Investigation of doped cuprous halides for photovoltaic and display applications
Vijayaraghavan, Rajani (2011) Investigation of doped cuprous halides for photovoltaic and display applications. PhD thesis, Dublin City University.
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The thesis mainly focuses on the growth and optoelectronic characterisation of the doped cuprous halides (CuX) with high UV/blue emission properties and the light harvesting in the CuBr/Si based heterojunction photovoltaic (PV) cells. Since cuprous halides are short wavelength emitters with high excitonic binding energies, growth of lower resistivity, highly luminescent p and n-type films are essential for the development of the future excitonic based light emitting devices with these materials. We describe the deposition and characterisation of the Zn doped n-type CuCl and oxygen doped p-type CuBr with higher carrier concentration using pulsed dc magnetron sputtering and thermal evaporation followed by oxygen plasma exposure, respectively.
The structural and morphological properties of the n-type Zn doped CuCl films are investigated using XRD, SEM and AFM measurements. Our findings show that, the crystallinity of CuCl increases with doping of Zn and the maximum is obtained for the 3 % doped film, beyond which crystallinity decreases. The Zn doping has no deleterious impact on the structural and luminescent properties of CuCl up to a doping percentage of 5. An order of magnitude reduction in the resistivity of the CuCl films is obtained as a result of Zn doping. The resistivity, n-type carrier concentration and carrier mobility corresponding to the 3 % Zn doped films were, respectively 6 Ωcm, ~ 9.8×1018 cm-3 and 0.1 cm2V-1s-1.
The influence of Zn doping on the electronic structure of CuCl is investigated using photoemission spectroscopic studies. Our studies on the Cu and Cl core level spectra show the presence of trace amounts of Cu2+ species in the undoped CuCl sample along with the major Cu+ species. This is verified by the observation of the satellite and shoulder peaks in the Cu 2p core level and a higher binding energy tail in the Cl 2p core level spectra. The disappearance of the cupric species with doping of Zn (3 %) is also observed. Furthermore, the shifting of the valence band towards the higher binding energy confirms the filling of the conduction band owing to the Zn doping, which explains the improvement of the conductivity of the doped films.
We have successfully deposited p-type CuBr films by doping of oxygen. Our findings show that, there is no significant influence on the structural properties of the CuBr up to an oxygen plasma exposure time of 5 min. The investigation of the optical properties confirms good luminescence of the CuBr films up to a plasma exposure time of 3 min. The electrical characterisations of the oxygen plasma exposed films reveal that, oxygen act as a good acceptor for CuBr. The resistivity of the 3 min oxygen plasma exposed samples reduces to the order of ~ 1 Ωcm. SIMS analysis shows that, the diffusion of oxygen is quite good in the CuBr films.
The realization of the heterojunction PV cell based on p-CuBr/n-Si is investigated. The I-V characteristics confirm the rectification behaviour of the p-n diode with a turn on voltage of ~ 1 V. The photoresponse properties of the heterojunction are studied by measuring the I-V characteristics under illumination. The photogenerated carrier formation is confirmed by the increased reverse current under illumination of the heterojunction. The wavelength dependence of the photo current was also studied using LED illumination.
Development of ultrathin transparent Cr contacts, useful for the electroluminescent device fabrication was also discussed. This can be used as an alternative to well-known Indium Tin Oxide films for the future fabrication of the CuX-based display devices.
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