Growth of Cu2ZnSnSe4 by cosputtering and reactive annealing atmosphere

Bodeux, Romain; Mollica, Fabien; Delbos, Sébastien

doi:10.1016/j.solmat.2014.08.001

Cited by 23 publications

(21 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The intimate mixing of all these phases and the presence of both, Sn-Se and Cu-Sn-Se coexisting in the bulk of the same absorber suggests that most probably these two reaction pathways are competing and contributing both to the formation of kesterites under the studied conditions. As is clear, somewhere between the point D (350 ºC) and point E (400 ºC) the kesterite starts to be formed, in good agreement with previous published data 17,20 . In our case, the heating ramp is 180 ºC/min, i.e.…”

Section: Resultssupporting

confidence: 91%

“…This is among others very relevant for understanding the role of the different possible secondary phases during the kesterite formation, and in the properties of the resulting absorbers. Thus, Table 1 summarizes some of the most relevant works published in this subject [15][16][17][18][19][20] , where it is clear that for the different possible materials and processes, relatively different pathways have been deduced.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Insights into the Formation Pathways of Cu₂ZnSnSe₄ Using Rapid Thermal Processes

Hernández-Martínez

Placidi

Arqués

et al. 2018

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

Recent advances in Cu2ZnSn(S,Se)4 (CZTSe) thin film photovoltaics open the possibility for the future industrialization of this technology. Nevertheless, major progresses in CZTSe have been achieved using conventional thermal processing annealing routes (CTP), which rely on timeconsuming processes with tubular furnaces, incompatible with the requisites of fast methodologies for the Industry. Changing from conventional to rapid thermal processes (RTP) using halogen lamps as heating method is not at all obvious, since the system becomes kinetically controlled, and the CZTSe formation mechanisms as well as crystallization pathways can drastically change. In this work we present the transfer of our kesterite production baseline (Cu2ZnSnSe4:Ge) from a conventional thermal process using a tubular furnace, towards a rapid thermal process using an adapted system, by comparing them and analyzing the differences between both processes in terms of formation mechanisms as well as photovoltaic absorber properties. For this purpose, the rapid annealing process is stopped at different steps, analyzing the compositional, structural and morphological properties of the CZTSe absorber at these different stages. Using a combination of XRF, SEM, Raman spectroscopy and XRD characterization techniques it is demonstrated that in contrast to CTP routes, when RTP is used, kesterite is being formed in large amounts in the very early stages. This suggests a fast formation of CZTSe promoted by the higher Se vapor pressure that can be quickly achieved with this methodology. The formation of kesterite seems to proceed via two competitive reactions (binaries vs ternary compound). Additionally, the fast reaction observed in the system avoids the possible Sn-loss in an efficient way. Through the optimization of this RTP treatment a device with 8.3% efficiency has been obtained (the total time of the thermal process is 12 min), comparable with the efficiencies obtained so far with CTP routes. Finally, the consequences of all these changes for the future interpretation of the formation reaction mechanisms of kesterites are discussed.

show abstract

Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Insights into the Formation Pathways of Cu₂ZnSnSe₄ Using Rapid Thermal Processes

Hernández-Martínez

Placidi

Arqués

et al. 2018

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

show abstract

“…The other Raman peaks of pure CZTS are detected at 285.7 and 369.3 cm À 1 and pure CZTSe at 171.6 and 231 cm À 1 , which are consistent with the reported data [42,43]. According to the literature [44,45], the corresponding vibration peaks of the secondary phases located at: 351 cm À 1 for ZnS, 163 cm À 1 and 189 cm À 1 for SnS, 251 cm À 1 for ZnSe, 352 cm À 1 for Cu 2 SnS 3 , 180 cm À 1 for Cu 2 SnSe 3 . There is no obvious evidence for these typical impurity phases from the Raman spectra.…”

Section: Characterization Of Cztsse Thin Filmssupporting

confidence: 91%

Pulsed laser deposition of Cu2ZnSn(SxSe1−x)4 thin film solar cells using quaternary oxide target prepared by combustion method

Jin

Chen

Zhang

et al. 2016

Solar Energy Materials and Solar Cells

View full text Add to dashboard Cite

“…Thereafter, extensive research in this route led to a great efficiency improvement, especially for pure-sulfide compounds which recently reached a new world-record efficiency of 11.04% [5]. In the case of mixed CZTSSe-devices obtained by a co-sputtering method [73][74][75], the best efficiency is 9.7% [31], well below the efficiencies reached with sequential sputtering approach, whereas no pure selenide device grown by co-sputtering route has been reported so far. For this reason, this section will be mainly focused on progresses related to CZTS based devices.…”

Section: Sequential Sputtering/co-sputteringmentioning

confidence: 99%

Physical routes for the synthesis of kesterite

et al. 2019

View full text Add to dashboard Cite

This paper provides an overview of the physical vapor technologies used to synthesize Cu 2 ZnSn(S,Se) 4 thin films as absorber layers for photovoltaic applications. Through the years, CZT(S,Se) thin films have been fabricated using sequential stacking or co-sputtering of precursors as well as using sequential or co-evaporation of elemental sources, leading to high-efficient solar cells. In addition, pulsed laser deposition of composite targets and monograin growth by the molten salt method were developed as alternative methods for kesterite layers deposition. This review presents the growing increase of the kesterite-based solar cell efficiencies achieved over the recent years. A historical description of the main issues limiting this efficiency and of the experimental pathways designed to prevent or limit these issues is provided and discussed as well. A final section is dedicated to the description of promising process steps aiming at further improvements of solar cell efficiency, such as alkali doping and bandgap grading. intensive research on Cu 2 ZnSn(S,Se) 4 (CZT(S,Se)) kesterite compounds as CRM-free absorber layers for PV applications is essential. This article aims at establishing a complete overview of the physical routes used for the synthesis of kesterite thin films as absorber layers in solar cells. The following sections are devoted to that objective and will take on the main issues which have been raised so far as well as how the processes have evolved through the years to meet the requirements of the market. Some major advancements in terms of deposition or post-deposition treatments are introduced. Advantages and drawbacks of each of the physical methods presented in this review are described in detail and compared to other physical or chemical synthesis routes. Physical routes: status overviewWe performed an extensive identification of the common processes and methods used for the synthesis of kesterite thin films or for the design of solar cell devices. In order to avoid unnecessary repetitions along this paper, this section first explains these well-known and commonly used experimental processes and methods. Historically, based on the similarities between kesterite and chalcopyrite compounds, the standard device structure adopted for Cu(In,Ga)(S,Se) 2 (CIGSSe) was directly extended to CZTSSe, by simply replacing the CIGSSe absorber layer with a p-type CZTSSe thin film. CZTSSe solar cells are then typically produced using a soda-lime glass (SLG) substrate coated with a sputtered Mo layer acting as rear metallic contact. Typical sputter-deposited Mo layer thickness is around 500 nm up to 1 μm [12]. The kesterite absorber is then deposited onto the Mo layer.The fabrication of this absorber consists in the deposition of a precursor layer via a physical or a chemical route, which is then annealed in a reactive atmosphere containing either S (sulfurization) or Se (selenization). As a common result of the reactive annealing, a thin Mo(S,Se) 2 layer is naturally formed at the CZTSSe/Mo interface, betw...

show abstract

Growth of Cu2ZnSnSe4 by cosputtering and reactive annealing atmosphere

Cited by 23 publications

References 40 publications

Insights into the Formation Pathways of Cu₂ZnSnSe₄ Using Rapid Thermal Processes

Insights into the Formation Pathways of Cu₂ZnSnSe₄ Using Rapid Thermal Processes

Pulsed laser deposition of Cu2ZnSn(SxSe1−x)4 thin film solar cells using quaternary oxide target prepared by combustion method

Physical routes for the synthesis of kesterite

Contact Info

Product

Resources

About

Growth of Cu2ZnSnSe4 by cosputtering and reactive annealing atmosphere

Cited by 23 publications

References 40 publications

Insights into the Formation Pathways of Cu2ZnSnSe4 Using Rapid Thermal Processes

Insights into the Formation Pathways of Cu2ZnSnSe4 Using Rapid Thermal Processes

Pulsed laser deposition of Cu2ZnSn(SxSe1−x)4 thin film solar cells using quaternary oxide target prepared by combustion method

Physical routes for the synthesis of kesterite

Contact Info

Product

Resources

About

Insights into the Formation Pathways of Cu₂ZnSnSe₄ Using Rapid Thermal Processes

Insights into the Formation Pathways of Cu₂ZnSnSe₄ Using Rapid Thermal Processes