Size dependent photoluminescence of SiC nanocrystals

M. Morales Rodriguez1, A. Díaz Cano2, T. V. Torchynska2, G. Polupan3 and S. Ostapenko4

1
PCIM, Universidad Autónoma Metropolitana, Azcapotzalco, Mexico D.F. 02200 , Mexico
2
ESFM and 3ESIME-National Polytechnic Institute, Mexico D.F. 07738, Mexico
4
NNRC at University of South Florida, Tampa, FL 33620, USA

The paper presents the results of porous SiC study using photoluminescence and scanning
electronic microscopy. It is shown that the intensity of defect-related PL bands (2.08, 2.27, 2.44 and
2.63 eV) increases monotonically with the rise of PSiC thickness from 2.1 up to 12.0 µm. These
luminescence centers are assigned to surface defects which appear at the PSiC etching process.
Photoluminescence intensity stimulation for surface defects is attributed to rise of defect
concentrations with increasing of porous layer thickness and to realization of the hot carrier
ballistic mechanism at surface defect excitation. Intensity enhancement for exciton-related PL
bands (2.79, 2.98 and 3.26 eV ) is attributed to increasing the exciton recombination rate as result
of exciton weak confinement in big size SiC NCs of different polytypes (6H-PSiC with inclusions
of 15R- and 4H-PSiC).
Key words: photoluminescence, SiC nanocrystals, electron-hole confinement,
PACS: 78.55.Mb, 78.67.Hc, 73.21.Hb.

Introduction.
The big interest in last 10 years appears to the different applications of SiC nanocrystal

(NC) structures. The large SiC band gap makes SiC NCs a good candidate for light emitters and

color displays. The high chemical and thermal stability of SiC NCs make them very promising for

using in harsh environments. Biocompatibility and blood compatibility of SiC NCs can be

potentially useful in biology [1].

The most typical SiC NC systems include porous SiC (PSiC) layers, SiC NCs embedded in

different (inorganic or organic) matrices, as well as SiC nanowires, nanorods or nanotubes. Porous

SiC has been studied extensively in the last ten years for potential application as nanoscale

light emitters for blue and UV spectral ranges [2-4]. It was shown that luminescence of

PSiC can span a wide spectral range from 1.8 up to 3.2 eV and strongly depends on

fabrication regimes. The mechanism of this luminescence are still under discussion.
 At the same time some prospective applications of SiC-based homoepitaxial [5, 6]

or GaN-based heteroepitaxial [7, 8] device structures formed on PSiC substrates have been

presented as well. Despite the technological progress, fundamental properties of SiC NCs

and methods of NC characterizations for future technological applications are under

developing. This paper presents the results of PSiC characterizations using

photoluminescence (PL) and scanning electronic microscopy (SEM).

Samples and Experimental setup.

The PSiC layers were formed by surface anodization of n-type 6H-SiC substrate

with resistivity of 0.052 Ώ cm and orientation (0001) in 3% aqueous HF solution at the

permanent dc etching current density 80 mA/cm2 and variable durations: 1min (PSiC1),

3min (PSiC2), 6min (PSiC3) without external illumination (Table 1). After the surface

anodization, PSiC layers were RIE plasma treated for 2 minutes with the gas flow components

O2:H2:SF6 = 2:1:4 at room temperature.

Photoluminescence (PL) was measured using SPEX 500 spectrometer coupled with

a photomultiplier at the temperature of 4.2-80 K under the excitation by 325nm He-Cd laser

line with up to 55mW power. A thickness of porous layers (Table 1) and the morphology

were estimated using planar and cross sectional SEM images, obtained on XL-FEG (FEI-

Sirion).

Results and discussion.

The typical SEM image of PSiC is presented in figure 1. As it follows from cross-

sectional SEM results (not presented) the thickness of PSiC layers varies from 2.1 up to

12.0 µm versus etching durations (Table 1). Diameters of pores are of 100-400 nm. The

diameter of SiC wires decreases from 200-250 nm (Fig.1) down to 50-70 nm with PSiC

porosity increasing at the duration rise from 1 to 6 min, respectively.

 PL spectra of bulk SiC and PSiC layers are presented in figure 2. The PL spectra are

obviously a superposition of strongly overlapping sub-bands and could be numerically

deconvoluted on a set of individual components in a spectral range of 1.20 – 3.40 eV (Fig.2

and 3). The spectrum of bulk SiC includes low energy PL bands (1.26, 1.50, 1.78 and 2.63

eV) only (Fig.2, curve 1). PSiC spectra include low energy PL bands (group 1) with peak

positions at 1.78 (8), 2.08 (7), 2.27 (6), 2.44(5) and 2.63eV (4) and a half-width from the

range of 200-400 meV, as well as high energy PL bands (group 2) with maxima at 2.79 (3),

2.98 (2) and 3.26eV (1) and half-widths 150-200 meV (Fig.2 and 3).

PL bands with the peaks at 1.26, 1.50 and 1.78eV dominate in a PL spectrum of the

bulk SiC (Fig.2). Integrated intensities of these PL bands increase with temperature rising

from 4.2 up to 80K (Fig.4a). Temperature related PL enhancement in indirect band gap

crystals, as a rule, is attributed to the stimulation of phonon assisted recombination

processes.

The high energy PL bands (2.79, 2.98 and 3.26 eV) in PSiC have narrower half-

widths, which allow assigning them to exciton recombination in SiC NCs of different

polytypes. We have shown in [9] based on Raman scattering data that investigated SiC

wafers are comprised of 6H-SiC with inclusions of 4H-SiC and 15R-SiC polytypes. It was

shown earlier [10] that free exciton PL bands in SiC polytypes exhibit the peaks at: 3.26 eV

(4H-SiC), 2.86 eV(indirect) and 3.00eV(direct) for (6H-SiC) and 2.99eV (15R-SiC) at

4.2K. The exciton related nature of high energy PL bands in studied samples is confirmed

as well by their temperature dependences (Fig.4b). The integrated intensity of PL bands

(2.79, 2.98 and 3.26 eV) decreases versus temperatures with small activation energies from

the range 11.5-12.0 meV typical for exciton bonding energy.

 Low energy PL bands in PSiC layers (1.78, 2.08, 2.27, 2.44 and 2.63eV) can be

attributed to defect related PL. The first PL band with the peak at 1.78eV deals with bulk

SiC defects which were inherited, apparently, from the SiC wafer. Note that a set of defect

related PL bands in the green-yellow spectral range with peak energy 2.43, 2.22, 2.07 and

1.93eV was studied earlier in PSiC layers and is assigned to defect states produced at

etched SiC surface [2-4].

It is essential that in our case the integrated intensity of defect-related PL bands (2.08,

2.27, 2.44 and 2.63eV) monotonically enlarges when PSiC layer thickness increase from

2.1 up to 12.0 µm (Fig.5a). At the same time the SiC NC size decreases and surface area

rises (Table 1). The integrated intensity of these PL bands does not depend on the

temperature in the range of 4.2 - 80K. Both these facts permit to attribute four PL bands

(2.08, 2.27, 2.44 and 2.63eV) to defect related states produced on PSiC surface at chemical

etching.

Physical reasons for intensity enhancement of defect related PL bands in PSiC with

SiC NC size decreasing can be connected with the rise of radiative recombination rate. The

later is due to the growth of surface area and defect concentrations and/or to the realization

of ballistic effect at hot carrier excitation of surface defect PL in SiC NCs. The last effect

was revealed earlier in porous Si and it leads to intensity stimulation of the red PL band

[11, 12].

Integrated intensities of high energy PL bands (2.79, 2.98 and 3.26 eV) increase with

PSiC thickness as well (Fig.5b). It is essential that at the same time the SiC NC size

decreases (Table 1). SiC NC sizes (60-250nm) are too large for quantum confinement

effects, which require a SiC NC size of 2-4 nm [1]. In this case the intensity stimulation of

exciton related PL bands with NC size decreasing can be attributed to exciton

recombination rate increasing due to the realization of electron-hole (exciton) weak

confinement in SiC NCs of different polytypes (6H-PSiC with inclusions of 15R- and 4H-

PSiC).

Acknowledgement. The work was supported by SIP-IPN, Mexico. Authors would like to thank

Dr. M. Mynbaeva from Ioffe Institute, St. Petersburg, Russia, for preparation of porous SiC layers.

References.

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Ostapenko, M. Mynbaeva, J. Appl.Phys, 97, 033507 (2005).

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This paper (#28) was presented on International Conference on Amorphous and

Nanocrystalline Structures, Colorado, USA, August 2007.

Figure captions

Figure 1: SEM images of the PSiC1 sample.

Figure 2: PL spectra of the bulk SiC (1) and PSiC samples (2-PSiC1, 3-PSiC2, 4-PSiC3).

Figure 3: PL spectrum deconvolution on eight elementary PL bands.

Figure 4a: Integrated intensity dependences for PL bands: 1.26 (1), 1.50(2) and 1.78 (3)

eV versus temperatures in the bulk SiC.

Figure 4b: Integrated intensity dependences for PL bands: 2.79 (1), 2.98 (2), and 3.26 (3)

eV versus temperatures in PSiC.

Figure 5a: Integrated intensity dependences for PL bands: 2.27(1), 2.08(2), 1.78(3),

2.44(4) and 2.63(5) eV versus thicknesses in PSiC layers.

Figure 5b: Integrated intensity dependences for PL bands: 2.79 (1), 2.98 (2) and 3.26 (3) eV

versus thicknesses in PSiC layers

 Fig.1

100 4
80
PL intensity (arb.un.)

60
3
40

20
2
0 1

1,2 1,6 2,0 2,4 2,8 3,2 3,6

Emission energy (eV)

Fig.2
 80

PL intensity (arb. un.)

60

40
4 3 2
20 5 1
8 7 6
0

1,0 1,5 2,0 2,5 3,0 3,5

Emission energy (eV)

Fig.3

11
Integrated PL intensity (arb. un.)

10
9 1
8
7 2
6
5
4
3 3
2
0 10 20 30 40 50 60 70 80 90
T (K)

Fig.4a
 40 100
a Ea1=0.0115 eV b

Integrated PL intensity
(I - I(T)) (arb. un.)
Ea2=0.0120 eV

Integrated PL intensity (arb. un.)

10 Ea3=0.0117 eV
30
1
2
1
3

0
0 20 40 60 80 100
20
103/T (K)
1
2
3
0 10 20 30 40 50 60 70 80 90
T (K)

Fig.4b

16

14
Integrated PL intensity (arb. un.)

12

10

8 5

6 4
3
4 2
2 1

0
2 4 6 8 10 12
Thickness of PSiC (µm)

Fig.5a
 18
16

Integrated PL intensity (arb. un.)

14
12 1
10 2

8 3
6
4
2
0
2 4 6 8 10 12
Thickness of PSiC (µm)

Fig.5b

Table 1. Parameters of PSiC layers

Samples Etching current Thickness (μm). SiC nanocrystal
density, mA/cm2 sizes, nm
PSiC1 80 2.1 213-253
PSiC2 80 6.3 80-150
PSiC3 80 12.0 50-70