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Multijunction solar cells in a tandem configuration could further lower the costs of electricity if crystalline Si (c-Si) is used as the bottom cell. However, for direct monolithic integration on c-Si, only a restricted number of top and bottom cell architectures are compatible, due to either epitaxy or high-temperature constraints, where the interface between subcells is subject to a trade-off between transmittance, electrical interconnection, and bottom cell degradation. Using polySi/SiOx passivating contacts for Si, this degradation can be largely circumvented by tuning the polySi/SiOx stacks to promote gettering of contaminants admitted into the Si bottom cell during the top cell synthesis. Applying this concept to the low-cost top cell chalcogenides Cu2ZnSnS4 (CZTS), CuGaSe2 (CGSe), and AgInGaSe2 (AIGSe), fabricated under harsh S or Se atmospheres above 550 degrees C, we show that increasing the heavily doped polySi layer thickness from 40 to up to 400 nm prevents a reduction in Si carrier lifetime by 1 order of magnitude, with final lifetimes above 500 mu s uniformly across areas up to 20 cm(2). In all cases, the increased resilience was correlated with a 99.9% reduction in contaminant concentration in the c-Si bulk, provided by the thick polySi layer, which acts as a buried gettering layer in the tandem structure without compromising the Si passivation quality. The Si resilience decreased as AIGSe > CGSe > CZTS, in accordance with the measured Cu contamination profiles and higher annealing temperatures. An efficiency of up to 7% was achieved for a CZTS/Si tandem, where the Si bottom cell is no longer the limiting factor.

Herein, a new route of sulfur grading in CuInSe2 (CISe) thin-film solar absorbers by introducing an ultrathin (<50 nm) sacrificial sputtered CuInS2 (CIS) layer on top of the CISe. Different CIS top layer compositions (Cu-poor to Cu-rich) are analyzed, before and after a high-temperature treatment in selenium (Se)- or selenium+sulfur (SeS)-rich atmospheres. An [S]/([S] + [Se]) grading from the surface into the bulk of the Se- and SeS-treated samples is observed, and evidence of the formation of a mixed CuIn(S,Se)2 phase by Raman analysis and X-ray diffraction is provided. The optical bandgap from quantum efficiency measurements of solar cells is increased from 1.00 eV for the CISe reference to 1.14 and 1.30 eV for the Se- and SeS-treated bilayer samples, respectively. A ≈150 mV higher VOC is observed for the SeS-treated bilayer sample, but the cell exhibits blocking characteristics resulting in lower efficiency as compared with the CISe reference. This blocking is attributed to an internal electron barrier at the interface to the sulfur-rich surface layer. The difference in reaction routes and possible ways to improve the developed sulfurization process are discussed.

The Cu2ZnGe X Sn1-X S4 (CZGTS) thin-film solar cells have a limited open-circuit voltage (V OC) due to bulk and interface recombination. Since the standard CdS buffer layer gives a significant cliff-like conduction band offset to CZGTS, alternative buffer layers are needed to reduce the interface recombination. This work compares the performance of wide bandgap Cu2ZnGeS4 (CZGS) solar cells fabricated with nontoxic Zn x Sn1–x O y (ZTO) buffer layers grown by atomic layer deposition under different conditions. The V OC of the CZGS solar cell improved significantly to over 1 V by substituting CdS with ZTO. However, V OC is relatively insensitive to ZTO bandgap variations. The short-circuit current is generally low but is improved with KCN etching of the CZGS absorber before deposition of the ZTO buffer layer. A possible explanation for the device behavior is the presence of an oxide interlayer for nonetched devices., Title in thesis list of papers: Record 1.1 V open circuit voltage for Cu2ZnGeS4 based thin-film solar cells using atomic layer deposition Zn1-xSnxOy buffer layers

Chalcopyrite Cu(In,Ga)Se-2 (CIGSe) solar absorbers are renowned for delivering high solar power conversion efficiency despite containing high concentration of lattice defects amounting to copper deficiencies of several atomic percent. The unique ability to incorporate this deficiency without triggering decomposition (i.e. "tolerance to off-stoichiometry") is viewed by many as the key feature of CIGSe. In principle, this property could benefit any solar absorber, but remarkably little attention has been paid to it so far. In this study, we assess the tolerance to off-stoichiometry of thin-film photovoltaic materials by carrying out ab initio analysis of group-I-poor ordered defect compounds (ODCs) in the extended family of I-III-VI systems (where I = Cu, Ag, III = Al, Ga, In, and VI = S, Se, Te). We analyze convex hulls and structural evolution with respect to group-I content, link them with experimental phase diagrams, and determine two empirical principles for the future identification of solar energy materials with high tolerance to off-stoichiometry. Practical implications for the deposition of I-III-VI absorbers are also discussed in light of our computational results and recent experimental findings.

Kesterite Cu2ZnSnS4 (CZTS), used for thin film solar cells, has a band gap energy around 1.5–1.6 eV with possibilities for further increase through alloying. In some applications for wide band gap solar cells, reduced absorber thickness can be beneficial, to allow partial light transmission. Reduced thickness can also be beneficial to reduce bulk recombination, and so called ultrathin solar cells (<700 nm thick) have been studied for several materials systems. Here, we report performance for CZTS devices down to 250 nm thickness and show that performance loss from thickness reduction is relatively small, partly due to short minority carrier diffusion length. Insertion of thin passivation layers (Al2O3, SiO2 or HfO2) at the Mo/CZTS interface gives improved performance of ultrathin devices, from 4.7% to 5.6% efficiency for best performing cells having 250 nm thick CZTS with Mo as compared to Mo/Al2O3 back contact. The approach of NaF post deposition for making isolating passivation layers conductive is tested for the first time for CZTS and is shown to work. For fabrication of CZTS devices on transparent ITO back contact, the insertion of passivation layers can reduce diffusion of indium into CZTS, but device performance is lower than on Mo back contacts.

The Cu2ZnGe X Sn1-X S4 (CZGTS) thin-film solar cells have a limited open-circuit voltage (V OC) due to bulk and interface recombination. Since the standard CdS buffer layer gives a significant cliff-like conduction band offset to CZGTS, alternative buffer layers are needed to reduce the interface recombination. This work compares the performance of wide bandgap Cu2ZnGeS4 (CZGS) solar cells fabricated with nontoxic Zn x Sn1–x O y (ZTO) buffer layers grown by atomic layer deposition under different conditions. The V OC of the CZGS solar cell improved significantly to over 1 V by substituting CdS with ZTO. However, V OC is relatively insensitive to ZTO bandgap variations. The short-circuit current is generally low but is improved with KCN etching of the CZGS absorber before deposition of the ZTO buffer layer. A possible explanation for the device behavior is the presence of an oxide interlayer for nonetched devices., Title in thesis list of papers: Record 1.1 V open circuit voltage for Cu2ZnGeS4 based thin-film solar cells using atomic layer deposition Zn1-xSnxOy buffer layers

Kesterite-based solar cells are mainly restricted by their lower than expected open-circuit voltage (Voc) due to non-radiative recombination. Therefore, an approach to reduce bulk and interface recombination through band gap grading to induce a back surface field is attempted. This contribution presents the challenges in the formation of compositional grading of the wide bandgap material Cu2ZnGexSn1−xS4 (CZGTS) and successful fabrication of solar cells with an additional adhesive TiN interlayer. It is observed that the TiN interlayer improves adhesion between CZGTS and the back contact. The microstructure of the Cu2ZnSnS4 (CZTS) film is significantly affected by the concentration of Ge, and the existence of a Ge concentration gradient is strongly correlated to the formation of smaller Ge-rich and larger Sn-rich grains. The bandgap grading is exploited with a moderate Ge concentration of up to (Ge/(Ge+Sn) = 0.25) in CZTS. As the Ge profile stretched all the way to the front interface, the cliff-like band alignment at the front interface of the absorber could negate the beneficial effect of Ge inclusion in the bulk and back interface of the absorber. Ordering the absorber can introduce an additional downward shift in the valence band. In one of the samples, the increased ordering and high concentration of Ge in CZTS are suggested to enhance the hole barrier at the back interface. It is concluded that the effect of the bandgap grading with Ge can only be realized with optimization of interface band alignment and back contact formation.

Silver alloying of Cu(In,Ga)Se-2 absorbers for thin film photovoltaics offers improvements in open-circuit voltage, especially when combined with optimal alkali-treatments and certain Ga concentrations. The relationship between alkali distribution in the absorber and Ag alloying is investigated here, combining experimental and theoretical studies. Atom probe tomography analysis is implemented to quantify the local composition in grain interiors and at grain boundaries. The Na concentration in the bulk increases up to similar to 60 ppm for [Ag]/([Ag] + [Cu]) = 0.2 compared to similar to 20 ppm for films without Ag and up to similar to 200 ppm for [Ag]/([Ag] + [Cu]) = 1.0. First-principles calculations were employed to evaluate the formation energies of alkali-on-group-I defects (where group-I refers to Ag and Cu) in (Ag,Cu)(In,Ga)Se-2 as a function of the Ag and Ga contents. The computational results demonstrate strong agreement with the nanoscale analysis results, revealing a clear trend of increased alkali bulk solubility with the Ag concentration. The present study, therefore, provides a more nuanced understanding of the role of Ag in the enhanced performance of the respective photovoltaic devices.

This contribution evaluates the effect of absorber off‐stoichiometry in wide‐gap (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells. It is found that ACIGS films show an increased tendency to form ordered vacancy compounds (OVCs) with increasing Ga and Ag contents. Very little tolerance to off‐stoichiometry is detected for absorber compositions giving the desired properties of 1) an optimum bandgap (EG) for a top cell in tandem devices (EG = 1.6–1.7 eV) and at the same time 2) a favorable band alignment with a CdS buffer layer. Herein, massive formation of either In‐ or Ga‐enriched OVC patches is found for group I‐poor ACIGS. As a consequence, carrier transport and charge collection are significantly impeded in corresponding solar cells. The transport barrier appears to be increasing with storage time, questioning the long‐term stability of wide‐gap ACIGS solar cells. Furthermore, the efficiency of samples with very high Ga and Ag contents depends on the voltage sweep direction. It is proposed that the hysteresis behavior is caused by a redistribution of mobile Na ions in the 1:1:2 absorber lattice upon voltage bias. Finally, a broader perspective on OVC formation in the ACIGS system is provided and fundamental limitations for wide‐gap ACIGS solar cells are discussed.

Cu2ZnSnS4 (CZTS) has attracted interest for applications in thin-film solar cells. In this study, the annealing process for CZTS fabrication is systematically varied, resulting in a large variation of materials properties. These variations are connected to the sulfur partial pressure during the annealing. A well-known phenomenon in CZTS is the presence of a high density of Cu-Zn antisite defect pairs, also known as Cu-Zn disorder. Faster Cu-Zn ordering occurs in samples with a similar starting composition annealed in an atmosphere with a higher sulfur partial pressure. This is explained by a higher density of vacancies in these samples. The results indicate that reduction of the vacancy concentration in CZTS annealed in insufficient sulfur partial pressure reduces diffusion, which results in more defective material with a higher density of tail states and poorer device performance.

Gallium alloying and grading in Cu(In,Ga)Se-2 (CIGS) are well-established strategies for improving performance of thin-film solar cells by tailoring band profiles within the absorber. Similarly, Ag incorporation is considered to be an effective complementary route towards further advancement of the field. Herein, we explore thermodynamics of the formation of (Ag,Cu)(In,Ga)Se-2 (ACIGS) alloy. Using first-principles methods, we reveal the existence of a miscibility gap in the Ga-rich alloys at temperatures close to those employed for the co-evaporation growth. We demonstrate that this property can result in phase separation and the formation of Ag gradients throughout the film thickness. We prove experimentally that the phase separation can indeed occur during low-temperature growth and/or post-deposition treatments. Furthermore, we uncover the anticorrelation between Ag and Ga contents, and demonstrate thermodynamically-driven formation of [Ag]/([Ag] + [Cu]) gradients in films with a steep [Ga]/([Ga] + [In]) profile. Finally, we discuss how these phenomena can influence solar cell devices. The presented results are expected to provide fundamental insight into the physics of growth and processing of ACIGS absorbers, which could be utilized to further boost the efficiency of thin-film solar cells.

Herein, sulfurization of CuInSe(2)and CuGaSe2(CGSe) absorber layers is compared to improve the understanding of sulfur incorporation into Cu(In,Ga)Se(2)films by annealing in a sulfur atmosphere. It is found for Cu-poor CuInSe(2)that for an annealing temperature of 430 degrees C, sulfur is incorporated into the surface of the absorber and forms an inhomogeneous CuIn(S,Se)(2)layer. In addition, at 530 degrees C, a surface layer of CuInS(2)is formed. In contrast, for Cu-poor CuGaSe(2)samples, S can only be introduced at 530 degrees C, mainly forming an alloy of CuGa(S,Se)(2), where no closed CuGaS(2)layer is found. In Cu-rich CuGaSe(2)samples, however, selenium is substituted by S already at 330 degrees C, which can be explained by a rapid phase transformation of Cu2 - xSe into Cu2 - x(S,Se). This transformation facilitates S in-diffusion and catalyzes CuGa(S,Se)(2)formation, likewise that previously reported to occur in CuInSe2. Finally, the Cu-poor CuInSe(2)solar cell performance is improved by the sulfurization step at 430 degrees C, whereas for the 530 degrees C sample, a decreasing fill factor and short-circuit current density are observed, indicating lower diffusion length accompanied by possible formation of an electron transport barrier. In contrast, the electrical characteristics deteriorate for all sulfurized Cu-poor CuGaSe(2)cells.

Alloying of Cu2ZnSnS4 (CZTS) with Ge can potentially promote grain growth and suppress the formation of Sn‐related defects. Herein, a two‐step fabrication route based on compound co‐sputtering and sulfurization at a high temperature is used to prepare Ge‐incorporated CZTS (Cu2ZnGexSn1 − xS4 [CZGTS]). For Cu2ZnGeS4 (CZGS), films deposited using elemental Ge and binary GeS targets are compared. The recrystallization is shown to be promoted for the absorbers deposited using Ge target, possibly due to lower sulfur content in the precursor suppressing the formation of wurtzite‐like phases during sputtering. The grain growth and crystallinity in CZGTS are slightly improved for x = 0.2 but not for higher concentration of the incorporated Ge. Owing to the composition‐dependent electronic properties, compositionally graded CZGTS films may be beneficial for reducing recombination towards the back contact. Hence, herein, the successful formation of a steep concentration gradient with Ge and Sn is demonstrated by the deposition of a CZGS/CZTS precursor stack followed by sulfurization with varying time periods.

Surface sulfurization of Cu(In,Ga)Se-2 (CIGSe) absorbers is a commonly applied technique to improve the conversion efficiency of the corresponding solar cells, via increasing the bandgap towards the heterojunction. However, the resulting device performance is understood to be highly dependent on the thermodynamic stability of the chalcogenide structure at the upper region of the absorber. The present investigation provides a high-resolution chemical analysis, using energy dispersive X-ray spectrometry and laser-pulsed atom probe tomography, to determine the sulfur incorporation and chemical re-distribution in the absorber material. The post-sulfurization treatment was performed by exposing the CIGSe surface to elemental sulfur vapor for 20 min at 500 degrees C. Two distinct sulfur-rich phases were found at the surface of the absorber exhibiting a layered structure showing In-rich and Ga-rich zones, respectively. Furthermore, sulfur atoms were found to segregate at the absorber grain boundaries showing concentrations up to similar to 7 at% with traces of diffusion outwards into the grain interior.

Cu2ZnSnS4(CZTS) thin-film solar cell absorbers with different bandgaps can be produced by parameter variation during thermal treatments. Here, the effects of varied annealing time in a sulfur atmosphere and an ordering treatment of the absorber are compared. Chemical changes in the surface due to ordering are examined, and a downshift of the valence band edge is observed. With the goal to obtain different band alignments, these CZTS absorbers are combined with Zn1−xSnxOy (ZTO) or CdS buffer layers to produce complete devices. A high open circuit voltage of 809 mV is obtained for an ordered CZTS absorber with CdS buffer layer, while a 9.7% device is obtained utilizing a Cd free ZTO buffer layer. The best performing devices are produced with a very rapid 1 min sulfurization, resulting in very small grains.

It is investigated if the performance of Cu(In,Ga)Se-2 (CIGSe) solar cells produced by co-evaporation can be improved by surface sulfurization in a postdeposition treatment. The expected benefit would be the formation of a sulfur/selenium gradient resulting in reduced interface recombination and increased open-circuit voltage. In the conditions used here it was, however, found that the reaction of the CIGSe layer in a sulfur environment results in the formation of a CuInS2 (CIS) surface phase containing no or very little selenium and gallium. At the same time, a significant pile up of gallium was observed at the CIGSe/CIS boundary. This surface structure was formed for a wide range of annealing conditions investigated in this paper. Increasing the temperature or extending the time of the dwell stage had a similar effect on the material. The gallium enrichment and CIS surface layer widens the surface bandgap and therefore increases the open-circuit voltage. At the same time, the fill factor is reduced, since the interface layer acts as an electron barrier. Due to the balance of these effects, the conversion efficiency could not be improved.

In this work, we have demonstrated the extreme radiation hardness of thin film CZTSSe solar cells. Thin film solar cells with CZTSSe, CZTS and CIGS absorber layers were irradiated with 3 MeV protons. No degradation in device parameters was observed until a displacement damage dose of 2 x 10(10) MeV/g for CZTS and CZTSSe. CIGS solar cells degraded by 13% at the same dose. For the highest proton dose both the CZTSSe and CZTS degraded by 16% while CIGS suffered from 34% degradation in efficiency. The degradation in efficiency maybe attributed to the reduction in the minority carrier lifetime due to radiation induced lattice defects. Comparisons with previously available literature show that our CZTS technology has superior radiation hardness by about two orders of magnitude compared to existing state of the art Si and GaAs technology.

Chalcogen-based materials like Cu2ZnSnS4 (CZTS) have attracted extensive attention for applications such as photovoltaics and water splitting. However, an inability to monitor the sulfur partial pressure (PS2) during the non-equilibrium annealing process at high temperatures complicates the synthesis of CZTS with controlled optoelectronic properties. Here we demonstrate that PS2 can be monitored by investigating the Sn–S phase transformation. We showed that PS2 drops considerably over the annealing time, causing gradual alterations in CZTS: (i) a change in defect type and (ii) evolution of ZnS and SnxSy phases. With additional ordering treatment, we observed that the low room-temperature photoluminescence energy usually seen in CZTS can result from insufficient PS2 during annealing. It is proven that remarkable Voc beyond 700 mV for solar cells with nonoptimal CdS buffer can be repeatedly achieved when CZTS is prepared under a sufficiently high PS2. An ordering treatment before CdS deposition can further improve Voc to 783 mV.

Recent studies demonstrate that air annealing can have a positive effect on the device performance of Cu2ZnSn(SxSe1-x)(4)[CZTSSe] solar cells. In this work air annealing of the selenium containing CZTSSe is compared to the pure sulfide CZTS. It is discovered that the selenium containing absorbers benefit from air annealing at higher temperatures than selenium free absorbers. The highest efficiency obtained utilizing the air annealing treatment on selenium containing absorbers is 9.7%. We find that the band gap is narrowed when air annealing, which is partially explained by increased Cu-Zn disorder. Furthermore Zn enrichment of the surface after etching is identified as a possible cause of enhanced device performance. It is additionally observed that elemental selenium present on the CZTSSe surface is reduced in the air annealing treatment. Selenium removal is another possible explanation for the enhanced performance caused by the air annealing treatment., Surface modification through air annealing Cu2ZnSn(S,Se)(4) absorbers