Structural variations of Si1−xC x and their light absorption controllability
© Moon et al.; licensee Springer. 2012
Received: 11 July 2012
Accepted: 31 August 2012
Published: 6 September 2012
The emergence of third-generation photovoltaics based on Si relies on tunable bandgap materials with embedded nanocrystalline Si. One of the most promising approaches is based on the mixed-phase Si1 − xC x . We have investigated the light absorption controllability of nanocrystalline Si-embedded Si1 − xC x produced by thermal annealing of the Si-rich Si1 − xC x and composition-modulated superlattice structure. In addition, stoichiometric SiC was also investigated to comparatively analyze the characteristic differences. As a result, it was found that stoichiometric changes of the matrix material and incorporation of oxygen play key roles in light absorption controllability. Based on the results of this work and literature, a design strategy of nanocrystalline Si-embedded absorber materials for third-generation photovoltaics is discussed.
KeywordsNanocrystalline Si Solar cell Silicon carbide Light absorption Superlattice PACS 78.20. + e 78.30.Ly 78.40.Fy.
Amorphous materials with embedded nanocrystals enable a design method for specific optical and electrical properties of thin film materials. This design enablement of this mixed-phase material originates from the well-known physical principle called quantum confinement. The size-dependent bandgap tuning of nanocrystals embedded in a material with a larger bandgap has been experimentally demonstrated by several groups [1–3], and its application has been also successfully demonstrated in the fields of single-electron devices , memories , light-emitting devices , and solar cells . In solar cells, nanocrystals and their quantum confinement serve a route to the third-generation photovoltaics . For example, intermediate band solar cells  and multi-exciton collection [7, 10] have been demonstrated, which were expected to provide groundbreaking enhancement of solar cell efficiency. However, those demonstrations for third-generation photovoltaics are based on III-V epitaxial thin films or lead chalcogenide-based colloidal nanocrystals, which might not be cost-effective or environmentally friendly. On the other hand, an aggressive consideration called all-Si tandem solar cells is under research in some research groups . They have suggested multi-junction solar cells composed of silicon nanocrystals whose bandgaps are controlled by their sizes. Some fundamental works such as size-dependent photoluminescence wavelength [1, 2, 11], window layer application of heterojunction Si solar cells , and primitive absorber layer application in thin film Si solar cells  have been reported.
Previous works on the Si nanocrystal in Si1 − xC x demonstrated that thermal annealing can be used to control the bandgap of this mixed-phase film within the range between 1.4 and 2.2 eV, which renders the optimal combination of triple-junction all-Si tandem solar cells. This bandgap variation was mainly attributed to the bandgap increase of the Si1 − xC x matrix due to the limited effect of the quantum confinement of Si nanocrystals . According to this argument, the Si nanocrystal is not necessary in the formation of all-Si tandem solar cells, which is well supported by earlier findings on the bandgap tunability of amorphous SiC . Nevertheless, the inclusion of silicon nanocrystal would provide additional opportunities for breaking the Shockley-Queisser limit  via intermediate band solar cells  or multiple exciton generation . Therefore, the research on the Si nanocrystal is still meaningful for the potential third-generation photovoltaics. In this work, we have performed structural and optical characterization of thermally annealed SiC thin films with structural variations. As a result of systematic analysis, we have found that nanocrystalline Si (nc-Si) formation significantly affects the optical properties due to the stoichiometric changes of the matrix material, which also seems to be related to the oxygen incorporation. This coupled effect of stoichiometric change and oxygen incorporation will be discussed in detail, and a novel strategy on the tunable absorber design of solar cells will be also presented.
Si1 − xC x thin films were deposited on Si wafers and quartz substrates simultaneously by radio frequency (RF) magnetron co-sputtering at 200°C. High-purity (4N) Si and C targets (diameter, 4 in.) were used. After cleaning the substrates, the Si wafers were dipped in 5% HF solution for 1 min just before loading into the chamber to remove native oxides. The composition of Si1 − xC x films was controlled by adjusting RF powers to each target material. We have chosen two kinds of composition for the annealing experiment of Si1 − xC x : stoichiometric SiC (SSC) with x = 0.56 and Si-rich SiC (SRSC) with x = 0.08, where the composition was characterized by Rutherford backscattering spectroscopy. SSC and SRSC samples were prepared to have a film thickness of 150 nm for all the experiment and characterization. In addition, superlattice structures (SL) were also prepared by alternative deposition of 36 periods of SSC layers (approximately 1 nm) and SRSC layers (approximately 4 nm), which has a total film thickness around 180 nm. Thermal annealing experiments for SSC, SRSC, and SL samples were performed in a quartz tube furnace at 800°C, 900°C, and 1,000°C for 20 min in nitrogen atmosphere.
The structural and crystallographic characterization of the nanocrystals in the SL was performed by high-resolution transmission electron microscopy (HRTEM), transmission electron diffraction (TED), and grazing incidence X-ray diffraction (GIXRD). Raman spectroscopy was used to analyze the crystal volume fractions, and chemical bonding configurations were studied with Fourier transform infrared (FTIR) spectroscopy and X-ray photoemission spectroscopy (XPS). Photoluminescence (PL) characteristics were studied with an Ar+ laser (λ = 488 nm) excitation source within the temperature range from 5 K to room temperature. Optical transmission and reflection measurements within the wavelength range between 300 and 1,800 nm were performed with an ultraviolet-visible-near infrared spectrophotometer, and optical bandgaps were determined from the Tauc plot.
Results and discussion
Light absorption in Si1 − xC x is basically controlled by its stoichiometry  and bonding configurations . This may enable the all-Si1 − xC x tandem solar cell structure, but employing the mixed-phase structure, i.e., nc-Si with various Si1 − xC x , would provide more opportunities in high-efficiency strategies such as intermediate bands or multiple exciton generation. It is evident that tuning the sizes of nc-Si is not a very efficient method to cover a broad range of absorption band, but tuning the stoichiometry of the matrix material would be highly viable. In addition, both the stoichiometry of the matrix material and the oxygen incorporation can be applied to tune the absorption property of the material. In this work and several previous reports [14–16], thermal annealing methods have been presented to demonstrate bandgap tuning properties of mixed-phase Si1 − xC x thin films; however, direct forming methods using low-temperature deposition tools are highly necessary to attain progresses towards device demonstration. There have been several reports regarding the mixed-phase Si1 − xC x thin film using low-temperature processes [33, 34], polymorphous Si thin films in fast deposition regime [35–37], and formation of nc-Si using atomic hydrogen treatment which have been known to be feasible for photovoltaic thin film production . Using these pre-existing technologies, further investigation on nc-Si-embedded mixed-phase Si1 − x − yC x O y seems to provide a promising route for Si-based third-generation photovoltaics.
In summary, we have performed thermal annealing experiments on Si1 − xC x with various film structures and compositions. As a result, we have found that stoichiometric changes and oxygen incorporation of the matrix Si1 − xC x significantly affects the light absorption properties of mixed-phase Si1 − xC x thin films. This clarifies the strategy towards implementing a light absorber of third-generation photovoltaics: nc-Si-embedded mixed-phase Si1 − -x − yC x O y with pre-existing low-temperature deposition technologies.
This work was supported by the Korea Institute of Energy Research (No. GP2012-0002) and by the IT R&D program of MKE/KEIT [10039200, Development of High Performance Phase Change Materials].
- Takagi H, Ogawa H, Yamazaki Y, Ishizaki A, Nakagiri T: Quantum size effects on photoluminescence in ultrafine Si particles. Appl Phys Lett 1990, 56: 2379–2381. 10.1063/1.102921View Article
- Kim T-W, Cho C-H, Kim B-H, Park S-J: Quantum confinement effect in crystalline silicon quantum dots in silicon nitride grown using SiH and NH. Appl Phys Lett 2006, 88: 123102. 10.1063/1.2187434View Article
- Nozik AJ, Beard MC, Luther JM, Law M, Ellinson RJ, Johnson JC: Semiconductor quantum dots and quantum dot arrays and applications of multiple exciton generation to third-generation photovoltaic solar cells. Chem Rev 2010, 110: 6873–6890. 10.1021/cr900289fView Article
- Ding Y, Dong Y, Bapat A, Nowak JD, Carter CB, Kortshagen UR, Campbell SA: Single nanoparticle semiconductor devices. IEEE Trans Electron Devices 2006, 53: 2525–2531.View Article
- Baik SJ, Lim KS: Characteristics of silicon nanocrystal floating gate memory using amorphous carbon/SiO tunnel barrier. Appl Phys Lett 2002, 81: 5186–5188. 10.1063/1.1533119View Article
- Sun Q, Wang YA, Li LS, Wang D, Zhu T, Xu J, Yang C, Li Y: Bright, multicoloured light-emitting diodes based on quantum dots. Nature Photonics 2007, 1: 717–722. 10.1038/nphoton.2007.226View Article
- Semonin OE, Luther JM, Choi S, Chen H-Y, Gao J, Nozik AJ, Beard MC: Peak external photocurrent quantum efficiency exceeding 100% via MEG in a quantum dot solar cell. Science 2011, 334: 1530–1533. 10.1126/science.1209845View Article
- Green MA: Third generation photovoltaics: ultra‒high conversion efficiency at low cost. Prog Photovol: Res Appl 2001, 9: 123–135. 10.1002/pip.360View Article
- Luque A, Marti A: Increasing the efficiency of ideal solar cells by photon induced transitions at intermediate levels. Phys Rev Lett 1997, 78: 5014–5017. 10.1103/PhysRevLett.78.5014View Article
- Sambur JB, Novet T, Parkinson BA: Multiple exciton collection in a sensitized photovoltaic system. Science 2010, 330: 63–66. 10.1126/science.1191462View Article
- Conibeer G, Green M, Corkish R, Cho Y, Cho E-C, Jiang C-W, Fangsuwannarak T, Pink E, Huang Y, Puzzer T, Trupke T, Richards B, Shalav A, Lin K-L: Silicon nanostructures for third generation photovoltaic solar cells. Thin Solid Films 2006, 511–512: 654–662.View Article
- Cho E-C, Park S, Hao X, Song D, Conibeer G, Park S-C, Green MA: Silicon quantum dot/crystalline silicon solar cells. Nanotechnology 2008, 19: 245201. 10.1088/0957-4484/19/24/245201View Article
- Kim S-K, Cho C-H, Kim B-H, Park S-J, Lee JW: Electrical and optical characteristics of silicon nanocrystal solar cells. Appl Phys Lett 2009, 95: 143120. 10.1063/1.3242030View Article
- Song D, Cho E-C, Conibeer G, Cho Y-H, Huang Y, Huang S, Flynn C, Green MA: Fabrication and characterization of Si nanocrystals in SiC matrix produced by magnetron cosputtering. J Vac Sci Technol B 2007, 25: 1327. 10.1116/1.2756556View Article
- Song D, Cho E-C, Conibeer G, Huang Y, Huang S, Flynn C, Green MA: Structural characterization of annealed SiC/SiC multilayers targeting formation of Si nanocrystals in a SiC matrix. J Appl Phys 2008, 103: 83544. 10.1063/1.2909913View Article
- Song D, Cho E-C, Cho YH, Conibeer G, Huang Y, Huang S, Green MA: Evolution of Si (and SiC) nanocrystal precipitation in SiC matrix. Thin Solid Films 2008, 516: 3824. 10.1016/j.tsf.2007.06.150View Article
- Anderson DA, Spear WE: Electrical and optical properties of amorphous silicon carbide, silicon nitride and germanium carbide prepared by the glow discharge technique. Phil Mag 1977, 35: 1–16. 10.1080/14786437708235967View Article
- Schokley W, Queisser HJ: Detailed balance limit of efficiency of p‒n junction solar cells. J Appl Phys 1961, 32: 510. 10.1063/1.1736034View Article
- Krishna P, Marshall RC: The structure, perfection and annealing behaviour of SiC needles grown by a VLS mechanism. J Cryst Growth 1971, 9: 319–325.View Article
- Zacharias M, Streitenberger P: Crystallization of amorphous superlattices in the limit of ultrathin films with oxide interfaces. Phys Rev B 2000, 62: 8391–8396. 10.1103/PhysRevB.62.8391View Article
- Xia Z, Huang S: Structural and photoluminescence properties of silicon nanocrystals embedded in SiC matrix prepared by magnetron sputtering. Solid State Communications 2010, 150: 914–918. 10.1016/j.ssc.2010.02.032View Article
- Matsui T, Kondo M, Matsuda A: Origin of the improved performance of high-deposition-rate micro-crystalline silicon solar cells by high-pressure glow discharge. Jpn J Appl Phys 2003, 42: L901-L903. 10.1143/JJAP.42.L901View Article
- Coble RL: A model for boundary diffusion controlled creep in polycrystalline materials. J Appl Phys 1963, 34: 1679–1682. 10.1063/1.1702656View Article
- Bernstein MP, Cruikshank DP, Sandford SA: Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures. Icarus 2005, 179: 527. 10.1016/j.icarus.2005.07.009View Article
- Shimizu-Iwayama T, Kurumado N, Hole DE, Townsend PD: Optical properties of silicon nanoclusters fabricated by ion implantation. J Appl Phys 1998, 83: 6018. 10.1063/1.367469View Article
- Iacona F, Franzò G, Spinella C: Correlation between luminescence and structural properties of Si nanocrystals. J Appl Phys 2000, 87: 1295. 10.1063/1.372013View Article
- Vasin AV, Ishikawa Y, Kolenik SP, Konchits AA, Lysenko VS, Nazarov AN, Rudko GY: Light-emitting properties of amorphous Si:C:O:H layers fabricated by oxidation of carbon-rich a-Si:C:H films. Solid State Sciences 2009, 11: 1833–1837. 10.1016/j.solidstatesciences.2009.05.030View Article
- Delerue C, Allan G, Lannoo M: Theoretical aspects of the luminescence of porous silicon. Phys Rev B 1993, 48: 11024–11036. 10.1103/PhysRevB.48.11024View Article
- Beard MC, Knutsen KP, Yu P, Luther JM, Song Q, Metzger WK, Ellingson RJ, Nozik AJ: Multiple exciton generation in colloidal silicon nanocrystals. Nano Lett 2007, 7: 2506–2512. 10.1021/nl071486lView Article
- Shah AV, Platz R, Keppner H: Thin-film silicon solar cells: a review and selected trends. Solar Energy Materials and Solar Cells 1995, 38: 501–520. 10.1016/0927-0248(94)00241-XView Article
- Robertson J, O’Reilly EP: Electronic and atomic structure of amorphous carbon. Phys Rev B 1987, 35: 2946–2957. 10.1103/PhysRevB.35.2946View Article
- Han SZ, Lee HM, Kwon H-S: Bonding structure and optical bandgap of rf sputtered hydrogenated amorphous silicon carbide alloy films. J Non-Cryt Solids 1994, 170: 199–204. 10.1016/0022-3093(94)90047-7View Article
- Demichelis F, Pirri CF, Tresso E, Dellamea G, Rigato V, Rava P: Physical properties of undoped and doped microcrystalline SiC:H deposited by PECVD. MRS Proceedings 1991, 219: 413.View Article
- Klein S, Houben L, Carius R, Finger F, Fischer W: Structural properties of microcrystalline SiC deposited at low substrate temperatures by HWCVD. J Non-Cryst Solids 2006, 352: 1376–1379. 10.1016/j.jnoncrysol.2006.01.047View Article
- Li SB, Wu ZM, Jiang YD, Li M, Liao NM, Yu JS: Structure and 1/f noise of boron doped polymorphous silicon films. Nanotechnology 2008, 19: 085706. 10.1088/0957-4484/19/8/085706View Article
- Li S, Jiang Y, Wu Z, Wu J, Ying Z, Wang Z, Li W, Salamo G: Origins of 1/f noise in nanostructure inclusion polymorphous silicon films. Nanoscale Res Lett 2011, 6: 281. 10.1186/1556-276X-6-281View Article
- Li S-B, Wu Z-M, Jiang Y-D, Yu J-S, Li W, Liao N-M: Growth mechanism of microcrystalline and polymorphous silicon film with pure silane source gas. J Phys D: Appl Phys 2008, 41: 105207. 10.1088/0022-3727/41/10/105207View Article
- Sriraman S, Agarwal S, Aydil ES, Maroudas D: Mechanism of hydrogen-induced crystallization of amorphous silicon. Nature 2002, 418: 62–65. 10.1038/nature00866View Article
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