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Abstract
We report on the basic properties of amorphous/crystalline hetero-junctions (a-Si:H/c-Si), their effects on the recombination of excess carriers
and its influence on the a-Si:H/c-Si hetero-junction solar cells. For that purpose we measured the gap state density distribution of thin a-Si:H layers
and determined its dependence on deposition temperature and doping by an improved version of near-UV-photoelectron spectroscopy.
Furthermore, the Fermi level position in the a-Si:H and the valence band offset were directly measured. In combination with interface sensitive
methods such as surface photovoltage analysis and our numerical simulation program AFORS-HET, we found an optimum in wafer pretreatment,
doping and deposition temperature for efficient a-Si:H/c-Si solar cells without an i-type a-Si:H buffer layer. We reached at maximum 19.8%
certified efficiency by a deposition at 210 C with an emitter doping of 2000 ppm of B2H6 on a well cleaned pyramidally structured c-Si(n) wafer.
2006 Elsevier B.V. All rights reserved.
Fig. 1. Band scheme of the a-Si:H/c-Si hetero-junction embedded into a 2.3. Electronic properties of thin a-Si:H layers
complete TCO/a-Si:H(n+)/c-Si(p)/a-Si:H(p+) solar cell structure. The symbols
are explained in the text.
The a-Si:H layer thickness d shows an optimum at about
5 nm b d 10 nm for application as an emitter. This follows from
wafers with randomly distributed upside pyramids are used to the experimental results of solar cell performance in [3,9] and
optimize the light trapping properties. our numerical simulations of the open circuit voltage VOC(d) and
Non-destructive and surface sensitive techniques such as the the short circuit current values ISC(d). Such layer thicknesses
large-signal field-modulated surface photovoltage (SPV) method correspond to a sequence of about 2040 SiSi bonding lengths.
[6] and spectroscopic ellipsometry (SE) [7] have been utilized to For such extremely thin layers we have to determine the Fermi
investigate the relation between structural imperfections at silicon level position, the gap state density distribution N(E) and the
surfaces, interface state densities and stability of surface passiv- band offsets with the adjacent crystalline silicon.
ation. Both, the density of surface states on H-terminated surfaces An adequate method for measuring the electronic structure of
and the stability against native oxidation in clean-room air were the 510 nm thin a-Si:H emitter is photoelectron spectroscopy
found to be strongly related to the interface micro-roughness [8]. excited by near-ultraviolet light, NUV-PES [4,1013]. The
After RCA cleaning, a high density of surface states Dit(E) was NUV-excitation leads to an increased electron escape depth of
observed. Conventional HF treatment (HF-dip) reduces the surface up to 10 nm. This is attributed to the absence of surface or bulk
state density, as shown in Fig. 2. The density of rechargeable plasmon generation, which would need energies of about 10 eV.
surface states can be further reduced by preparing atomically flat This is well above the UV excitation energies of h = 38 eV.
and well-ordered silicon surfaces through the application of special
hot water oxidation and H-termination procedures. It was shown
that the ideally H-terminated surface is characterized by a very low
density of surface states [8] which are in shape and quantity com-
parable to well thermally oxidized surfaces.
The densities of interface states on the initially H-terminated
silicon surfaces were found to increase drastically during the first
monolayer of oxide growth. The duration of the initial phase of
oxidation in air ranges from a couple of minutes on HF-treated
surfaces up to some hours on conventionally H-terminated surfa-
ces and Si (100) substrates. Highest stabilities in clean-room air
with initial phases up to 48 h have been found on Si (111) after
applying a special H-termination procedure. Further on, it was
shown that by storage in dry nitrogen atmosphere, the re-oxidation
of H-terminated surfaces can be decelerated, but not completely
prevented because of reactions with moisture adsorbates. Conse-
quently, the time between surface cleaning, smoothing, H-passi-
vation and the a-Si:H deposition has to be as short as possible.
Fig. 7. Decay of VSPV over time for 10 nm thick a-Si:H(i) on c-Si(p, (111))
prepared at different deposition temperatures. The measurements were
performed at room temperature. The dotted straight line marks the maximum
Fig. 5. Calculated dependence of a-Si:H(n)/c-Si(p) solar cell efficiency on the of detected photovoltage of 600 mV, which corresponds to the initial band
minority charge carrier band offset with a variation of interface state density Dit bending in c-Si.
as parameter (given in the inset). The rear side recombination velocity was set to
107 cm/s and LD = 400 m.
surface photovoltage of the sample is measured capacitively via
interface recombination as expected from Fig. 5 and shown by the insulating slab as photovoltage pulse VSPV. The sample is
corresponding calculations in [9]. illuminated at a photon energy smaller than the band gap of a-Si:H
This emphasizes that recombination at the amorphous/ (1.7 eV). Thus, the latter acts as an additional window layer, the
crystalline silicon interface is one key parameter, that can excitation of charge carriers takes place in the crystalline substrate
reduce the solar cell performance of TCO/a-Si:H/c-Si solar cells and their main recombination path is via the defect states at the a-
significantly. Si:H/c-Si interface. From measurements of VSPV depending on
In order to study the band bending, interface state densities and the external field, the distribution Dit of a-Si:H/c-Si interface gap
effective interface recombination excess charge carriers are opti- states can be calculated [6]. The precondition is that no change of
cally generated in the c-Si absorber of Si/SiO2 and a-Si:H/c-Si the a-Si:H charge state and of the interface states takes place
hetero-structures and the surface photovoltage method (SPV) and during the light pulse. The results of such investigations are
photoluminescence measurements (PL) were applied. shown in Figs. 2 and 6.
In SPV measurements, the sample under test is sandwiched in A comparison of the Dit(E) spectra of Si/SiO2 (thermally
a structure consisting of a transparent conductive front contact grown at 1100 C in dry O2 followed by forming gas annealing)
(TCO), an insulating slab of mica, the sample and a metallic back with the a-Si:H(i)/c-Si hetero-junction shows a similar distri-
contact. Thus, an artificial metal-insulator-semiconductor (MIS) bution and a low quantitative difference. The SPV measure-
structure is created. Upon intense illumination of the sample by a ments have been carried out for i-type a-Si:H layers on c-Si
laser pulse (hV = 1.35 eV, pulse duration 160 ns, intensity 1019 because only undoped layers allow the modulation of band
photons/(cm2 s)) through the TCO, excess charge carriers are bending in c-Si by an external field. Deep temperatures were
generated in the c-Si, leading to a flattening of the bands and a needed (120 K) to suppress recharging effects of the a-Si:H
split-up of the quasi-Fermi levels of electrons and holes. The during the laser pulse excitation. This effect can still not be
completely excluded, so that the measured Dit(E) spectrum
gives an upper limit of the true interface state distribution,
solar cell structure, TCO/a-Si:H(p)/c-Si(n)/a-Si:H(n+), we obtain at [3] M. Taguchi, A. Terakawa, E. Maruyama, M. Tanaka, Prog. Photovolt. Res.
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3. Conclusion [5] R. Stangl, A. Froitzheim, M. Schmidt, W. Fuhs, Proc. of the 3rd WCPEC,
Osaka, Japan, May 1118, 2003, p. 45.
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model system of silicon based hetero-junctions. For the appli- [8] H. Angermann, W. Henrion, M. Rebien, A. Rseler, Appl. Surf. Sci. 235
cation of this structure in solar cells we obtained valuable hints on (2004) 322.
the most relevant parameters. If we compare the calculated with [9] A. Froitzheim, PhD thesis, Hetero-Solarzellen aus amorphem und
the measured data we notice that there exists a potential for kristallinem Silizium, Philipps-Universitt Marburg (2003).
improving the solar cell efficiency further, predominantly by [10] K. Winer, L. Ley, Phys. Rev., B 36 (1987) 6072.
[11] L.D. Sebastiani, Gaspare, G. Capellini, C. Bittencourt, F. Evangelisti,
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plasma post-treatment and annealing processes as well as [12] L. Korte, PhD thesis, Die elektronische Struktur des amorph-kristallinen
modifications of the wafer pre-cleaning procedure are under way. Silizium-Heterostruktur-Kontakts, Philipps-Universitt Marburg (2006).
[13] W.B. Jackson, S.-J. Oh, C.C. Tsai, J.W. Allen, Phys. Rev. Lett. 53 (1984)
Acknowledgements 1481.
[14] A. Laades, PhD thesis, Preparation and Characterization of Amorphous/
Crystalline Silicon Heterojunctions, Technische Universitt Berlin (2005).
This work was financially supported by the German [15] A. Laades, K. Kliefoth, L. Korte, K. Brendel, R. Stangl, M. Schmidt, W.
Bundesministerium fr Bildung und Forschung, contract Fuhs, Proc. of the 19th EPVSEC, Paris, France, June 711, 2004, p. 1170.
number 01SF0012. The authors would like to thank K. Jacob, [16] S. Dauwe, J. Schmidt, R. Hezel, Proc. of the 29st IEEE PVSEC, New
C. Klimm, T. Lussky and D. Patzek for technical support. Orleans, USA, May 2024, 2002, p. 1246.
[17] L. Korte, A. Laades, M. Schmidt, J. Non-Cryst. Solids 352 (2006) 1217.
[18] K.v. Maydell, J. Schmidt, M. Scherff, W. Fahrner, H. Windgassen, W.A.
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