Rapid thermal annealing and crystallization mechanisms study of silicon nanocrystal in silicon carbide matrix
© Wan et al; licensee Springer. 2011
Received: 10 November 2010
Accepted: 10 February 2011
Published: 10 February 2011
In this paper, a positive effect of rapid thermal annealing (RTA) technique has been researched and compared with conventional furnace annealing for Si nanocrystalline in silicon carbide (SiC) matrix system. Amorphous Si-rich SiC layer has been deposited by co-sputtering in different Si concentrations (50 to approximately 80 v%). Si nanocrystals (Si-NC) containing different grain sizes have been fabricated within the SiC matrix under two different annealing conditions: furnace annealing and RTA both at 1,100°C. HRTEM image clearly reveals both Si and SiC-NC formed in the films. Much better "degree of crystallization" of Si-NC can be achieved in RTA than furnace annealing from the research of GIXRD and Raman analysis, especially in high-Si-concentration situation. Differences from the two annealing procedures and the crystallization mechanism have been discussed based on the experimental results.
Shockly and Queisser  have calculated the upper theoretical efficiency limitation for on p-n junction silicon solar cell as 30%. In order to further obtain a higher efficiency, multi-junction solar cells with different materials have been designed and fabricated . However, to create different band gap solar cell layers, expensive and perhaps toxic materials have to be involved and this is assumed to be the main obstacle for the wide use of multi-junction solar cell. As a result, in recent years, the theory of "all silicon multi-junction solar cell" has been developed [3, 4], and silicon nanocrystals (Si-NCs) in various dielectric materials study have gained researchers' interests in all silicon multi-junction solar cell applications . Due to quantum size effect, three-dimensional quantum-confined silicon dots have been proven to be able to tune the bandgap in a wide range by controlling the dot size. The bandgap of each cell layer can be adjusted by the wavelength of different light spectrum and all silicon multi-junction solar cells with high efficiency can be well expected.
Many research efforts have been allocated in looking for a better dielectric material as a matrix to embed the Si-NC. Comparing the band gap with different materials such as silicon dioxide (approximately 8.9 eV) and silicon nitride (approximately 4.3 eV), the band gap of silicon carbide (approximately 2.4 eV) is the lowest . The small SiC bandgap increases the electron tunnelling probability. Increased carrier transportation performance and greater current can be expected from these multi-junction solar cells. Kurokawa et al. and M. Künle et al. [6, 7] have reported the fabrication of good quality Si-NC in SiC matrix film by plasma-enhanced chemical vapor deposition (PECVD) system. However, the main disadvantages of PECVD deposition are extremely time consuming in superlattice structure and in toxic, explosive, and expensive gases involved, such as silane (SiH4), monomethylsilane (MMS), methane (CH4), and hydrogen (H2) etc. In our group, Si-NCs in a SiC matrix deposited by a sputtering process have been intensively investigated in order to overcome the disadvantages listed above.
In our previous research, Si-NCs are fabricated by post-deposition annealing of Si-rich SiC (SRC) layer in a nitrogen furnace for a long time (more than 1 h) [8, 9]. Both Si and SiC NC have been clearly observed in x-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements when annealing temperature rise above 900°C. After annealing, SiC-NCs in beta phase (β-SiC) as well as amorphous Si are found surrounding the Si-NC. Rapid thermal annealing (RTA) has been considered as a primary annealing technique in semiconductor industry because of the low energy cost and better crystallization result [10, 11] In nanocrystalline system, better crystallization has also been reported in RTA because heating of the structure is caused by light directly absorbed in the layers . In this paper, we compare two annealing techniques: conventional furnace annealing and RTA upon Si and SiC nanocrystalline system, and subsequently research the differences of structural characterization. By investigating the crystallization differences, we try to explain the crystallization mechanism of Si and SiC-NC.
Sample names and deposition conditions
(volume percentage v%)
Sample structure/thickness (nm)
Single layer/approximately 600
Single layer/approximately 600
Single layer/approximately 600
Single layer/approximately 600
Single layer/approximately 600
Temperature ramping profile for conventional furnace annealing and RTA
Room temperature, approximately 500°C
500°C to approximately 900°C
900°C to approximately 1,100°C
Conventional furnace annealing
The structural properties including the nanocrystal size, shape, and phase separation are studied using TEM (Phillips CM200) at 200 kV. The crystalline properties are evaluated by grazing incidence XRD using a Philips's X'Pert Pro material research diffraction system at a voltage of 45 kV and a current of 40 mA, using Cu Kα radiation (λ = 1.5418 Å). The glancing angle of the incident x-ray beam is optimised by omega scan and set between 0.2° and 0.4° The nanocrystal size is estimated using the Scherrer equation. Additional structural properties such as phase separation and crystallinity are studied by Raman spectroscopy (Renishaw, RM2000) in backscattering configuration. The power of the Ar ion laser (514 nm) was reduced below 8 mW to avoid local crystallization by laser beam.
Results and discussion
X-ray diffraction investigation
It should be noted that there is no Bragg peak of β-SiC phase detected from a sputtered stoichiometric SiC film, indicating that SiC film does not crystallize under 1,100°C annealing condition itself due to insufficient kinetic energy . That both Si and SiC-NC appear in silicon-rich carbide samples could be due to the Si inducement. Some researchers reported sputtered Si starts to crystallize at 900°C . Si and SiC-NC could be observed after annealing at 900°C in our previous research [8, 9]. From these results, we propose that at annealing temperatures of 900°C, the formation of Si-NC , act as nuclei for SiC nanocrystal growth. As a result, both Si and SiC diffraction peaks could be observed in silicon-rich carbide samples while no SiC peak observed in sputtered stoichiometric SiC film.
In both RTA and furnace annealing samples, we can see that when Si concentration increases, Si grain size which is calculated from formula (1) also tends to increase. But the change is not significant until the Si concentration reaches 60 v% and grain size in furnace annealing samples tends to increase faster in high Si concentration (>70 v%). The same trend can also be observed in SiC-NC, the grain size of SiC crystal start to decrease when Si concentration falls below 60 v%.
Discussion of structural difference and crystallization mechanism
RTA is considered as a positive annealing method in Si/SiC nanocrystalline system compared with furnace annealing. For the purpose of quantitative investigation, we calculate the degree of crystallization in all Si concentration range by comparing the RTA and furnace value ratio (D RTA/D furance) from the result of both XRD Si peak intensity (Figure 8) and Raman peak intensity ratio (Figure 10).
Degree of crystallization from RTA and furnace annealing in all Si concentration
(50 to approximately 60 v%)
++Degree of crystallization: D RTA/D furance (from XRD)
Degree of crystallization: D RTA/D furnace (from Raman)
The Si degree of crystallization ratio behaves in a similar overall increase trend from both XRD and Raman results. It's further confirmed that better Si nanocrystal crystallization could be obtained from RTA since more Si-NC are formed and less amorphous Si remained, especially under high Si concentration.
There are two possible crystal mechanisms to explain the main structural difference coming from RTA and furnace annealing procedure as we discussed above:
1. Si-NC have not reached nucleation equilibrium in RTA
When r < r*, because of the decrease of the total free energy, NC tend to reduce in size and vanish in equilibrium. On the other hand, when r > r*, the NC must grow in size to reduce the total free energy until they reach equilibrium.
In our situation, obtaining reliable γ is extremely difficult, but J. K. Bording's group predicted the r* theoretically to be about 2 nm  for crystals and this value matches well with all our measured average SiC-NC size value in Figure 5. Basing on this theory, we may conclude, especially in high Si concentration, Si-NC may have not reached the equilibrium before the annealing temperature (1,100°C) drops in RTA. So, Si-NC whose grain size less is than 2 nm may have not completely vanished, thus more Si-NCs would be observed. The grain size increase trend in Figure 5 can further prove this point, we can see in high Si concentration region (70-80 v%) the Si grain size in RTA is smaller than furnace. This means Si-NCs in RTA could still grow up compare with samples of same Si concentration in furnace, which indicates Si-NC have not reached the equilibrium in RTA.
2. Less SiC-NC pre-existed during ramping-up period before Si nanocrystal grow fast at high temperature
This explanation relies on the crystallization sequence. For both annealing techniques, the peak annealing temperatures (1,100°C) are the same, however the duration of temperature raise (from 500-1,100°C) is different. For the RTA system, it takes 45 s to increase but 40 min are needed to ramp up in furnace annealing situation. We believe the time period of temperature ramping up is crucial to Si crystallization process. From the result of Si degree of crystallization, much larger quantity of Si-NC are observed in RTA, which means Si-NC can be crystallized better in short ramping time situation. It may be because of the existence of SiC-NC before Si nanocrystal fast grows. As discussed earlier, Si nanocrystal start to form around 900°C, meanwhile, SiC-NC are induced to crystallize. Short ramping-up time in RTA may lead to less SiC nanocrystal before 1,100°C. As soon as the temperature rise up to Si fast crystallization point at 1,100°C, more Si-NC could be formed in RTA due to the decrease in SiC-NC.
Si-rich SiC (SRC) layers with various Si concentrations were prepared by co-sputtering Si and SiC targets. Furnace annealing and RTA techniques were compared by studying the precipitation and crystallization of Si and SiC-NC with varying Si/SiC ratio after annealing.
Si and SiC-NC were observed by TEM in both furnace and RTA annealed at 1,100°C. SiC-NC are believed to be induced by Si nuclei from XRD spectra analysis. Meanwhile, when silicon concentration raised from 50 to 80 v%, increased size of Si nanocrystal (from 6 nm to 10 to approximately 12 nm) are observed but SiC nanocrystal size remains same (2 to approximately 4 nm).
Compared with furnace annealing, RTA samples reveal a better degree of crystallization on Si nanocrystal and less amorphous Si residual. More Si-NCs are detected by XRD and Raman analysis for this approach. This could possibly be explained by Si-NC not reaching nucleation equilibrium in the RTA or that less SiC-NC are present during the ramping-up period which increases Si-NC crystallization at high temperatures.
The authors thank other members of the Third Generation Group at the ARC Photovoltaics Centre of Excellence for their contributions to this project. This work was supported by the Australian Research Council ARC via its Centres of Excellence scheme.
- Shockley W, Queisser HJ: Detailed balance limit of efficiency of p-n junction solar cells. Journal of Applied Physics 1961, 32(3):510–519. 10.1063/1.1736034View ArticleGoogle Scholar
- King RR, Law DC, Edmondson KM, Fetzer CM, Kinsey GS, Yoon H, Sherif RA, Karam NH: 40% efficient metamorphic GaInP/GaInAs/Ge multijunction solar cells. Applied Physics Letters 2007, 90(18):183516. 10.1063/1.2734507View ArticleGoogle Scholar
- Conibeer G, Green M, Cho EC, König D, Cho YH, Fangsuwannarak T, Scardera 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(20):6748–6756. 10.1016/j.tsf.2007.12.096View ArticleGoogle Scholar
- 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: 654–662. 10.1016/j.tsf.2005.12.119View ArticleGoogle Scholar
- Jiang C, Green MA: Silicon quantum dot superlattices: Modeling of energy bands, densities of states, and mobilities for silicon tandem solar cell applications. Journal of Applied Physics 2006, 99(11):114902. 10.1063/1.2203394View ArticleGoogle Scholar
- Kurokawa Y, Miyajima S, Yamada A, Konagai M: Preparation of nanocrystalline silicon in amorphous silicon carbide matrix. Japanese Journal of Applied Physics Part 2: Letters 2006, 45: 37–41. 10.1143/JJAP.45.L1064Google Scholar
- Künle M, Hartel A, Löper P, Janz S, Eibl O: Preparation Of Si-Quantumdots In Sic: Single Layer Vs Multi Layer Approach. In 24th European Photovoltaic Solar Energy Conference. Hamburg, Germany; 2009.Google Scholar
- Song D, Cho EC, Conibeer G, Huang Y, Flynn C, Green MA: Structural characterization of annealed Si1-x Cx/SiC multilayers targeting formation of Si nanocrystals in a SiC matrix. Journal of Applied Physics 2008, 103(8):83544. 10.1063/1.2909913View ArticleGoogle Scholar
- Song D, Cho EC, 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(12):3824–3830. 10.1016/j.tsf.2007.06.150View ArticleGoogle Scholar
- Wang Y, Liao X, Ma Z, Yue G, Diao H, He J, Kong G, Zhao Y, Li Z, Yun F: Solid-phase crystallization and dopant activation of amorphous silicon films by pulsed rapid thermal annealing. Applied Surface Science 1998, 135(1–4):205–208. 10.1016/S0169-4332(98)00230-XView ArticleGoogle Scholar
- Szekeres A, Gartner M, Vasiliu F, Marinov M, Beshkov G: Crystallization of a-Si:H films by rapid thermal annealing. Journal of Non-Crystalline Solids 1998, 227–230(Part 2):954–957. 10.1016/S0022-3093(98)00263-4View ArticleGoogle Scholar
- Arguirov T, Mchedlidze T, Kittler M, Rolver R, Berghoff B, Forst M, Spangenberg B: Residual stress in Si nanocrystals embedded in a SiO[sub 2] matrix. Applied Physics Letters 2006, 89(5):053111. 10.1063/1.2260825View ArticleGoogle Scholar
- Schmidt H, Fotsing ER, Borchardt G, Chassagnon R, Chevalier S, Bruns M: Crystallization kinetics of amorphous SiC films: Influence of substrate. Applied Surface Science 2005, 252(5):1460–1470. 10.1016/j.apsusc.2005.02.116View ArticleGoogle Scholar
- Rüther R, Livingstone J, Dytlewski N: Large-grain polycrystalline silicon thin films obtained by low-temperature stepwise annealing of hydrogenated amorphous silicon. Thin Solid Films 1997, 310(1–2):67–74.View ArticleGoogle Scholar
- Carvalho AP, Brotas de Carvalho M, Pires J: Degree of crystallinity of dealuminated offretites determined by X-ray diffraction and by a new method based on nitrogen adsorption. Zeolites 1997, 19(5–6):382–386. 10.1016/S0144-2449(97)00101-2View ArticleGoogle Scholar
- Zi J, Büscher H, Falter C, Ludwig W, Zhang K, Xie X: Raman shifts in Si nanocrystals. Applied Physics Letters 1996, 69(2):200–202. 10.1063/1.117371View ArticleGoogle Scholar
- Kuenle M, Janz S, Eibl O, Berthold C, Presser V, Nickel KG: Thermal annealing of SiC thin films with varying stoichiometry. Materials Science and Engineering: B 2009, 159–160: 355–360. 10.1016/j.mseb.2008.10.056View ArticleGoogle Scholar
- Nakashima S, Harima H: Raman investigation of SiC polytypes. Physica Status Solidi (A) Applied Research 1997, 162(1):39–64. 10.1002/1521-396X(199707)162:1<39::AID-PSSA39>3.0.CO;2-LView ArticleGoogle Scholar
- Riabinina D, Durand C, Margot J, Chaker M, Botton GA, Rosei F: Nucleation and growth of Si nanocrystals in an amorphous Si O2 matrix. Physical Review B 2006, 74(7):075334. 10.1103/PhysRevB.74.075334View ArticleGoogle Scholar
- Bording JK, Taftø J: Molecular-dynamics simulation of growth of nanocrystals in an amorphous matrix. Physical Review B 2000, 62(12):8098. 10.1103/PhysRevB.62.8098View ArticleGoogle Scholar
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