 Nano Express
 Open Access
 Published:
New Sibased multilayers for solar cell applications
Nanoscale Research Letters volume 6, Article number: 156 (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
Figure 1 shows the FTIR spectra obtained for the nonannealed SRSO/SiO_{2}, SiN_{ x }/SiO_{2}, and SRSO/SiN_{ x }multilayers. The spectra were recorded at the Brewster angle of 65° that enables the detection of the LO_{3} mode of silica at about 1250 cm^{1} in addition to the TO_{3} mode located near 1080 cm^{1}.
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
The PL emission spectra of the annealed multilayer structures were measured using 488 nm excitation wavelength and the spectrum was recorded in the visible range. Two different annealing treatments were chosen for the study1 min1000°C (rapid thermal annealingRTA) and 1 h1100°C under N_{2} atmosphere, the latter being the classical annealing treatment used for recovering defects in SiO_{2} matrix to favor luminescence from Sinc [3]. Figure 2 shows the effect of the annealing treatment on the PL intensity of the three kinds of multilayer structures. All the curves are normalized to a total thickness of 100 nm. Since the number of periods and the sublayer thickness remains the same for each of these films, i.e., N _{periods}(t _{sublayer1}/t _{sublayer2}) = 50(3.5/3.5 nm), it becomes possible to make a comparative analysis from the PL spectrum of these three different multilayer structures. The interference effect in PL intensity has been investigated by the method proposed by Holm et al. [19] for all the spectra presented in this article. This method gives us the PL intensity versus layer and substrate parameters (refractive indices, thicknesses). We assume and homogenous density of emitting centers, an average refractive index within the thickness of multilayer. For measurements on Figure 2 no important change in PL has been found due to interference.
It can be noticed from the spectrum that when the multilayers are subjected to the classical annealing treatment of 1 h1100°C, there is no emission from the SRSO/SiN_{ x }while the SRSO/SiO_{2} structure shows a strong PL signal and has a wide range of emission spectrum. At the same time, it is interesting to note a very weak PL signal in the case of SiN_{ x }/SiO_{2}. The PL peaks appear in a region usually related to the optical transitions in the SiO_{2} matrix due to the presence of defects [3, 17]. The lower part of Figure 2 shows the PL spectrum recorded after annealing the multilayer structures for 1 min at 1000°C (RTA). The response of the multilayers to this annealing treatment shows almost a reversed trend of what was observed in the case of classical annealing treatment. It can be noted that the SRSO/SiN_{ x }has the highest intensity. No PL emission has been recorded from the SRSO/SiO_{2} system. We may note from the figures that the luminescence peak arising from the SiN_{ x }/SiO_{2} structure around 1.9 eV is the same whatever the annealing temperature. The fitting of the PL curve recorded from the SRSO/SiN_{ x }film evidences the presence of two emission bands centered at 1.65 and 1.37 eV. Though this result is interesting and shows the possibility of exploiting SRSO alternated with the SiN_{ x }sublayer to achieve a control over the thermal budget, it also has to be mentioned that the PL intensity obtained is one order of magnitude lower than the emission of SRSO/SiO_{2} subjected to classical annealing. Hence, two methods of fabrication were attempted with the aim of increasing the PL intensity: (i) increasing the SiN_{ x }sublayer thickness to 5 nm and (ii) doubling the number of periods, i.e., fabricating 100 periods of 3.5 nm SRSO alternated with 5 nm SiN_{ x }. Figure 3 shows the effect of the aforesaid fabrication methods on the PL spectrum of the SRSO/SiN_{ x }multilayers. All the spectra have been normalized to 100 nm thickness for comparison. The interference effect in PL intensity has been also investigated by the previously mentioned method PL intensity from both 50 periods multilayers should be decreased by about 15%, in order to take into account the enhancement effect due to maxima of interference. The first method adopted reveals that the SiN_{ x }thickness has some significant contribution toward the luminescence. There is a slight change in the emission wavelength from 1.59 eV with 3.5 nm SiN_{ x }sublayer to 1.55 eV in the case of 5 nm SiN_{ x }sublayer. Irrespective of the number of periods deposited, for a given sublayer thickness the wavelength of emission peak remained constant. It is interesting to note that the emission intensity increases with the SiN_{ x }thickness. This result motivated toward trying out the second method mentioned and it can be noticed that the PL signal increases 7.4 times when the number of (3.5 nm)SRSO/(5 nm)SiN_{ x }pattern is increased from 50 to 100. For that case one can notice is the presence of a small peak between 1.90 and 1.65 eV and another one around 1.5 eV. The inset in Figure 3 shows a comparison between the SRSO/SiO_{2} annealed at 1 h1100°C and SRSO/SiN_{ x }structure subjected to RTA. One can notice that the emission peak from the SRSO/SiN_{ x }system shifts in the visible region and this is one of the advantageous aspects for the solar cell application. It is very interesting to note that the SRSO/SiN_{ x }annealed for a very short time of 1 min at 1000°C is 1.43 times more intense than the SRSO/SiO_{2} structure annealed for a long time of 1 h and at higher temperature. Accounting for the interference effect, we can infer that SRSO/SiN_{ x }exhibits higher PL intensity than SRSO/SiO_{2}. Thus, it can be seen that a replacement of the SiO_{2} sublayer by the SiN_{ x }sublayer and alternating it with the SRSO sublayer not only favors luminescence but paves way to achieve a control over the thermal budget.
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.
References
Conibeer G, Green M, Corkish R, Cho Y, Cho EC, Jiang CW, Fangsuwannarak T, Pink E, Huang Y, Puzzer T, Trupke T, Richards B, Shalav A, Lin KL: "Silicon nanostructures for third generation photovoltaic solar cells". Thin Solid Films 2006, 511–512: 6542. 10.1016/j.tsf.2005.12.119
Conibeer G, Green M, Cho EC, Konig D, Cho D, Fangsuwannarak T, Scadera G, Pink E, Huang Y, Puzzer T, Huang S, Song D, Flynn C, Park S, Hao X, Mansfield D: "Silicon quantum dot nanostructures for tandem photovoltaic cells". Thin Solid Films 2008, 516: 6748. 10.1016/j.tsf.2007.12.096
Gourbilleau F, Ternon C, Maestre D, Palais O, Dufour C: " Siliconrich SiO _{ 2 } / SiO _{ 2 } multilayers: A promising material for the third generation of solar cell". J Appl Phys 2009, 106: 013501. 10.1063/1.3156730
Canham LT: " Silicon quantum wire array fabrication by electrochemical and chemical dissolution of wafers". Appl Phys Lett 1990, 57: 1046–1048. 10.1063/1.103561
Wolkin MV, Jorne J, Fauchet PM, Allan G, Delerue C: "Electronic states and luminescence in porous silicon quantum dots: the role of oxygen". Phys Rev Lett 1999, 82: 197. 10.1103/PhysRevLett.82.197
Puzder A, Williamson AJ, Grossman JC, Galli G: "Surface control of optical properties in silicon nanoclusters". J Chem Phys 2002, 117: 6721. 10.1063/1.1504707
Tan WK, Yu MB, Chen Q, Ye JD, Lo GQ, Kwong DL: "Red light emission from controlled multilayer stack comprising of thin amorphous silicon and silicon nitride layers". Appl Phys Lett 2007, 90: 221103. 10.1063/1.2743743
Gourbilleau F, Portier X, Ternon C, Voivenel P, Madelon R, Rizk R: "Si rich/SiO _{ 2 } nanostructured multilayers by reactive magnetron sputtering". Appl Phys Lett 2001, 78: 3058. 10.1063/1.1371794
Von Behren J, Van Buuren T, Zacharias M, Chimowitz EH, Fauchet PM: "Quantum confinement in nanoscale silicon: The correlation of size with bandgap and luminescence". Solid State Commun 1998, 105: 317. 10.1016/S00381098(97)100990
Furukawa S, Miyasato T: "Quantum size effects on the optical bandgap of microcrystalline Si:H". Phys Rev B 1988, 38: 5726. 10.1103/PhysRevB.38.5726
Lockwood DJ, Lu ZH, Baribeau JM: "Quantum confined luminescence in Si/SiO _{ 2 } superlattices". Phys Rev Lett 1996, 76: 539. 10.1103/PhysRevLett.76.539
Zacharias M, Heitmann J, Scholz R, Kahler U, Schmidt M, Bläsing J: "Size controlled highly luminescent silicon nanocrystals: A SiO/SiO _{ 2 } superlattice approach". Appl Phys Lett 2002, 80: 661. 10.1063/1.1433906
Ternon C, Gourbilleau F, Portier X, Voivenel P, Dufour C: "An original approach for the fabrication of Si/SiO _{ 2 } multilayers using reactive magnetron sputrering". Thin Solid Films 2002, 419: 5. 10.1016/S00406090(02)002948
Olsen JE, Shimura F: "Infrared reflection sprectroscopy of the SiO _{ 2 } silicon interface". J Appl Phys 1989, 66: 1353. 10.1063/1.344435
Dupont G, Caquineau H, Despax B, Berjoan R, Dollet A: "Structural properties of N rich aSiN:H films with a low electron trapping rate". J Phys D Appl Phys 1997, 30: 1064. 10.1088/00223727/30/7/002
Scardera G, Puzzer T, Conibeer G, Green MA: "fourier transform infrared spectroscopy of annealed silicon rich silicon nitride thin films". J Appl Phys 2008, 104: 104310. 10.1063/1.3021158
Delachat F, Carrada M, Ferblantier G, Grob JJ, Slaoui A, Rinnert H: "The structural and optical properties of SiO _{ 2 } /Si rich SiN _{ x } Sincs". Nanotechnology 2009, 20: 275608. 10.1088/09574484/20/27/275608
Bae S, Farber DG, Fonash SJ: "Characteristics of low temperature silicon nitride (SiN _{ x } :H) using electron cyclotron resonance plasma". Solid State Electron 2000, 44: 1355. 10.1016/S00381101(00)000861
Holm RT, McKnight SW, Palik ED: "Interference effects in luminescence studies of thin films". Appl Opt 1982, 21: 2512. 10.1364/AO.21.002512
Di D, PerezWurfl I, Conibeer G, Green MA: "Formation and photoluminescence of Si quantum dots in SiO _{ 2 } /Si _{ 3 } N _{ 4 } hybrid matrix for all Si tandem solar cells". Sol Energy Mater Sol Cells 2010, 94: 2238. 10.1016/j.solmat.2010.07.018
Acknowledgements
This study is supported by the DGA (Defense Procurement Agency) through the research program no. 2008.34.0031.
Author information
Affiliations
Corresponding author
Additional information
Competing interests
The authors declare that they have no competing interests.
Authors' contributions
RPN fabricated the multilayers under investigation and carried out the characterization studies.CD and JC made significant contribution to the optical properties and interference effect. FG conceived of the study and participated in the coordination and writing of the manuscript. All authors read and approved the final manuscript.
Authors’ original submitted files for images
Below are the links to the authors’ original submitted files for images.
Rights and permissions
Open Access This article is distributed under the terms of the Creative Commons Attribution 2.0 International License ( https://creativecommons.org/licenses/by/2.0 ), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
About this article
Cite this article
Nalini, R.P., Dufour, C., Cardin, J. et al. New Sibased multilayers for solar cell applications. Nanoscale Res Lett 6, 156 (2011). https://doi.org/10.1186/1556276X6156
Received:
Accepted:
Published:
DOI: https://doi.org/10.1186/1556276X6156
Keywords
 Annealing Treatment
 Multilayer Structure
 Solar Cell Device
 SiO2 Matrix
 Reactive Magnetron Sputtering