ZnO Transparent conductive oxide for thin film silicon solar cells

There is general agreement that the future production of electric energy has to be renewable and sustainable in the long term. Photovoltaic (PV) is booming with more than 7GW produced in 2008 and will therefore play an important role in the future electricity supply mix. Currently, crystalline silicon (c-Si) dominates the market with a share of about 90%. Reducing the cost per watt peak and energy pay back time of PV was the major concern of the last decade and remains the main challenge today. For that, thin film silicon solar cells has a strong potential because it allies the strength of c-Si (i.e. durability, abundancy, non toxicity) together with reduced material usage, lower temperature processes and monolithic interconnection. One of the technological key points is the transparent conductive oxide (TCO) used for front contact, barrier layer or intermediate reflector. In this paper, we report on the versatility of ZnO grown by low pressure chemical vapor deposition (ZnO LP-CVD) and its application in thin film silicon solar cells. In particular, we focus on the transparency, the morphology of the textured surface and its effects on the light in-coupling for micromorph tandem cells in both the substrate (n-i-p) and superstrate (p-i-n) configurations. The stabilized efficiencies achieved in Neuchâtel are 11.2% and 9.8% for p-i-n (without ARC) and n-i-p (plastic substrate), respectively.

L'oxyde de zinc par dépôt chimique en phase vapeur comme contact électrique transparent et diffuseur de lumière pour les cellules solaires

Sylvie Faÿ

Zinc oxide (ZnO) is a material that belongs to the family of Transparent Conductives Oxides (TCO). Its non-toxicity and the abundant availability in the Earth's crust of its components make it an ideal candidate as electrical transparent contact for thin-film amorphous and/or microcrystalline silicon solar cells. The Low-Pressure Chemical Vapour Deposition (LP-CVD) method allows one to obtain rough ZnO layers, which can effectively scatter the light that passes through them. This high scattering capacity increases the path of the light within the solar cell and therefore enhances its probability to be absorbed by the solar cell, and consequently the photogenerated current. This thesis work studies in detail the LP-CVD technology used for deposition of ZnO layers, which are employed as TCO layers for amorphous, microcrystalline and "micromorph" (microcrystalline/amorphous tandem) solar cells developped at the Institute of Microtechnology of the University of Neuchâtel. The chapter 3 is a detailed study of the growth of ZnO layers on a glass substrate. This study reveals a columnar microstructure of the ZnO layers, which are composed of large conical monocrystals. The tops of these monocrystals emerge at the surface of the ZnO layers as pyramids, which give to such layers their rough aspect and therefore their capacity of scattering the light. The two following chapters represent a study of the effect of variations in deposition parameters on the optical properties (transparency and scattering power), electrical properties (conductivity), and structural properties of ZnO layers. The deposition parameters varied thereby are the various gas flows, the substrate temperature, and the process pressure. In particular, a strong influence of the substrate temperature on the microstructure of the ZnO layers is observed. A variation of ten degrees of this deposition temperature leads to abrupt variations of the optical and electrical properties of the layers. From these various studies, a strong correlation is established, between the scattering power, the electrical properties, and the microstructure of the ZnO layers deposited by LP-CVD: The higher the pyramidal grains at the surface of the layers, the higher the scattering capacity of these layers. The larger the monocrystals within the bulk of the layers, the higher the mobility of the free electrons. This enhanced mobility leads to an increase of the conductivity of the layers. Finally, the chapter 6 of this thesis work describes the various situations where LP-CVD ZnO layers are used as transparent electrical contacts and light scattering layers in thin-film silicon solar cells. It is schown that, by incorporating ZnO layers developped in this work in the photovoltaic devices, an increase of 8% in the photogenerated current is obtained, compared to the performances of solar cells using standard commercially available TCO.

EPFL2003

Explaining Morphological and Electrical Features of Boron-doped Zinc Oxide to Tailor New Electrodes for Photovoltaics

Lorenzo Fanni

TCOs are a class of metal oxides that combine transparency to visible light with electrical conductivity. Each TCO is characterized by the trade-off of these two properties which can be tuned for a particular application. This thesis is dedicated to the investigation of one TCO material: boron doped zinc oxide (ZnO:B) deposited by low-pressure chemical vapor deposition (LP-MOCVD). Its main distinction is low absorptance which makes ZnO films deposited by LP-MOCVD ideal as transparent electrodes in thin-film solar cells. Although ZnO:B properties have previously been optimized for this application, the exact processes behind the film formation have not been fully described. This thesis substantially clarifies the processes of the film nucleation and growth evolution, and the mechanisms of incorporation of the B atoms into the ZnO. First, for non-intentionally doped ZnO we establish that the main deposition parameters influencing the film properties are the deposition temperature, the gas precursor ratio and the total gas flow. We experimented with these three parameters across a wide range of parameter values. The films deposited were characterized at different stages of their growth using atomic force microscopy, X-ray diffraction and automated crystallographic orientation mapping. These data reveal the dependence of the film preferential orientation on the deposition conditions. We propose a model based on the adsorbed atom mean free path to explain this dependence. Using deposition parameters learnt from this model, we control the preferential orientation during film growth to increase the grain sizes. Second, we analyze the conductivity to B-doped ZnO films. Boron atoms act as electron donors in ZnO, increasing the electrical conductivity and decreasing the transparency. This work quantifies how the B concentration and spatial distribution affect the film conductivity. Quantification of the B atoms incorporated in the film was performed using nuclear reaction analysis. We found that a high level of O precursor gas favors B incorporation in the film. Combining nano secondary ion mass spectroscopy and Kelvin probe force microscopy we demonstrate that the dopant atoms incorporate in only one of the two sides of each grain. This is a new observation because dopant atoms are commonly assumed to be uniformly distributed in the film. The transparency and electrical conductivity of ZnO depend also on the carrier mobility. The sources of carrier scattering are investigated for intrinsic (i.e. O vacancies and Zn interstitials) and extrinsic (B atoms) impurity concentrations. We observed that for the same B concentration the source of electron scattering depends on the concentration of intrinsic defects: for films with a lower concentration of intrinsic defects, the main source of scattering is the grain boundaries; for films with a higher concentration of intrinsic defects, the main sources are the mechanisms happening in the crystalline region. Finally, LP-MOCVD ZnO:B films were optimized using the previous results and successfully applied in four different types of solar cells: amorphous/microcrystalline silicon, amorphous silicon, copper indium gallium selenide and silicon heterojunction. The advantages of the developed films to these four cells include the simplification of the fabrication process, the reduction of reflectance and parasitic absorption, and a better understanding of carrier transport mechanisms through the device.

EPFL2016

Low pressure chemical vapour deposition of ZnO layers for thin-film solar cells: Temperature-induced morphological changes

Cédric Bucher, Sylvie Faÿ, Arvind Shah

Zinc oxide (ZnO) is now often used as a transparent conductive oxide for contacts in thin-film silicon solar cells. This paper presents a study of ZnO material deposited by the low-pressure chemical vapour deposition technique, in a pressure range below the pressures usually applied for the deposition of this kind of material. A temperature series has been deposited, showing a morphological transition around 150 °C. ZnO samples deposited with temperatures just higher than this transition are constituted of large grains highly oriented along a single crystallographic orientation. These "monocrystals" lead to low resistivity values, showing a clear correlation between the size of the surface grains and the electrical performance of corresponding films. Additionally, these large grains also yield ZnO layers with high transparency and high light-scattering power, specially suitable for solar cell technology based on thin-film silicon. © 2004 Elsevier B.V. All rights reserved.