Optimisation of electrochemical sulphur treatment of GaSb and related semiconductors: application to surface passivation of GaSb/In(Al)GaAsSb TPV cells

Tadeusz T. Piotrowski 1Krystyna Golaszewska 1Ewa Papis 1Jaroslaw Rutkowski 2Renata Kruszka 1Jacek Szade 3Antoni Winiarski 3Anna Piotrowska 1

1. Institute of Electron Technology (ITE), al. Lotników 32/46, Warszawa 02-668, Poland
2. Military University of Technology, Institute of Applied Physics, ul. Kaliskiego 2, Warszawa 00-908, Poland
3. University of Silesia, August Chełkowski Institute of Physics, Department of Solid State Physics, Uniwersytecka 4, Katowice 40-007, Poland


GaSb and related quaternary semiconductors offer a great potential for application in mid-infrared photovoltaics (PV) and thermophotovoltaics (TPV). The implementation of these materials, however, has been hampered by an inability to reproducible control of their surface properties. The surface treatment in sulphur containing solutions has received much attention and was applied to the improvement of the GaSb-based photodiodes electro-optical parameters. Little was reported about long-term stability of GaSb-based TPV cells.

In this work we have used heterojunction photodiodes grown by liquid phase epitaxy (LPE) on (100) n‑GaSb:Te substrates. The mesa-type devices with mesa size of 500 µm × 500 µm were formed using photolithography and reactive ion etching in BCl3 plasma. AgTe/Cr/Au and Au/Zn/Au metallizations were applied for backside n-type and front p-type ohmic contacts, respectively. The contacts were alloyed in H2 at 250°C for 3 min. The processing of device structures was completed by surface passivation of mesa side-walls.

(NH4)2S, Na2S, and (NH2)2CS have been chosen as sulphur sources in either aqueous or C3H7OH solutions. Electrochemical processing has been carried out at the current density of 0.4 – 4 mA/cm2 for 15 - 30 min at room temperature. The parameters of electrochemical treatment – the current density and processing time - were optimised so as to fabricate the thickest possible overcoat with acceptable surface morphology (surface roughness below 10 nm). The passivating coatings obtained as a result of electrochemical sulphuration processes have been characterised by complementary use of Variable Angle Spectroscopic Ellipsometry (VASE), and X-ray Photoelectron Spectroscopy (XPS). The photodiode characterisation involved measurements of the current-voltage (I-V) characteristics, spectral response, and low frequency noise at 300 K. The I-V measurements were done using a computer controlled Keithley SourceMeter 2400 programmable meter. The relative photoresponse spectra were measured with a transimpedance amplifier coupled to a Fourier transform infrared (FTIR) spectrometer. Long-term performance under air exposure has been monitored within the time of 12 - 36 months, in 3-moths intervals.

The results of VASE analyses have proven insulating character of passivating coatings (ε2 = 0.014 and ε2 = 0.029 at 1.1 eV). The spectroscopic dependence of ellipsometric functions ψ(λ) and Δ(λ) of n-GaSb surface passivated in 21%(NH4)2S-H2O measured immediately after sulphur treatment and 3 years later were compared. No change of ellipsometric characteristics ψ(λ) and Δ(λ), has been observed which indicates on good stability of the coating.

The key parameters of passivated GaSb/In(Al)GaAsSb photodiodes were monitored during 12 months. It has been found that after 12 months exposure of the photodiodes to ambient environment, the electrical and optical characteristics are unchanged. The above result confirms the chemical stability of applied passivating coatings.

Part of the research was supported by the grant no. 3T11B 00926 from the Ministry of Education and Science, Poland.


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Presentation: Poster at Joint Fith International Conference on Solid State Crystals & Eighth Polish Conference on Crystal Growth, by Ewa Papis
See On-line Journal of Joint Fith International Conference on Solid State Crystals & Eighth Polish Conference on Crystal Growth

Submitted: 2007-01-16 15:16
Revised:   2009-06-07 00:44