Journal of Materials Science and Engineering A 3 (9) (2013) 609-614

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Stable Blue Luminescence of Porous Silicon

afak Doan1, 2, Mehman irinov3, Ceren Bakse1, 2, Nihan Akn1, 2, Tark Asar1, 2, Emre Pikin1, 2, Tofig Memmedli1, 2 and Sleyman zelik1, 2
1. Department of Physics, Faculty of Science and Arts, University of Gazi, Teknikokullar, Ankara 06500, Turkey 2. Photonics Research Center, University of Gazi D-Block,Teknikokullar, Ankara 06500, Turkey 3. Department of Physics, Azerbaijan National Academy of Sciences, 1001 Az, Baku, Azerbaijan Republic Received: August 16, 2013 / Accepted: August 30, 2013 / Published: September 10, 2013. Abstract: In this study, porous silicon layers manufactured by using (100), 1-5 ohmcm p-type(boron doped) wafer by electrochemical etching in HF ethanol solution. Photoluminescence (PL) spectra, Fourier transform infrared spectroscopy (FTIR) features of anodically etched silicon obtained for different conditions studied and surface characteristics are investigated by atomic force microscopy (AFM). The room temperature PL spectra of chosen two samples prepared show a characteristic peak located at 652 nm (red) and 439 nm (blue). Obtained blue emission is high intense and stable. The porous layer of blue emitting sample is treated with acetone and HF in order to discern the blue PL mechanism source. Analysis of the FTIR data shows that the photoluminescence at this wavelength (439 nm) is not due to the oxide related defects and the carbon contamination but based on the porosity and surface related characteristics such as, the ratio of distance between pores and diameter of the pores obtained from AFM data. The blue emitting porous layers are obtained only by electrochemical etching without using special way of oxidizing, post illumination as done in many studies. The result may aid the development of light emitting diodes (LEDs), displays and photo detectors in the ultraviolet region which can be achieved by using only electrochemically etched silicon. Key words: Porous silicon, PL, FTIR, AFM, blue glow.

1. Introduction
Most common and easiest method of manufacturing porous silicon is electrochemical anodization. The foundation of porous silicon (PS) was first discovered in 1956 by Uhlir during silicon electro polishing experiments on silicon (Si) wafer by using hydrofluoric acid (HF) as an electrolyte while trying to etch the silicon. Under appropriate electrochemical conditions (current, HF concentration, doping concentration, etc.) it was observed that the silicon is not peeled of layer by layer, it preferred to form pores on it growing in the direction of the substrate [1]. Porous Si opens up exciting possibilities for creating optical devices in silicon and integrating electrical and optical devices with Si-based circuits. The

Corresponding: afak Doan, Ph.D. student, research field: solid state. E-mail: safak.dogan@selex-comms.com.tr.

characteristics of the PL change as the wavelength of emission changes from ultraviolet wavelengths to infrared wavelengths [2]. In 1990, the Photoluminescence of porous silicon firstly demonstrated in room temperature and gained much importance to define the mechanism behind this. Many models purposed to define the luminescence mechanism [3, 4]. In much studies, scientists give much attention to the red band emission of porous silicon because of the efficiency and stability of the PL peak and ease of obtaining [5-7]. In the literature, it is stated that the PL of the blue band is obtained when the sample contains a large amount of oxygen which has been achieved by oxidation, such as the exposure to boiling water [8]. Different to the oxidation process, blue PL can be achieved by applied illumination after anodized samples by white light without any oxidation processes

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and no direct evidence of surface oxides [9]. For the samples produced by post illumination, the intensity decays with time and not uniform across the material [4]. In rapid thermal oxidation (RTO) method and low temperature oxidation method after ageing, the full width half maximum (FWHM) of the PL increases and the red shift of obtained blue PL peak occurs [4]. It is stated that [10] to expand the band gap in order to obtain blue wavelength from porous silicon is limited due to the required limitation of the physical size of Si nanostructures which weakens the formed layers and results in fragile [11] and unaccepted layers for device fabrication. In some theoretical studies, it is stated that obtaining blue or shorter wavelength PL from porous silicon is achieved if Si crystal size is reduced to 20 or less. Very small physical sizes in the etched silicon can lead to quantum confinement effect based on a particle in box [12], calculated wire diameter 30 and corresponding PL peak data deep red in color. Quantum confinement energy calculated by pseudo potential technique [13], wire size of exceeding 25 obeys effective mass theory and blue light emission is achieved with wire diameter of 15 . Sanders [14] used semi-empirical tight binding model based on silicon atomic orbital and obtained 13.5 wire diameter is needed to obtain blue light. Confinement energy is also calculated by using a linear combination of atomic orbital [10] and 20 A particles can emit blue light. In this study, we report a stable, high intense blue luminescence from freshly prepared layer and it is stable exposure to ambient air after four mounts. No special method such as oxidizing or post illumination is used for manufacturing porous layers in order to obtain blue luminescence. The resulted layers are suitable for obtaining blue peak and the study states the contribution of species are not playing role for this kind of luminescence and the origin of the luminescence is included also by examining the AFM data and porosity calculated.

2. Materials and Methods

Porous silicon manufactured at room temperature and ambient light on silicon wafers of one side polished, p-type, boron doped, (100) oriented with 1-5 ohmcm resistivity and 381 20 m thickness. In the following study, the samples will be named as S1 (HF: Etanol-1:2, etching time 20 min) which emits in red color and S2 (HF:Etanol-1:3, etching time 60 min) which emits in blue color. A Pt mesh is used as cathode and during the anodization. To provide and guarantee the homogeneity of the porous layer magnetic stirring [15] is used. Etching time and anodization current were 60 min and 10 mA/cm2 for S2 and 20 min and 10 mA/cm2 for S1 and S2, respectively. After the anodization, the samples were quickly rinsed in DI water and 5 5 min DI water ultrasonic washing was done. Then the samples were dried by Argon.

3. Results and Discussion

Freshly prepared samples are excited by He-Cd laser at a wavelength of 325 nm with a low laser power of nearly 50 mW, and a strong visible blue luminescence is observed by naked eye. PL measurements were taken by using the Jobin Yvon Florong-550 PL system with a 50-mW He-Cd laser ( = 325 nm) as excitation light source at room temperature and the corresponding PL spectrum of the freshly prepared porous layers of sample S1 and S2 are given with the following Fig. 2; from the Fig. 2 chosen

Fig. 1 Schematic of Etching Cell.

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Fig. 2 PL Spectrum of freshly prepared porous layers.

two samples of prepared for various anodization conditions show different PL characteristics. To determine the stability of blue luminescent layer (S2), the porous layer of S2 aged at room conditions about four mounts and corresponding PL data recorded and no significant change observed as seen from Fig. 3. In order to understand the luminescence mechanism and if the blue emission is related to carbon contamination [16] the samples were rinsed in acetone for 1 h. With this treatment insignificant degradation of the luminescence is observed and the peak position almost remains same. The spectrum is relatively sharp and the peak position is located at about 439 nm and 437 nm before and after acetone washing, respectively. The oxide related effects playing an important role in blue luminescence [16] the layer is dipped in HF and also insignificant change in PL data as in Fig. 3. Fig. 4 includes PL data of freshly prepared porous silicon (S2), 4 mounts after the layer prepared (S2), after 1 hr acetone washing and HF dipping (S2). It is seen from Fig. 3 the photoluminescence peak intensity is 439 nm and the band width is 82 nm before and the after four mounts at atmospheric conditions. No change observed due to the aging of the sample at room conditions which shows the luminescence is stable and does not decay with time. After the surface acetone treatment only insignificant blue PL shift occurred and the band width decreased. Also insignificant PL blue shift observed due to surface HF treatment with increasing band width. In order to determine the blue luminescence source and identify the chemical composition FTIR spectrum

Fig. 3 PL spectrum of porous layer (S2), four mounts after preparation, porous layer after acetone treatment and porous layer after HF dipping.

Fig. 4 FTIR spectrum for freshly prepared porous layer, porous layer four mounts after preparation, after acetone treatment and after HF dipping.

of freshly prepared porous silicon(S2) (7,500-400 cm-1) aged for four months and after surface chemical treatments were recorded on a Bruker Vertex 80 IR Spectrometer and as given below; There are four distinct peaks with different intensities. The peak at 613 cm-1 is the most intensive one and it is related with the Si-Si bonds. The peak near 892 cm-1 is related with the SiH2 scissoring (24) and peak at 1,107 cm-1 is the Si-O-Si (18, 23) asymmetric stretching (oxide absorption band). The observed modes of from the FTIR transmission spectrum are at the frequencies 613 is Si-Si bonds[17], 892 cm-1 is the SiH2 scissoring (24) and 1,107 Si-O-Si asymmetric stretching(oxide absorption band) [18, 19]. In Fig. 4 it is observed that the FTIR spectrum for the observed frequencies of 613, 892 and 1,107 cm-1 does not change with time and surface chemical treatments.

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This is an indirect evidence of the blue luminescence of the porous layer is not due to the oxide related defects and carbon contamination. In order to explain the luminescence mechanism of porous layers S1 and S2 AFM measurements were done and the related results are given below; Fig. 5 shows the 2D and 3D views of sample S1 (red glowing) and S2 (blue glowing). From the AFM measurement data a great difference of pore diameters are observed. In sample S1 there are small pores on the order of 0.75 m and the S2 have larger pores with 2.23 m which directly contributes to the porosity is thought to the source of blue shift in PL measurement data. As the S2 has been treated with chemicals of acetone and HF the corresponding AFM data recorded before and after insignificant change observed. The diameter of the dominant pores of S1 sample and
Sample S1

S2 samples averaged over 4 points are 0.75 m and 2.23 m measured from 2D AFM views. The wall distances maximum and minimum are averaged also 4 points and found as 0.68 m & 0.5 m for sample S1 and 0.5 m & 0.2 m for sample S2. The corresponding q/d and m/d are 0.91 & 0.67 and 0.2 & 0.08 for S1 and S2 samples respectively which directly contributes the porosities of the layers. As seen from AFM data given by Figure 5, the pore diameter is large for sample S2 compared with sample S1. The calculated q/d & m/d gives a hint about porosities [20]. As the FTIR data of sample S2 treated with chemicals does not show any difference of observed modes is not used to explain the blue luminescence of the layer and the related porosities of the samples are calculated which is important for the wavelength of the emission.
Sample S2 (freshly prepared)

(a)

(b)

(c)

(d)

Fig. 5 AFM Data(30 m 30 m) porous silicon samples (a) 2D view of Sample S1; (b) 2D view of Sample S2; (c) 3D view of Sample S1 and (d) 3D view of Sample S2

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P=

m1 m2 m m3 and d = 1 m1 m3 S

Fig. 7 Schematic representation for porosity calculation.

4. Conclusions
Fig. 6 Schematic view of pores with diameter (d) and the ratios of the maximum (q) and the minimum wall thickness (m) as a function of porosity (P) [19].

It is stated that the PL peak shows blue shift as the porosity increases [21] and also for PS layer of > 80% porosity shows a green-blue to [22] blue peak emission, otherwise it should exhibit a red peak emission. To understand the source of blue PL peak the porosity of the samples are calculated and found to be 49% for sample S1 and 85% for sample S2 with the method given in the paper. The thickness of the porous layer can be measured by profilometer as given in the reference [23] by Veeco Dektak 150 stylus profilometer. The porosity is calculated as given in Fig. 7, by combining the gravimetric method and thickness measured from profilometer ; Not only the porosity plays role on luminescence mechanism alone but also the ratio of the distance between the pores and pore diameter is needed to be taken in consideration which directly contributes the porosity values. The obtained porosity of sample S2 is 85% by the method [22] is thought to explain the blue luminescence of the porous layer.

The freshly prepared porous layer glows blue when exited by the laser with wavelength 325 nm. This layer aged four mounts in air condition and the PL measurement data of freshly prepared silicon sample S2 and four mounts after preparation show that they have the same peak position of 439 nm and FWHM of 82 nm with the same intensity which indicates that the observed blue photoluminescence peak is stable and does not change in time. To discern the blue light mechanism, the layer is washed with acetone, before and after the surface treatment PL and FTIR measurements were done and surface treatment of porous silicon sample S2 with acetone and HF does not exhibit significant difference in PL spectrum and also the modes in FTIR data as given in the results and discussion part which may show the blue light luminescence is not from the carbon contamination and oxide related defects. The pore diameter obtained from AFM data and porosity calculated in sample S2 are large compared to the sample S1, ratio of the distance between the obtained pores and diameter of S2 is 1/5 (minimum wall distance) &1/9 (maximum wall distance) of the sample S1, calculated porosity which is 85% and the ratio of distance between pores and the pore diameter of sample S2 play role of blue luminescence.

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Stable Blue Luminescence of Porous Silicon a vertical optical cavity, Appl. Phys. Lett. 69 (1996) 2965. [10] J.P. Proot, C. Delerue, G. Allan, Electronic structure and optical properties of silicon crystallites: Application to porous silicon, Appl. Phys. Lett. 61 (1992) 1948. [11] F. Namavar, Silicon-based Blue Light Emitting Diode, Final Report submitted to U.S. Army Research Office (1994) 1. [12] N.S. Averkiev, V.M. Asnin, A.B. Churilov, I.I. Markov, N.E. Mokrousov, AYu. Silov, et al., Fine structure of the red photoluminescence band of porous silicon, JETP Lett. 55 (1992) 657. [13] A.J. Read, R.J. Needs, K.J. Nash, L.T. Canham, P.D.J. Calcott, A. Qteish, First-principles calculations of the electronic properties of silicon quantum wires, Phys. Rev. Lett. 69 (1992) 1232. [14] G.D. Sanders, Y.C. Chang, Optical properties of free standing silicon quantum wires, Appl. Phys. Lett. 60 (1992) 2525. [15] J.C. Lin, M.K. Hsu, H.T. Hou, S.H. Liu, Improvement of photoluminescence uniformity of porous silicon by using stirring anodization process, World Academy of Science, Engineering and Technology 61 (2012) 236. [16] Y.S. Kim, K.Y. Suh, H. Yoon, H.H. Lee, Stable blue photoluminescence from porous silicon, Journal of the Electrochemical Society 149 (2002) 50. [17] I. Mihalcescu, M. Ligeon, F. Mullen, R. Romestain, J.C. Vial, Surface passivation: A critical parameter for the visible luminescence of electrooxidised porous silicon, J. Luminescence 57 (1993) 111. [18] K.L. Pong, S.C. Chen, K.W. Cheah, Photoluminescence of laser ablated silicon, Solid State Communications 99 (1996) 887. [19] K. Hong, C. Lee, Dependence of electromagnetic wave absorption on ferrite, particle size in sheet-type absorbers, Journal of the Korean Physical Society 42 (2003) 671. [20] L. Lehmann, U. Gsele, Porous silicon formation: A quantum wire effect, App. Phys. Lett. 58 (1991) 856. [21] P. Kumar, P. Huber, Effect of etching parameter on pore size and porosity of electrochemically formed nanoporous silicon, Journal of Nanomaterials 2007 (2007) 1. [22] A.M. Alwan, Calculation of energy band gap of porous silicon based on the carrier transport mechanism, Eng. & Tech. Journal 25 (2007) 1143. [23] K. Behzad, W.M.M. Yunus, Z.A. Talib, A. Zakaria, A. Bahrami, E. Shahriari, Effect of etching time on optical and thermal properties of p-type porous silicon prepared by electrical anodisation method, Advances in Optical Technologies 2012 (2012) 1.

No significant change observed in the AFM data and porous layer thickness from profilometer of freshly prepared porous layer and after surface treatments, so the porosities remains same after surface treatments which confirms the PL data after. Briefly, the obtained blue emission is not caused from any carbon contamination and oxygen defects that can be explained with the porosity and the ratio of distance between pores and the pore diameter.

Acknowledgments
This study is supported by Republic of Turkey Ministry of Development with the project number 211K120290.

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