Tobias Törndahl

Zn(O,S) buffer layers by atomic layer deposition in Cu(In,Ga)Se2 based thin film solar cells: Band alignment and sulfur gradient

Thin film solar cells with the structure sodalimeglass∕Mo∕Cu(In,Ga)Se2∕Zn(O,S)∕ZnO∕ZnO:Al are studied for varying thickness and sulfur content of the Zn(O,S) buffer layer. These Zn(O,S) layers were deposited by atomic layer deposition (ALD) at 120°C. Devices with no or small concentrations of sulfur in the buffer layer show low open-circuit voltages. This is explained by the cliff, or negative conduction-band offset (CBO), of −0.2eV measured by photoelectron spectroscopy (PES) and optical methods for the Cu(In,Ga)Se2 (CIGS)∕ZnO interface. Devices with ZnS buffer layers exhibit very low photocurrent. This is expected from the large positive CBO (spike) of 1.2eV measured for the CIGS∕ZnS interface. For devices with Zn(O,S) buffer layers, two different deposition recipes were found to yield devices with efficiencies equal to or above reference devices in which standard CdS buffer layers were used; ultrathin Zn(O,S) layers with S∕Zn ratios of 0.8–0.9, and Zn(O,S) layers of around 30nm with average S∕Zn ratios...

Inline Cu(In,Ga)Se

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 Ångström Solar Center standard solar cell are given.

_{2}

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.

Co-evaporation for High-Efficiency Solar Cells and Modules

Cu2ZnSnS4 (CZTS) solar cells typically include a CdS buffer layer in between the CZTS and ZnO front contact. For sulfide CZTS, with a bandgap around 1.5 eV, the band alignment between CZTS and CdS ...

Zn(O, S) Buffer Layers and Thickness Variations of CdS Buffer for Cu

Zinc tin oxide (Zn(1-x)Sn(x)O(y)) has been proposed as an alternative buffer layer material to the toxic, and light narrow-bandgap CdS layer in CuIn(1-x),Ga(x)Se(2) thin film solar cell modules. In this present study, synchrotron-based soft X-ray absorption and emission spectroscopies have been employed to probe the densities of states of intrinsic ZnO, Zn(1-x)Sn(x)O(y) and SnO(x) thin films grown by atomic layer deposition. A distinct variation in the bandgap is observed with increasing Sn concentration, which has been confirmed independently by combined ellipsometry-reflectometry measurements. These data correlate directly to the open circuit potentials of corresponding solar cells, indicating that the buffer layer composition is associated with a modification of the band discontinuity at the CIGS interface. Resonantly excited emission spectra, which express the admixture of unoccupied O 2p with Zn 3d, 4s, and 4p states, reveal a strong suppression in the hybridization between the O 2p conduction band and the Zn 3d valence band with increasing Sn concentration.

_{2}

Films of copper(I) nitride were deposited by atomic layer deposition (ALD) using copper(II) hexafluoroacetylacetonate, water, and ammonia as precursors. Introduction of a water pulse in the ALD cycle was found to be crucial for initiating film growth on both amorphous SiO 2 and single-crystalline α-Al 2 O 3 (001) substrates. The water pulses generated an oxidic copper monolayer, which in a subsequent ammonia pulse was converted to the nitride. The films have been grown in the temperature range from 210 to 302°C. Phase pure films of Cu 3 N were obtained up to 265°C. At higher deposition temperatures such as 283°C, phase mixtures of Cu 3 N and Cu were obtained. For temperatures above 302°C films of only Cu were grown. Film growth rate was the same on the two different substrates. The films were randomly oriented on SiO 2 . Completely intact films were obtained at a thickness of 20 nm. The optical bandgap of the films was measured to be 1.6 eV.

ZnSnS

This study investigates the interplay between the absorber layer of Cu(In,Ga)Se2 solar cells and the other layers of these devices. Cu(In,Ga)Se2 devices with absorbers of different thicknesses and different buffer layers are fabricated. Absorber layers and finished devices are characterized. Good efficiencies are obtained, also for devices of substandard thickness down to 0.3 μm. Best open-circuit voltages and fill factors are found for cells with half the standard absorber thickness, but the highest efficiencies are found for cells with the standard thickness of 1.6 μm due to their higher short-circuit current density. Cu(In,Ga)Se2 cells with Zn(O,S) buffer layers are more efficient than CdS reference devices for the same absorber thickness due to a higher short-circuit current. For cells with thin absorber layers, a part of the higher current is caused by higher quantum efficiency at long wavelengths. Electrical simulations indicate that the loss in the open-circuit voltage for the thinnest devices is due to recombination in the back contact region. The difference in long-wavelength quantum efficiency between the buffer layers is attributed to a difference in the CIGS band bending. Acceptors at the Cu(In,Ga)Se2-CdS interface are proposed as an explanation for this difference. A low-quality back contact region enhances the effect.

_{4}

Cu(In,Ga)Se2 thin-film solar cells with Ga-graded absorber layers and a [Cu]/([In] + [Ga]) ratio varying between 0.5 and 1.0 were prepared by coevaporation and investigated. Except for the sample with a final [Cu]/([In] + [Ga]) ratio of 1.0, the samples were Cu-poor at all times during the evaporation. The variation in copper was found to influence the material properties in several ways: 1) Changing the Cu content had a strong impact on In and Ga interdiffusion, resulting in decreased Ga gradients in samples with large Cu deficiency; 2) the Cu-poor Cu(In,Ga)3Se5 phase was detected in absorbers with [Cu]/([In] + [Ga]) ratios of 0.65 and below; and 3) the grain size changed significantly with the Cu variation. We observe a trend of reduced solar cell efficiencies for [Cu]/([In] + [Ga]) ratios of 0.65 and below, with an efficiency of 13.4% for the sample with a [Cu]/([In] + [Ga]) ratio of only 0.5, i.e., far from stoichiometry. We tentatively attribute the efficiency loss to a high concentration of point defects caused by the Cu deficiency.

Solar Cells

Aluminum nitride thin films were deposited by reactive high power impulse magnetron sputtering (HiPIMS) and pulsed direct-current on Si (100) and textured Mo substrates, where the same deposition conditions were used for both techniques. The films were characterized by x-ray diffraction and atomic force microscopy. The results show a pronounced improvement in the AlN crystalline texture for all films deposited by HiPIMS on Si. Already at room temperature, the HiPIMS films exhibited a strong preferred (002) orientation and at 400 °C, no contributions from other orientations were detected. Despite the low film thickness of only 200 nm, an ω-scan full width at half maximum value of 5.1° was achieved on Si. The results are attributed to the high ionization of sputtered material achieved in HiPIMS. On textured Mo, there was no significant difference between the deposition techniques.

Reduced interface recombination in Cu2ZnSnS4 solar cells with atomic layer deposition Zn1−xSnxOy buffer layers

ZnO-based compounds are of interest as buffer layers in Cu(In,Ga)Se2 (CIGS) solar cells, due to the ability to change the electrical and optical properties of ZnO by addition of other elements. The device structure of a CIGS solar cell is; soda-lime glass/Mo/CIGS/buffer layer/ZnO/ZnO:Al. This contribution treats growth and characterization of Zn1-xMgxO and Zn(O,S) on glass substrates and as buffer layers in CIGS solar cell devices. The ZnO-based compounds are grown by atomic layer deposition at deposition temperatures below 200 °C using metal-organic precursors.