20th European Photovoltaic Solar Energy Conference, 6-10 June 2005, Barcelona, Spain

ELECTRICAL AND OPTICAL CHARACTERIZATION OF PASSIVATION LAYERS UNDER UV LIGHT SOAKING FOR CONCENTRATED PHOTOVOLTAIC APPLICATIONS Luca Serenelli1, Simona De Iuliis1, Massimo Izzi1, Giuseppe Arabito1, Mario Tucci1 Domenico Caputo2, Giampiero de Cesare2, Augusto Nascetti2 1 Enea Research Center Casaccia Via Anguillarese, 301 00060 S. Maria di Galeria Roma Italy 2 Department of Electronic Engineering University La Sapienza Via Eudossiana 18 Rome 00139 Italy ABSTRACT: In this paper we present an investigation of solar cells under UV light soaking. Those cells are made starting from a FZ 0.3 cm silicon wafer commonly adopted for concentrated sunlight applications. During the UV exposure we have found different behaviors depending on the passivation used on the emitter layer. In particular we compare the passivation obtained by a double layer of thermal silicon oxide and a PECVD silicon nitride with the passivation of a single layer of silicon nitride. This layer has been also used as antireflection coating. To get more details about the effective of passivation and the interface density of states between the insulator layers and the silicon substrate, lifetime has been evaluated during UV light soaking and finally capacitance-voltage measurement at different frequencies have been performed on MIS devices growth on similar p-type FZ silicon wafer having the same passivation layers as the investigated solar cells. Keywords: Silicon-nitride-1, solar cell-2, capacitance-3, defect density-4. 1. INTRODUCTION A key point in achieving high efficiency solar cells is the passivation of both front and bottom of the cell surfaces in order to reduce surface recombination losses as much as possible. This reduction becomes more relevant when the device is exposed to high concentrated sunlight. In this case, high cost technological steps, such as point rear contacts or particular pattern of front passivation layer before front metal grid realization, can be introduced in the fabrication process to obtain high photovoltaic conversion efficiency. A significant reduction of the process complexity can be obtained by replacing the high temperature step (deposition of SiO2 layer is at 900C) with a low temperature (<400C) plasma enhanced chemical vapor deposition (PECVD) of a silicon nitride (SiNx) layer. The goal of low process temperature is enhanced by an high atomic hydrogen content in the film, which can saturate silicon dangling bonds at the surface, and by a high density of positive fixed charge, which can create a repulsion field effect for minority carriers from recombination centers at the surface [1]. In recent years, a significant improvement of passivation quality of silicon nitride films has been achieved [2, 3] together with an improved antireflection function by adjusting its refractive index in the 1.9-2.3 range [4]. Silicon nitride has also application as back surface passivation on p-type silicon, especially for thin (100 to 300 m) solar cells, with effects comparable with BSF [5]. However, for both materials modification of electrical and optical characteristics under concentrated sunlight exposure due to UV region of the impinging spectrum have been observed [6]. In this work we investigate the effect of UV light soaking on solar cell designed for concentrated sun light applications, in which the front surface passivation is ensured in two different ways: by a thin SiO2 and a SiNx layers and by a SiNx layers only. The silicon nitride has been also used as antireflection layer for both kind of cell. To get more inside the effect of UV light exposure we also monitor the effective lifetimes of the same substrate of the solar cells passivated by SiO2 and/or SiNx. Finally we compare the capacitance of MIS structures Al/SiNx/SiO2/pSi/Al and Al/SiNx/pSi/Al realized on the same FZ silicon substrates before and after UV light soaking.

2. EXPERIMENTAL DETAILS The UV light has been obtained by filtering a 30 W deuterium lamp up to 330 nm and focusing that UV light to obtain a density of 500 W/cm2. With this radiation we have light soaked several solar cells based on 250 m thick Floating Zone 0.3 cm p-type <100> mono-crystalline silicon. After wafer cleaning procedure a n+ type emitter layer has been obtained on the flat side of the wafer with a diffusion step at 850C for 30 min starting with POCl3 gas mixture and subsequent performing a drive-in process at 940 C for 90 min. SIMS profile carried out on the n-p junction have ensured a gaussian doping distribution with a peak of 51019 and the n+ deepness of 1m from the surface of the wafer. On this emitter a 16 nm thick dry thermal oxide has been growth in order to passivate the silicon surface. We have verified the oxide thickness by a ellipsometric instrument. The back contact of the cell has been realized by a e-beam evaporation of 2 m Al layer annealed at 550 C for 20 min. No back surface field has been still imposed. The front contact has been realized by an e-beam evaporation of a tri-layer of Ti (50 nm), Pd (50 nm), Ag (2 m) on which a grid shape for the impinging light has been obtained by lift-off process. Finally a 15 m deep trench has been formed by a wet chemical etch around the perimeter of the cell to fix the total area of device to 1.21 cm2. At this stage we divide the solar cells into two kind the first as described above and the second has been obtained by removing the thermal oxide dipping the cells in a 1% HF bath. Then a silicon nitride layer has been

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20th European Photovoltaic Solar Energy Conference, 6-10 June 2005, Barcelona, Spain

deposited on the top of all the cells by direct parallel plate High Frequency (13.56 MHz) PECVD system with the following recipe. The reactants are silane (5% diluted in Argon) and ammonia, with gas ratio R = ?NH3)/?SiH4) = 1.6 . The deposition temperature is 300 C, the plasma power density 31 mW/ cm2 and the pressure has been fixed to 750 mTorr. A thickness layer of 70 nm, which gives an effective reflectance of about 13% on polished FZ silicon, with refractive index (measured by ellipsometry method) of 1.91 has been obtained. This thickness has been chosen as the best compromise of passivation and antireflection properties verified on polished 0.3 cm FZ p-type silicon wafer. Those cells have been characterized by I-V curves in AM1.5G, in dark conditions and by external quantum efficiency (QE) at different stages of the UV light soaking.In order to evaluate the UV light soaking effect on the silicon passivation we have deposited the above reported silicon nitride layer on both sides of FZ silicon ptype crystalline silicon wafers, several covered by 16 nm dry thermal oxide, others not. Then we have monitored the effective lifetime of these passivated silicon wafer in WTC100 tester at different time of UV light exposure. Moreover the density of states of the insulator\silicon interfaces have been extracted from capacitance-voltage measurement (CV) at different frequencies performed on MIS devices growth on similar p-type FZ silicon wafer having as insulator the same passivation layers as the above solar cells layer and a aluminum evaporated as metal contact both for front dot and rear of the MIS device. Those devices have been realized both before and after the UV light exposure of the insulator\silicon and the results have been compared on the basis of commonly adopted models reported in literature [7]. In order to better evaluate the status of the passivation on the top of the emitter of the solar cell described above, we have finally evaluated the C-V characteristics of an Al/SiNx/SiO2/n+-Si MIS text structure built on the emitter of the described solar cells. 3. RESULTS AND DISCUSSION

light soaked stage (0), as reported in Figure 3 (case of SiNx/SiO2/Si/SiO2/SiNx structure). Sample
A B C D E F

Passivation
SiNx/SiO2/Si p SiNx/SiO2/Si p 20h UV SiNx /Si p SiNx /Si p 20h UV SiNx/SiO2/Si n+ SiNx/SiO2/Si n+ 65h UV

VFB
(V) -2 -5 -31 -31.5 2 -34

(cm-2) 3.361011 1.611012 1.111013 1.201013 -1.41012 1.381013

Qox/q

(cm-2eV-1) 4.61012 6.11012 2.11013 2.21013

Dit

Table I. Fixed charge density and interface state density for MIS capacitors before and after 20 hours UV light soaking.
1.0 0.9 0.8 C/Cox 0.7 0.6 0.5 0.4 -10.0 -7.5 -5.0 -2.5 Voltage (V) 0.0 2.5 5.0
A B

Figure 1 Normalized C-V characteristics at high frequency (10KHz) of MIS samples A and B of Table I after and before 20 hours of UV light exposure.
1.0

During the plasma deposition process many traps have been induced at interface with the silicon wafer, but simultaneously passivated by hydrogen originating in the silicon nitride layer. These latent states can be activated by UV radiation with photon energies much lower than the bandgap energy of SiO2. These optically generated interface states due to breaking of Si-H bonds at SiO2/Si interface assume a donor like behavior. In Figure 1 we report the C-V curves of MIS structure in which the insulator is composed by both of SiNx and SiO2 layers. For the sake of clarity only the 10KHz curves are reported, since changing frequency no variation in the capacitance values occurs. After 20 hours of UV light soaking a shift in flat-band voltage (VFB) from 2V down to 5V is evident and is due to increment of fixed positive charge, as reported in Table I in terms of Qox/q as well as Dit for the samples A and B. This effect promotes a shift of Fermi levels toward mid-gap at the edge of p-type silicon wafer resulting in a higher recombination at interface and then a lowering of lifetime () with respect to the not UV

0.8 0.6 0.4 0.2 -40

C/Cox

C 0.1 kHz C 10 kHz D 0.1 kHz D 10 kHz

-35

-30

-25

-20

-15

-10

-5

Voltage (V) Figure 2 Normalized C-V characteristics at different frequencies (100Hz-10KHz) of MIS samples C and D of Table I after and before 20 hours of UV light exposure.

When the silicon nitride has been directly deposited on the p-type silicon surface the flat-band voltage greatly shifts

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toward high negative value. After 20 hours UV light soaking the flat-band voltage does not shift lower, leaving the number of fixed charges almost unchanged (as reported in Table I for the sample C and D). Moreover a tendency to easy create an inversion layer is evident again due to an increase of positive charge inside insulator. Whether an inversion layer (from p to n) has been induced close to the p-type silicon surface a shift of Fermi level toward conduction band has been produced, resulting in a reduced recombination at SiNx/Si interface. Therefore the effective lifetime () of SiNx/Si/SiNx sample can assume higher value with respect to the not UV light soaked stage (0), as reported in Figure 3. This figure also points out the stability of the induced fixed charges at interface near crystalline silicon also after prolonged UV exposition, indeed saturation of has been reached after few hours of light soaking.
2.25 2.00 1.75 1.50
/0

and B in Table I reported in the previous paragraph.

10 10
0 -1

Current density (mA/cm )

10 10 10 10 10 10 10

-2

-3

621-3 before SiNx 621-3 SiNx/n-si before UV 621-3 SiNx/n-si UV enhanc. 621-4 before SiNx 621-4 SiNx/SiO2/n-si UV enhanc. 621-4 SiNx/SiO2/n-si before UV

-4

-5

-6

-7

-8

10

-9

-1.0

-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

Voltage (V)

Figure 4 Dark current-voltage characteristics of solar cells passivated by SiNx/SiO2 (621-4) and by SiNx (621-3) before and after UV light soaking. From the I-V characteristics under AM1.5G taken at different stage of UV light soaking we have found, despite to the literature [6], a surprising increase of photovoltaic efficiencies in both kind of solar cells. Sample 621-4, having a SiO2 buffer layer, have sowed an enhancement of both Voc and Jsc values. Sample 621-3, having only SiNx, has demonstrated an enhancement of fill factor.
1.16 1.020 1.016 1.012
Voc/Voc0

1.25 1.00 0.75 0.50 0.25 0 2 4 6

SiNx/ p-Si / SiNx SiNx/ SiO2/ p-Si / SiO2/ SiNx

10 12 14 16 18 20

Time (hours)

1.14 1.12 1.10 Voc/Voc0 621-4 SiNx/SiO2/n-si Jsc/Jsc0 621-4 SiNx/SiO2/n-si Voc/Voc0 621-3 SiNx/n-si Jsc/Jsc0 621-3 SiNx/n-si 1.08 1.06 1.04 1.02 1.00
0.98 1.14
Jsc/Jsc0

Figure 3 Normalized lifetime of FZ silicon wafers passivated at both sides by SiNx/SiO2 or SiNx at different time of UV light exposure. Solar cells 621-4 621-4 621-3 621-3 Passivation SiO2/Si SiNx/SiO2/Si Si SiNx/Si VOC JSC (mV) (mA/cm2) 615 21.4 618 29.29 609 627 20.58 32.72 FF % 80 81.3 81.5 75.8 EFF % 10.5 14.7 10.2 15.5

1.008 1.004 1.000 0.996

1.05 1.04 1.03

FF/FF0

Table II. Photovoltaic parameters of the samples before and after silicon nitride deposition. Even if that silicon nitride can produce a good increment of Voc, as clear from photovoltaic parameters of sample 621-3 showed in Table II, still produces strong damages as evident from the current voltage characteristics performed in dark and room temperature conditions of the 621-3 sample reported in Figure 4. Indeed sample 621-3, realized without SiO2 buffer layer, show strong recombination after SiNx deposition due to hydrogen diffusion toward the junction during decomposition of silane during plasma process [8]. Then we deduce that the thin SiO2 layer works as a barrier against hydrogen diffusion toward the junction reducing the recombination process (as evident from the dark I-V of 6214 sample) and producing in higher photovoltaic performances. This results can be comparable to the difference in the density of interface states Dit of sample A

1.12 1.10 FF/FF0 621-4 SiNx/SiO2/n-si Eff/Eff0 621-4 SiNx/SiO2/n-si 1.08 FF/FF0 SiNx/n-si 1.06 Eff/Eff0 621-3 SiNx/n-si 1.04 1.02

Eff/Eff0

1.02 1.01 1.00 -20 0 20 40

1.00
60 80 100 120 140 160

Time (hours)

Figure 5 Normalized photovoltaic parameters of solar cells passivated by SiNx/SiO2 (621-4) and by SiNx (621-3) at different time of UV light exposure.

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20th European Photovoltaic Solar Energy Conference, 6-10 June 2005, Barcelona, Spain

We can explain these effects again in terms of positive fixed charges induced by UV exposure at insulator/semiconductor interface that promote electron migration inside n emitter layer toward the passivation layer. The accumulation of electrons close to the surface produces a shift of the Fermi level to the conduction band edge, reducing the surface recombination of the minority carriers. We have found also evidence of this effect looking at the dark I-V measurements. In particular we point out a reduction of recombination mechanism in the depletion region in the sample 621-3. This reduction reflects into an increment of the fill factor of the cell. On the other side the shifts of the Fermi near the conduction band enhances both the built-in potential and the electric field at the junction. Then a better collection of photo-generated charges has been obtained. This is more efficient for the carriers generated near the depletion region as evident by the Quantum Efficiency measurements in the blue region of the sun spectra. The relative increment of QE after UV light soaking with respect to the QE0 evaluated before the UV exposure is reported in Figure 6. Of course sample 621-4, that has a SiO2 buffer layer, shows better performances. In this sample photovoltaic parameters seems to be almost constant also after prolonged UV exposure confirming a stability of the induced charge inside the insulator. In order to finally verify our statements about the passivation effect of both SiNx and SiO2 layers on the emitter of the solar cell we have grown a MIS structure on the top of a solar cell as depicted in the inset of figure 7. We have found that when the MIS is not UV light soaked negative charges lay inside the insulator, as deduced from flat-band voltage. After 65 hours of UV light exposure s a strong shift in the flat-band voltage occurs, confirming the creation of positive charge inside the insulator that increase the majority carriers migration toward the SiO2/n+ Si interface. This also reduces the possibility to deplete the n+ layer of MIS structure, resulting in higher capacitance value when the MIS reaches the depletion stage of the C-V curve reported in figure 7.
2.4 2.2 2.0

1.01 1.00 0.99 0.98 0.97 0.96 0.95 0.94 -40 -30 -20
E F
Al SiN x SiO 2 n Si p Si Al
+

1.0 0.9 0.8 0.7 0.6 0.5 0.4 0 10

-10

Voltage (V)

Figure 7 Normalized C-V characteristics of Al/SiNx/emitter n+-Si MIS after and before 65 hours of UV light exposure. 6. CONCLUSIONS In this paper we have monitored, during the UV light soaking, the photovoltaic parameters of solar cells based on FZ 0.3 cm silicon wafer. We have found different behaviors depending on the passivation used on the emitter layer. In particular we have compared the passivation obtained by a double layer of thermal silicon oxide and silicon nitride with the passivation of a single layer of silicon nitride. We have noted that SiO2 layer works as a barrier against hydrogen diffusion toward the junction producing in higher photovoltaic performances in particular in terms of fill factor of the cell. Capacitance-voltage measurement, performed on MIS devices growth on 0.3 cm p-type FZ silicon wafer having the same passivation layers as the investigated solar cells, and lifetime measurements, resumed on silicon substrate passivated with silicon nitride and/or silicon oxide, have confirmed the formation of donor like optically generated state of charge. This UV induced charge can be able to increase the photovoltaic performances of the solar cells. REFERENCES [1] T. Lauinger, J. Schmidt, A.G. Aberle, R. Hezel, 13th EPSEC, 1291 (1995) [2] A.G. Aberle, Prog. Phot. Res. Appl., 5, 29 (1997) [3] C. Legujit et al, Sol. En. Mat. Sol. Cells, 40, 297 (1996) [4] H. Nagel, A.G. Aberle, R. Hezel, Progr. Photov. 7 245 (1999). [5] M. Hofmann, E. Schneiderlochner, W. Wolke, R. Preu, 19th EPVSEC (2004). [6] R. Hezel K. Jaeger. J. Electrochem. Soc 136 (2) 518 (1989) [7] E.H. Nicollian, J.R. Brews in MOS metal oxide semiconductors physics and technology Whiley Interscience (2003). [8] M. Tucci, E. Salurso, F. Roca, F. Palma, Thin Solid Films 403 307 (2002).

621-4 SiNx/SiO2/Si 621-3 SiNx/Si

QEUV deg/QE0

1.8 1.6 1.4 1.2 1.0 400 500 600 700 800 900 1000 1100 1200

wavelength (nm)

Figure 6 Enhancement of external quantum efficiency of solar cells passivated by SiNx/SiO2 (621-4) and by SiNx (621-3) due to UV light exposure.

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