New Sibased multilayers for solar cell applications
 R Pratibha Nalini^{1},
 Christian Dufour^{1},
 Julien Cardin^{1} and
 Fabrice Gourbilleau^{1}Email author
DOI: 10.1186/1556276X6156
© Nalini et al; licensee Springer. 2011
Received: 24 September 2010
Accepted: 18 February 2011
Published: 18 February 2011
Abstract
In this article, we have fabricated and studied a new multilayer structure SiSiO_{2}/SiN_{ x }by reactive magnetron sputtering. The comparison between SiO_{2} and SiN_{ x }host matrices in the optical properties of the multilayers is detailed. Structural analysis was made on the multilayer structures using Fourier transform infrared spectroscopy. The effect of specific annealing treatments on the optical properties is studied and we report a higher visible luminescence with a control over the thermal budget when SiO_{2} is replaced by the SiN_{ x }matrix. The latter seems to be a potential candidate to replace the most sought SiO_{2} host matrix.
Introduction
The third generation of solar cells aims at reducing the cost and at improving the efficiency. Thin film solar cells based on silicon nanostructures is one of the most researched system to achieve such a target [1–3]. Ever since the discovery of the visible luminescence of the porous Si by Canham [4] various research groups have exploited the room temperature photoluminescent nature of silicon by fabricating different kinds of Sibased nanostructures. The luminescence is attributed to the quantum confinement of carrier in Sinanoclusters (Sinc) [5–8]. Among the methods of obtaining the Si nanostructures we cite electrochemical etching [4, 9], fabrication of silicon dots by plasma sputtering technique [10], and multilayer approach [8, 11, 12].
The important part of the ongoing research involves Sinc embedded in an amorphous matrix such as SiO_{2}, SiN_{ x }, or amorphous silicon. Though Sinc embedded in SiO_{2} is the most common structure, the problem of carrier injection in this matrix comes as a major drawback owing to the large band gap of SiO_{2}. Hence the replacement of SiO_{2} by other dielectric matrices with smaller bandgap turns out to be a solution. SiN_{ x }matrix meets up these requirements and hence Sinc embedded in SiN_{ x }matrix has become a material of choice in the recent past. In this article, we develop a new multilayer composition siliconrich silicon oxide (SRSO)/SiN_{ x }to overcome the insulating nature of SiO_{2} by taking advantage of the reduced bandgap in SiN_{ x }. Using SiN_{ x }as the host matrix favors the electrical conductivity of carriers while we still maintain the quantum confinement as done with the SiO_{2} matrix. This study aims at fabricating and comparing the light emission properties of three different kinds of multilayer compositions: (a) SRSO/SiO_{2}, (b) SRSO/SiN_{ x }, (c) SiN_{ x }/SiO_{2}. Such a study is important to understand the influence of host matrices on the Sinc and consequently to achieve an optimized solar cell device in the future.
Experimental details
Three kinds of multilayer structures were fabricated on 2" Si wafer by reactive magnetron sputtering comprising 50 patterns of SRSO/SiO_{2}, SRSO/SiN_{ x }, and SiN_{ x }/SiO_{2}. We define the gas flow rate as r _{g} = f _{g}/(f _{g} + f _{Ar}) where f _{g} represents the N or H_{2} gas flow and f _{Ar} represents the Argon gas flow. The SiO_{2} sublayer was fabricated by sputtering the SiO_{2} cathode under pure Ar plasma. Reactive magnetron sputtering, an approach developed by our team, was used for the fabrication of SRSO sublayers. It takes advantage of the oxygen reducing capacity of hydrogen when introduced into the Ar plasma [8]. The hydrogenrich plasma favors Si excess in the SiO_{2} sublayer. Besides this in order to facilitate a higher incorporation of Si in the matrix, both SiO_{2} and Si cathodes were used to fabricate the SRSO sublayer. The powers of SiO_{2} and Si were maintained as 7.4 and 2.2 W/cm^{2}, respectively. The hydrogen rate r _{H} was maintained at 50% while the total flow f _{g} + f _{Ar} was fixed at 10 sccm. The pressure in the chamber was chosen as 3 mTorr. Thus the SRSO/SiO_{2} multilayer structure was deposited by an alternative reactive sputtering under hydrogenrich plasma for the SRSO layer and pure Ar plasma for the SiO_{2} sublayer. The SiN_{ x }layer was fabricated by sputtering the Si cathode and simultaneously introducing nitrogen into the Ar plasma. The nitrogen rate r _{N} was kept at 10% while the total flow rate was fixed at 10 sccm. The pressure in the chamber was chosen as 2 mTorr for SiN_{ x }layers. The temperature of deposition was maintained at 500°C for all the cases. The thickness of the SRSO sublayer was fixed to be 3.5 nm in order to be within the quantum confinement regime. In order to understand the influence of SiN_{ x }matrix, two different thicknesses of the SiN_{x} sublayer (3.5 and 5 nm) were chosen.
The FTIR spectra of these samples were recorded in absorption configuration using Nicolet Nexus spectrometer at Brewster's angle (65°). The photoluminescence (PL) spectra of the annealed samples were obtained in the visible range using Jobin Yvon monochromator in the wavelength range 5501100 nm. The excitation wavelength of 488 nm (Ar laser) was used for measurements.
Results and discussions
FTIR spectroscopy
In SRSO/SiO_{2} around 1225 and 1080 cm^{1} we notice the LO_{3} and TO_{3} peak from the SiO stretching, the TO_{4}LO_{4} doublet between the 11001200 cm^{1} and the TO_{2}LO_{2} asymmetric stretching of SiO from SiO_{2} at 810 and 820 cm^{1}, respectively [13]. The presence of Sinc is attested by the intensity of the LO_{3} peak which is representative of the SiO bond at the interface [14] between silicon and silica while the TO_{3} vibration mode at about 1080 cm^{1} is the signature of the volumic silica.
The SiN_{ x }/SiO_{2} film has a broad peak in the 1250950 cm^{1} region which can be due to the contributions of both LO and TO modes from SiO_{2} and SiN stretching mode [15–17]. The absorption band located around 860 cm^{1} could be attributed to the SiN asymmetric stretching mode.
In the case of SRSO/SiN_{ x }films, the shoulder around 1190 cm^{1} may be due either to NH bond [16, 18] or to a contribution of the LO_{3} mode of SiOSi bonds at 180° [13]. Such a result is the signature of the Si nanoparticles formation within either the SiN_{ x }[19] and/or the SRSO sublayer [13]. Between 1050 and 1070 cm^{1} lies the LO peak of aSi_{ x }N_{ y }H_{ z }from SiN as it has been observed in the SiN_{ x }/SiO_{2} spectrum adding the contribution of the TO SiO mode.
PL spectra
Discussion
The PL spectra of the SRSO/SiN_{ x }subjected to two different annealing treatments show that the quenching of the PL signal after an RTA can be attributed to the nonradiative defects either at the interface of Sinc and the SiO_{2} matrix or within the SiO_{2} matrix itself which traps the photon arising from the recombination of the exciton within the Sinc. On the contrary, it can be seen that the SiN_{ x }sublayer favors luminescence even if this later could be attributed to the defects in the matrix. Noticing the shift in emission peak from 1.9 to 1.6 eV in the case of SiN_{ x }/SiO_{2} and SRSO/SiN_{ x }, respectively, it can be said that the sandwiching of SRSO between SiN_{ x }instead of SiO_{2} sublayers not only favors luminescence but also exhibits luminescence in a region attributed to the emission from Sinc. This implies that though at this temperature SiN_{ x }shows a defectrelated PL, when alternated with SRSO, the emission from Sinc becomes dominant.
On the other hand, the quenching of PL in classically annealed SRSO/SiN_{ x }is quite surprising as several authors have noticed an increase of the PL signal either from SRSO or SiN_{ x }after such annealing. It also should be noted that the 'SRSO sublayer' fabricated under the same conditions and alternated with SiO_{2} sublayer has a high emission. Hence one can conclude that the presence of the SiN_{ x }sublayer quenches the PL. This can be attributed either to the coalescence of Si clusters at such an annealing treatment thereby overcoming the quantum confinement regime or to the nonradiative defects at the interface between SRSO and SiN_{ x }or in SiN_{ x }. The increase of the PL emission when increasing the number of layer could be the result of H diffusion during the deposition process which favors the recovering of the defects and the Si nanoparticles formation. Such a hypothesis is supported by the presence of NH bonds revealed by FTIR experiments in the nonannealed multilayers and that can be attributed to the Sinc formation [17]. Another explanation could be the increase of strain with the number of layer that favors the Sinp formation resulting in an increase of the Sinp density and hence in the PL emission. However, the comparison in the inset of Figure 3 of the two types of multilayers demonstrates the advantage to replace the SiO_{2} sublayer by the SiN_{ x }. HRTEM experiments are in progress to understand the optical behavior of these multilayers.
Conclusion
The multilayers were fabricated using the sputtering technique and the FTIR spectrum revealed its characteristic peaks. Although SiO_{2} is the most sought host matrix, we evidenced the interest of replacing it with the SiN_{ x }matrix. A higher intensity of PL emission was obtained for RTA when SiN_{ x }matrix was used whereas from the SiO_{2} matrix there was no considerable intensity at such an annealing treatment. We have achieved comparable intensity of emission within one minute of annealing and at a lesser temperature, in comparison to the classical annealing treatment that is done for longer time and slightly higher temperature. We also observe an increase in the PL emission with increase in the number of periods. Highresolution electron microscopy experiments are in progress to understand the effect of the annealing process on the achieved optical properties. This set of abovementioned results paves the way for the fabrication of novel structures for solar cell device applications similar to the one recently reported by Di et al. [20].
Abbreviations
 PL:

photoluminescence
 RTA:

rapid thermal annealing
 Sinc:

Sinanoclusters
 SRSO:

siliconrich silicon oxide.
Declarations
Acknowledgements
This study is supported by the DGA (Defense Procurement Agency) through the research program no. 2008.34.0031.
Authors’ Affiliations
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