Blue and red light-emitting non-stoichiometric silicon nitride-based structures

The two triple-layered SiO₂ /SiN_x /SiO₂  structures with Si-rich and N-rich silicon nitride active layer were fabricated on p-type Si-substrates by chemical vapour deposition. The SiN_x  layer of different composition (x = 0.9 and x = 1.4) was obtained by changing the ratio of the SiH₂ Cl₂ /NH₃ flow rates during deposition of a silicon nitride active layer (8/1 and 1/8, respectively). The spectroscopic ellipsometry and photoluminescence (PL) measurements showed that the refractive index, the absorbance and luminescence properties depend on a chemical composition of silicon nitride layers. The structures with Si-rich and N-rich SiN_x  active layers emit in the red (1.9 eV) and blue (2.6 eV) spectral ranges, respectively. The PL intensities of different structures are comparable. The rapid thermal annealing results in the intensity decrease and in the PL spectra narrowing in the case of SiN_1,4 active layer, whereas the increase in the emission intensity and the PL spectra broadening are observed in the case of the annealed sample with a SiN_0,9 active layer. The PL origin and the effect of annealing treatment have been discussed, taking into account the band tail mechanism of radiative recombination. Multilayered (SiO₂ /SiN_x )_n /Si structures are of practical interest for creation of effective light sources on the basis of current Si technology.

1. Rodríguez-Gómez A., Moreno-Rios M., García-García R., Pérez-Martínez A.L., Reyes-Gasga J. Role of the substrate on the growth of silicon quantum dots embedded in silicon nitride thin films. Materials Chemistry and Physics, 2018, vol. 208, pp. 61-67. https://doi.org/10.1016/j.matchemphys.2018.01.032

2. Shuleiko D. V., Zabotnov S. V., Zhigunov D. M., Zelenina A. A., Kamenskih I. A., Kashkarov P. K., Photoluminescence of Amorphous and Crystalline Silicon Nanoclusters in Silicon Nitride and Oxide Superlattices. Semiconductors, 2017, vol. 51, no. 2, pp. 196-202. https://doi.org/10.1134/S1063782617020208

3. Kistner J., Chen X., Wenig Y., Strunk H. P., Schubert M. B., Werner J. H. Photoluminescence from silicon nitride - no quantum effect. Journal of Applied Physics, 2011, vol. 110, no. 2, p. 023520 (5 p.). https://doi.org/10.1063/1.3607975

4. Hiller D., Zelenina A., Gutsch S., Dyakov S. A., Lopez-Vidrier L., Estrade S., Peiro F., Garrido B., Valenta J., Korinek M., Trojanek F., Maly P., Schnabel M., Weiss C., Janz S., Zachrias M. Absence of quantum confinement effects in the photoluminescence of Si3 N4 -embedded Si nanocrystals. Journal of Applied Physics, 2014, vol. 115, no. 20, p. 204301 (9 p.). https://doi.org/10.1063/1.4878699

5. Parkhomenko I., Vlasukova L., Komarov F., Milchanin O., Makhavikou M., Mudryi A., Zhivulko V., Żuk J., Kopyciński P., Murzalinov D. Origin of visible photoluminescence from Si-rich and N-rich silicon nitride films. Thin Solid Films, 2017, vol. 626, pp.70-75. https://doi.org/10.1016/j.tsf.2017.02.027

6. Kanicki J., Warren W. L. Defects in amorphous hydrogenated silicon nitride films. Journal of Non-Crystalline Solids, 1993, vol. 164-166, pp. 1055-1060. https://doi.org/10.1016/0022-3093(93)91180-B

7. Singh S. P., Srivastava P. Recent progress in the understanding of Si-nanostructures formation in a-SiN :H thin film for Si-based optoelectronic devices. Solid State Phenomena, 2011, vol. 171, pp. 1-17. https://doi.org/10.4028/www.scientific.net/SSP.171.1

8. Torchynska T. V., Casas Espinola J. L., Vergara Hernandez E., Khomenkova L., Delachat F., Slaoui A. Effect of the stoichiometry of Si-rich silicon nitride thin films on their photoluminescence and structural properties. Thin Solid Films, 2015, vol. 581, pp. 65-69. https://doi.org/10.1016/j.tsf.2014.11.070

9. Mercaldo L. V., Esposito E. M., Veneri P. D., Rezgui B., Sibai A., Bremond G. Photoluminescence properties of partially phase separated silicon nitride films. Journal of Applied Physics, 2011, vol. 109, no. 9, p. 093512 (5 p.). https://doi.org/10.1063/1.3575172

10. Wang M., Xie M., Ferraioli L., Yuan Z., Li D., Yang D., Pavesi L. Light emission properties and mechanism of low temperature prepared amorphous SiNx films. I. Room-temperature band tail states photoluminescence. Journal of Applied Physics, 2008, vol. 104, no. 8, p. 083504 (4 p.). https://doi.org/10.1063/1.2996292

11. Xie M., Li D., Wang F., Yang D. Luminescence properties of silicon-rich silicon nitride films and light emitting devices. ECS Transactions, 2011, vol. 35, no. 18, pp. 3-19. https://doi.org/10.1149/1.3647900

12. Koutsoureli M., Michalas L., Gantis A., Papaioannou G. A study of deposition conditions on charging properties of PECVD silicon nitride films for MEMS capacitive switches. Microelectronics Reliability, 2014, vol. 54, no. 9-10, pp. 2159−2163. https://doi.org/10.1016/j.microrel.2014.08.002

13. Necas D., Perina V., Franta D., Ohlídal I., Zemek J. Optical characterization of non-stoichiometric silicon nitride films. Physical Status Solidi C, 2008, vol. 5, no. 5, pp. 1320-1323. https://doi.org/10.1002/pssc.200777767

14. Maeda K., Umezu I. Atomic micro structure and electronic properties of a-SiN :H deposited by radio frequency glow discharge. Journal of Applied Physics, 1991, vol. 70, no 5, pp. 2745-2754. https://doi.org/10.1063/1.350352

15. Banerji N., Serra J., Chiussi S., Leo Ân B., Pe Ârez-Amor M. Photo-induced deposition and characterization of variable bandgap a-SiN:H alloy films. Applied Surface Science, 2000, vol. 168, no. 1-4, pp. 52-56. https://doi.org/10.1016/S0169-4332(00)00583-3

16. Debieu O., Nalini R. P., Cardin J., Portier X., Perriere J., Gourbilleau F. Structural and optical characterization of pure Si-rich nitride thin films. Nanoscale Research Letters, 2013, vol. 8, no. 1, p. 31. https://doi.org/10.1186/1556-276X-8-31

17. Wang M., Li D., Yuan Z., Yang D., Quen D. Photoluminescence of Si-rich silicon nitride defect-related states and silicon nanoclusters. Applied Physics Letters, 2007, vol. 90, no. 13, p. 131903 (3 p.). https://doi.org/10.1063/1.2717014

18. Wang X., Liu Y., Chen D., Dong L., Chen C. Photoluminescence of Si-rich SiNx films deposited by LPCVD under different conditions. International Journal of Modern Physics B, 2007, vol. 21, no. 26, pp. 4583-4592. https://doi.org/10.1142/S0217979207037995

19. Volodin V. A., Bugaev K. O., Gutakovsky A. K., Fedina L. I., Neklyudova M. A., Latyshev A. V., Misiuk A. Evolution of silicon nanoclusters and hydrogen in SiN :H films: Influence of high hydrostatic pressure under annealing. Thin Solid Films, 2012, vol. 520, no. 19, pp. 6207-6214. https://doi.org/10.1016/j.tsf.2012.05.019

20. Jackson W. A., Searly T. M., Austin I. G., Gibson R. A. Photoluminescence excitation studies of a-SiNx :H alloys. Journal of Non-Crystalline Solids, 1986, vol. 77-78, pp. 909-912. https://doi.org/10.1016/0022-3093(85)90808-7

21. Mohammed S., Nimmo M. T., Malko A. V., Hinkle C. L. Chemical bonding and defect states of LPCVD grown silicon-rich Si3N4 for quantum dot applications. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, 2014, vol. 32, no. 2, p. 021507 (7 p.). https://doi.org/10.1116/1.4861338

22. Krückel C. J., Fülöp A., Ye Z., Andrekson P. A., Torres-Company V. Optical bandgap engineering in nonlinear silicon nitride waveguides. Optics Express, 2017, vol. 25, no. 13, pp. 15370-15380. https://doi.org/10.1364/OE.25.015370

23. Charifi H., Slaoui A., Stoquert J. P., Chaib H., Hannour A. Opto-structural properties of silicon nitride thin films deposited by ECR-PECVD. World Journal of Condensed Matter Physics, 2016, vol. 6, no. 1, pp. 7-16. https://doi.org/10.4236/wjcmp.2016.61002

24. Smietana M., Bock W. J., Szmidt J. Evolution of optical properties with deposition time of silicon nitride and diamond-like carbon films deposited by radio-frequency plasma-enhanced chemical vapor deposition method. Thin Solid Films, 2011, vol. 519, no. 19, pp. 6339-6343. https://doi.org/10.1016/j.tsf.2011.04.032

25. Joshi B. C., Eranna G., Runthala D. P., Dixit B. B., Wadhawan O. P., Vyas P. D. LPCVD and PECVD silicon nitride for microelectronics technology. Indian Journal of Engineering and Materials Sciences, 2000, vol. 7, pp. 303-309. URL http://hdl.handle.net/123456789/24418

26. Robertson J. Defects and hydrogen in amorphous silicon nitride. Philosophical Magazine B, 1994, vol. 69, no 2, pp. 307-326. https://doi.org/10.1080/01418639408240111

27. Goirgis F., Vinegoni C., Pavesi L. Optical absorption and photoluminescence properties of a-Si1-x Nx :H films deposited by plasma-enhanced CVD. Physical Review B, 2000, vol. 61, no. 7, pp. 4693-4698. https://doi.org/10.1103/PhysRevB.61.4693

28. Austin I. G., Jackson W. A., Searle T. M., Bhat P. K., Gibson R. A. Photoluminescence properties of a-SiNx :H alloys. Philosophical Magazine B, 1985, vol. 52, no. 3, pp. 271-288. https://doi.org/10.1080/13642818508240600

29. Hasegawa S., Matuura M., Kurata Y. Amorphous SiN:H dielectrics with low density of defects, Applied Physics Letters, 1986, vol. 49, no. 19, pp. 1272-1274. https://doi.org/10.1063/1.97383

30. Kato H., Kashio N., Ohki Y., Seol K. S., Noma T. Band-tail photoluminescence in hydrogenated amorphous silicon oxynitride and silicon nitride films. Journal of Applied Physics, 2003, vol. 93, no. 1, pp. 239-244. https://doi.org/10.1063/1.1529292

31. Dyakov S. A., Zhigunov D. M., Hartel A., Zacharias M., Perova T. S., Timoshenko V. Yu. Enhancement of photoluminescence signal from ultrathin layers with silicon nanocrystals. Applied Physics Letters, 2012, vol. 100, no. 6, p. 061908 (4 p.). https://doi.org/10.1063/1.3682537

32. Gritsenko V. A. Atomic structure of the amorphous nonstoichiometric silicon oxides and nitrides. Physics-Uspekhi, 2008, vol. 51, no. 7, pp. 699-708. https://doi.org/10.3367/UFNr.0178.200807c.0727

33. Gritsenko V. A., Novikov Yu. N., Chin A. Short-range order and charge transport in SiOx : experiment and numerical simulation. Technical Physics Letters, 2018, vol. 44, no. 6, pp. 541-544. https://doi.org/10.1134/S1063785018060196