close to the value of the CdS devices. The results presented in this contribution indicate that the main beneficial effects from KFPDT in our devices are neither associated with the CdS CBD process nor due to the formation of a K-In-Serich phase on the CIGS surface.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
CIGS, KF-PDT, Zinc oxysulfide, Buffer layers, Interfaces
National Category
Other Electrical Engineering, Electronic Engineering, Information Engineering Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-358259 (URN)10.1016/j.solmat.2018.03.045 (DOI)000435624400002 ()
Funder
Swedish Energy Agency, 2017-004796
Available from: 2018-08-27 Created: 2018-08-27 Last updated: 2022-10-18Bibliographically approved
4. Atomic layer deposition of amorphous tin-gallium oxide films
Open this publication in new window or tab >>Atomic layer deposition of amorphous tin-gallium oxide films
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2019 (English)In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films, ISSN 0734-2101, E-ISSN 1520-8559, Vol. 37, no 3, article id 030906Article in journal (Refereed) Published
Abstract [en]

A wide range of applications benefit from transparent semiconducting oxides with tunable electronic properties, for example, electron transport layers in solar cell devices, where the electron affinity is a key parameter. Presently, a few different ternary oxides are used for this purpose, but the attainable electron affinity range is typically limited. In this study, the authors develop a low-temperature atomic layer deposition (ALD) process to grow amorphous Sn1-xGaxOy thin films from dimethylamino-metal complexes and water. This oxide is predicted to provide a wide selection of possible electron affinity values, from around 3 eV for pure Ga2O3 to 4.5 eV for pure SnO2. The ALD process is evaluated for deposition temperatures in the range of 105-195 degrees C by in situ quartz crystal microbalance and with ex situ film characterization. The growth exhibits an ideal-like behavior at 175 degrees C, where the film composition can be predicted by a simple rule of mixture. Depending on film composition, the growth per cycle varies in the range of 0.6-0.8 angstrom at this temperature. Furthermore, the film composition for a given process appears insensitive to the deposition temperature. From material characterization, it is shown that the deposited films are highly resistive, fully amorphous, and homogeneous, with moderate levels of impurities (carbon, nitrogen, and hydrogen). By tailoring the metal cation ratio in films grown at 175 degrees C, the optical bandgap can be varied in the range from 2.7 eV for SnO2 to above 4.2 eV for Ga2O3. The bandgap also varies significantly as a function of deposition temperature. This control of properties indicates that Sn1-xGaxOy is a promising candidate for an electron transport layer material in a wide electron affinity range. Published by the AVS.

Place, publisher, year, edition, pages
A V S AMER INST PHYSICS, 2019
National Category
Condensed Matter Physics Materials Chemistry Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-390540 (URN)10.1116/1.5092877 (DOI)000472182400033 ()
Funder
Swedish Energy Agency, 2017-004796Swedish Research Council, 2017-00646 9Swedish Foundation for Strategic Research , RIF14-0053
Available from: 2019-08-12 Created: 2019-08-12 Last updated: 2020-08-03Bibliographically approved
5. Amorphous tin-gallium oxide buffer layers in (Ag,Cu)(In,Ga)Se2 solar cells
Open this publication in new window or tab >>Amorphous tin-gallium oxide buffer layers in (Ag,Cu)(In,Ga)Se2 solar cells
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2020 (English)In: Solar Energy Materials and Solar Cells, ISSN 0927-0248, E-ISSN 1879-3398, Vol. 215, article id 110647Article in journal (Refereed) Published
Abstract [en]

Amorphous tin-gallium oxide (a-SGO) grown with atomic layer deposition was evaluated as a buffer layer in (Ag,Cu)(In,Ga)Se2 thin-film solar cells in search for a new material that is compatible with a variety of absorber band gaps. Hard and soft X-ray photoelectron spectroscopy on absorber/a-SGO stacks combined with J–V characterization of solar cells that were fabricated, showed that the conduction band alignment at the absorber/a-SGO interface can be tuned by varying the cation composition and/or growth temperature. Here, the surface band gap was 1.1 eV for the absorber. However, optical band gap data for a-SGO indicate that a suitable conduction band alignment can most likely be achieved even for wider absorber band gaps relevant for tandem top cells. A best efficiency of 17.0% was achieved for (Ag,Cu)(In,Ga)Se2/a-SGO devices, compared to η = 18.6% for the best corresponding CdS reference. Lower fill factor and open-circuit voltage values were responsible for lower cell efficiencies. The reduced fill factor is explained by a larger series resistance, seemingly related to interface properties, which are yet to be optimized. Some layer constellations resulted in degradation in fill factor during light soaking as well. This may partly be explained by light-induced changes in the electrical properties of a-SGO, according to analysis of Al/SGO/n-Si metal-oxide-semiconductor capacitors that were fabricated and characterized with J–V and C–V. Moreover, the introduction of a 1 nm thick Ga2O3 interlayer between the absorber and a-SGO improved the open-circuit voltage, which further indicates that the absorber/a-SGO interface can be improved.

Keywords
GIGS, ACIGS, Buffer layers, Atomic layer deposition, Band gap engineering, Interfaces
National Category
Condensed Matter Physics Other Electrical Engineering, Electronic Engineering, Information Engineering
Identifiers
urn:nbn:se:uu:diva-416748 (URN)10.1016/j.solmat.2020.110647 (DOI)000574947200001 ()
Funder
Swedish Energy Agency, 2017-004796
Available from: 2020-08-03 Created: 2020-08-03 Last updated: 2020-12-11Bibliographically approved
6. Atomic Layer Deposition of Ternary Compounds on Cu(In,Ga)Se2: An In Situ Quartz Crystal Microbalance Study
Open this publication in new window or tab >>Atomic Layer Deposition of Ternary Compounds on Cu(In,Ga)Se2: An In Situ Quartz Crystal Microbalance Study
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2020 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 3, no 7, p. 7208-7215Article in journal (Refereed) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020
National Category
Engineering and Technology
Identifiers
urn:nbn:se:uu:diva-416749 (URN)10.1021/acsaem.0c01284 (DOI)000557375200131 ()
Available from: 2020-08-03 Created: 2020-08-03 Last updated: 2020-12-15Bibliographically approved

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