• Energy Research

Abstract We review the present state-of-the-art within back and front contacts in kesterite thin film solar cells, as well as the current challenges. At the back contact, molybdenum (Mo) is generally used, and thick Mo(S, Se)2 films of up to several hundred nanometers are seen in record devices, in particular for selenium-rich kesterite. The electrical properties of Mo(S, Se)2 can vary strongly depending on orientation and indiffusion of elements from the device stack, and there are indications that the back contact properties are less ideal in the sulfide as compared to the selenide case. However, the electronic interface structure of this contact is generally not well-studied and thus poorly understood, and more measurements are needed for a conclusive statement. Transparent back contacts is a relatively new topic attracting attention as crucial component in bifacial and multijunction solar cells. Front illuminated efficiencies of up to 6% have so far been achieved by adding interlayers that are not always fully transparent. For the front contact, a favorable energy level alignment at the kesterite/CdS interface can be confirmed for kesterite absorbers with an intermediate [S]/([S]+[Se]) composition. This agrees with the fact that kesterite absorbers of this composition reach highest efficiencies when CdS buffer layers are employed, while alternative buffer materials with larger band gap, such as Cd1−x Zn x S or Zn1−x Sn x O y , result in higher efficiencies than devices with CdS buffers when sulfur-rich kesterite absorbers are used. Etching of the kesterite absorber surface, and annealing in air or inert atmosphere before or after buffer layer deposition, has shown strong impact on device performance. Heterojunction annealing to promote interdiffusion was used for the highest performing sulfide kesterite device and air-annealing was reported important for selenium-rich record solar cells.

AbstractA surface treatment by evaporated selenium on Cu(In,Ga)Se2 (CIGS) is shown to improve open circuit voltage, Voc, and in some cases fill factor, FF, in solar cells with CdS, (Zn,Mg)O or Zn(O,S) buffer layers. Voc increases with increasing amount of crystalline Se, while FF improves only for small amounts. The improvements are counteracted by a decreasing short circuit current assigned to absorption in hexagonal Se. Improved efficiency is shown for device structures with (Zn,Mg)O and Zn(O,S) buffer layers by atomic layer deposition. Analysis by grazing incidence X‐ray diffraction and photoelectron spectroscopy show partial coverage of the CIGS surface by hexagonal selenium. The effects on device performance from replacing part of the CIGS/buffer interface area by a Se/buffer junction are discussed. Copyright © 2010 John Wiley & Sons, Ltd.

Photoluminescence (PL) is commonly used for investigations of Cu2ZnSnS(e)4 [CZTS(e)] and Cu(In,Ga)Se2 (CIGS) thin film solar cells. The influence of interference effects on these measurements is, however, largely overlooked in the community. Here, it is demonstrated that PL spectra of typical CZTS absorbers on Mo/glass substrates can be heavily distorted by interference effects. One reason for the pronounced interference in CZTS is the low reabsorption of the PL emission that typically occurs below the band gap. A similar situation occurs in band gap graded CIGS where the PL emission originates predominantly from the band gap minimum located at the notch region. Based on an optical model for interference effects of PL emitted from a thin film, several approaches to reduce the fringing are identified and tested experimentally. These approaches include the use of measured reflectance data, a calculated interference function, use of high angles of incidence during PL measurements as well as the measurement of polarized light near the Brewster angle.

ABSTRACTCu2ZnSnS4 (CZTS) is a promising thin‐film absorber material that presents some interesting challenges in fabrication when compared with Cu(In,Ga)Se2. We introduce a two‐step process for fabrication of CZTS films, involving reactive sputtering of a Cu‐Zn‐Sn‐S precursor followed by rapid annealing. X‐ray diffraction and Raman measurements of the sputtered precursor suggest that it is in a disordered, metastable CZTS phase, similar to the high‐temperature cubic modification reported for CZTS. A few minutes of annealing at 550 °C are sufficient to produce crystalline CZTS films with grain sizes in the micrometer range. The first reported device using this approach has an AM1.5 efficiency of 4.6%, with Jsc and Voc both appearing to be limited by interface recombination. Copyright © 2012 John Wiley & Sons, Ltd.

CdS is conventionally used as a buffer layer in Cu(In,Ga)Se2, CIGS, solar cells. The aim of this thesis is to substitute CdS with cadmium-free, more transparent and environmentally benign alternative buffer layers and to analyze how the material properties of alternative layers affect the solar cell performance. The alternative buffer layers have been deposited using Atomic Layer Deposition, ALD. A theoretical explanation for the success of CdS is that its conduction band, Ec, forms a small positive offset with that of CIGS. In one of the studies in this thesis the theory is tested experimentally by changing both the Ec position of the CIGS and of Zn(O,S) buffer layers through changing their gallium and sulfur contents respectively. Surprisingly, the top performing solar cells for all gallium contents have Zn(O,S) buffer layers with the same sulfur content and properties in spite of predicted unfavorable Ec offsets. An explanation is proposed based on observed non-homogenous composition in the buffer layer. This thesis also shows that the solar cell performance is strongly related to the resistivity of alternative buffer layers made of (Zn,Mg)O. A tentative explanation is that a high resistivity reduces the influence of shunt paths at the buffer layer/absorber interface. For devices in operation however, it seems beneficial to induce persistent photoconductivity, by light soaking, which can reduce the effective Ec barrier at the interface and thereby improve the fill factor of the solar cells. Zn-Sn-O is introduced as a new buffer layer in this thesis. The initial studies show that solar cells with Zn-Sn-O buffer layers have comparable performance to the CdS reference devices. While an intrinsic ZnO layer is required for a high reproducibility and performance of solar cells with CdS buffer layers it is shown in this thesis that it can be thinned if Zn(O,S) or omitted if (Zn,Mg)O buffer layers are used instead. As a result, a top conversion efficiency of 18.1 % was achieved with an (Zn,Mg)O buffer layer, a record for a cadmium and sulfur free CIGS solar cell.

To improve the conduction band alignment and explore the influence of the buffer-absorber interface, we here investigate an alternative buffer for Cu2ZnSnS4 (CZTS) solar cells. The Zn(O, S) system was chosen since the optimum conduction band alignment with CZTS is predicted to be achievable, by varying oxygen to sulfur ratio. Several sulfur to oxygen ratios were evaluated to find an appropriate conduction band offset. There is a clear trend in open-circuit voltage (Voc), with the highest values for the most sulfur rich buffer, before going to the blocking ZnS, whereas the fill factor peaks at a lower S content. The best alternative buffer cell in this series had an efficiency of 4.6% and the best CdS reference gave 7.3%. Extrapolating Voc values to 0 K gave activation energies well below the expected bandgap of 1.5 eV for CZTS, which indicate that recombination at the interface is dominating. However, it is clear that the values are affected by the change of buffer composition and that increasing sulfur content of the Zn(O, S) increases the activation energy for recombination. A series with varying CdS buffer thickness showed the expected behavior for short wavelengths in quantum efficiency measurements but the final variation in efficiency was small.

In this paper, co-evaporation of Cu(In,Ga)Se2 (CIGS) in an inline single-stage process is used to fabricate solar cell devices with up to 18.6% conversion efficiency using a CdS buffer layer and 18.2% using a Zn1-xSnxOy Cd-free buffer layer. Furthermore, a 15.6-cm2 mini-module, with 16.8% conversion efficiency, has been made with the same layer structure as the CdS baseline cells, showing that the uniformity is excellent. The cell results have been externally verified. The CIGS process is described in detail, and material characterization methods show that the CIGS layer exhibits a linear grading in the [Ga]/([Ga]+[In]) ratio, with an average [Ga]/([Ga]+[In]) value of 0.45. Standard processes for CdS as well as Cd-free alternative buffer layers are evaluated, and descriptions of the baseline process for the preparation of all other steps in the Angstrom Solar Center standard solar cell are given.