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Photoluminescence of copper-doped porous silicon

Y. M. Huang
Materials Research Center, Nanyang Institute of Science and Technology, Nanyang 473066, Henan,
People’s Republic of China
~Received 25 September 1995; accepted for publication 26 August 1996!
In this letter, we report the results of copper-doped porous silicon. In the photoluminescence
spectrum of porous silicon without Cu doping, only one red luminescence band appears with a peak
at 676.5 nm; while in the photoluminescence spectrum of Cu-doped porous silicon, red and near
infrared luminescence bands appear with peaks at 660.6 and 802.2 nm, respectively. Energy
dispersive x-ray spectroscopy and Fourier transform infrared spectroscopy indicate the near infrared
luminescence band is related to copper impurity in porous silicon. We assign the red luminescence
band to band-to-band emission, and the near infrared luminescence band to band-to-acceptor
emission. © 1996 American Institute of Physics. @S0003-6951~96!02745-3#

Because the discovery of visible photoluminescence about peak position and FWHM were obtained by Gaussian
~PL! in porous silicon ~PS! has enormous potential applica- curve fitting the corresponding spectrum.
tions in silicon-based optoelectronics, there is great interest Figure 2 shows the energy dispersive x-ray ~EDX! spec-
in PS.1–3 Doping is the most widely used method for impart- tra of the control PS sample and the Cu-doped PS sample.
ing the required properties to semiconductor materials, and Curve ~a! is the EDX spectrum of the control PS sample, and
materials doped with deep-level impurities, are used exten- curve ~b! is the EDX spectrum of the Cu-doped PS sample. It
sively in modern microelectronics. For example, copper, the is obvious that: ~1! the Au- and Si-related peaks appear in
best known activator of efficient luminescence in II–VI com- both curves, of which the Au-related peaks are due to speci-
pounds, introduces a series of broad luminescence bands men coating; and ~2! characteristic lines from Cu appear only
throughout the visible and into the near infrared spectral re- in curve ~b!. Quantitative analysis indicates that copper con-
gion. Among the impurities used for doping, a special place centration in Cu-doped PS varies from 1.75 to 6.1 at. % at
is occupied by transition metals. Therefore, we surmise, the different measurement spots. Whether the copper is on the
optical properties of transition-metal doped PS may possibly surface or actually internal to the silicon, will require further
contain much more information about carrier recombination. research.
It shall be the purpose of this letter to report on the results of Figure 3 shows the Fourier transform infrared ~FTIR!
transition-metal ~copper! doped PS, and to try to understand absorption spectra of control PS sample and Cu-doped PS
the basic physical mechanisms involved in carrier recombi- sample. Curve ~a! is the FTIR absorption spectrum of the
nation. control PS sample, and curve ~b! is the FTIR absorption
PS films were formed in a boron-doped, p-type silicon spectrum of Cu-doped PS sample. It is obvious that: ~1! hy-
wafer of ~100! orientation and resistivity of 15 V cm. Silicon drogen and oxygen related absorption peaks appear in both
wafers were etched in a 1:1 mixture of HF ~40 wt %!: H2 O at curves; ~2! one absorption peak appears at 1720.3 cm21
100–145 mA/cm2 for 10 min. Gravimetric porosity of PS ~0.213 eV! in curve ~b!; and ~3! a small hump appears at
films was around 86%. The typical thickness of the PS films
was about 32 mm. Each PS sample was cut into halves: one
was used as a control sample, and the other was dipped into
dilute ~;0.002 mol! aqueous CuF2 solution for about 5 s. In
this letter, CuF2 immersed PS samples are denoted as Cu-
doped PS samples. PL spectra of the control PS samples and
Cu-doped samples were performed at room temperature em-
ploying a spectrometer ~SPEX 1404!. An argon ion laser was
used as a light source, having an emission wavelength of
514.5 nm and a power output of 10 mW.
Figure 1 shows the PL spectra of one pair of the control
PS sample and Cu-doped PS sample. Curve ~a! is the PL
spectrum of the control PS sample. This is a red lumines-
cence band with a peak at 676.5 nm ~1.833 eV! and full
width at half-maximum ~FWHM! of 0.318 eV. Curve ~b! is
the PL spectrum of the Cu-doped PS sample, which consists
of two luminescence bands: one red luminescence band with
a peak at 660.6 nm ~1.877 eV! and FWHM of 0.316 eV;
another near infrared luminescence band with peak at 802.2
nm ~1.546 eV! and FWHM of 0.126 eV. For clarity, curve FIG. 1. Photoluminescence spectra of one pair of ~a!: a control porous
~b! was shifted upwards 80 arbitrary units. All the values silicon sample; and ~b!: a Cu-doped porous silicon.

Appl. Phys. Lett. 69 (19), 4 November 1996 0003-6951/96/69(19)/2855/3/$10.00 © 1996 American Institute of Physics 2855
FIG. 4. Proposed energy diagram for Cu-doped porous silicon.

FIG. 2. Energy dispersive x-ray spectra of ~a!: a control porous silicon

sample; and ~b!: a Cu-doped porous silicon. ally considered to be at E v 10.24, 10.37, and 10.52 eV.4,5
The E v 10.24 eV level has been ascribed to Cu atoms, but
2949.2 cm21 ~0.366 eV! in curve ~b!, as shown in the inset. some workers ascribe it to Cu–O complexes.4 The E v
This small hump is not due to water in the samples, because 10.52 eV level is sometimes thought to be related to thermal
three absorptions in water molecules have been reported in lattice defects.4 Akhmedova et al. found one E v 10.22 eV
literature locating at 1595 cm21 ~symmetric bending!, 3652 level in Cu-doped silicon.6 Theoretical calculations indicate
cm21 ~symmetric stretching!, and 3756 cm21 ~antisymmet- donor or acceptor levels are practically independent of par-
ric stretching!, respectively. In our FTIR absorption spectra ticle size in porous silicon.7 So we surmise that copper has
of water contaminated PS samples, no small humps were introduced two deep levels into the band gap of Cu-doped
detected near 2949 cm21 . We have also noted that Cu-doped PS, and absorptions at 0.213 and 0.366 eV are possibly
PS is much more oxidized. However, this enhanced oxida- caused by electron excitation to E v 10.213 eV and E v
tion is not sufficient to produce the additional PL peak in our 10.366 eV deep levels from the valence band of PS.
experiment. We stored the control PS sample in high purity The origin of the efficient visible luminescence of PS is
oxygen ~as well as in wet oxygen and in H2 O2 ! for further extensively studied, but unfortunately, the physical mecha-
oxidation. With the progress of oxidation, no additional peak nisms responsible for the light emission of PS are not clari-
was observed in its PL spectrum, although the red lumines- fied completely yet. Several models have been proposed in
cence band shifted. No data are available for Cu impurity in trying to elucidate the origin of PL in PS, one of the most
PS, but it is well known that transition metals give rise to a possible candidates is the quantum confinement model with
sequence of levels deep in the band gap of silicon. Previous emphasis on recombination in small silicon crystallites.1 Our
studies have shown that, in Cu-doped silicon, the presence of results in Figs. 2 and 3 indicate the 1.546 eV near infrared
copper has been associated with three acceptor levels gener- luminescence band is related to copper impurity in PS. It is
well known that deep centers act primarily as carrier traps or
recombination centers. In the case of our experiment, we are
inclined to agree that the increase in the band gap of nano-
scale silicon is due to quantum size confinement after taking
into consideration two facts: ~1! the peak energy values in
the PL spectra of both PS samples are much higher than the
band-gap value of crystalline Si; and ~2! only one particle
size distribution exists in our Cu-doped PS samples.8 In or-
der to illustrate carrier recombination processes, we present,
in Fig. 4, a schematic picture of excitation and recombination
processes for Cu-doped PS. Under the excitation of laser,
electrons in the valence band are excited up to the conduc-
tion band. After relaxation, the generated electrons are back
to the bottom of the conduction band, and the holes back to
the top of valence band, respectively. Then, the electrons can
recombine with holes by transition from conduction band to
valence band, or by transition from conduction band to ac-
ceptors. These recombination processes cause band-to-band
emission, which results in the 1.877 eV red luminescence
FIG. 3. Fourier transform infrared absorption spectra of ~a!: a control porous band, and band-to-acceptor emission, which results in the
silicon sample; and ~b!: a Cu-doped porous silicon. 1.546 eV near infrared luminescence band, respectively. Un-

2856 Appl. Phys. Lett., Vol. 69, No. 19, 4 November 1996 Y. M. Huang
is the PL spectrum of the corresponding Cu-doped PS
sample. It can be decomposed into two luminescence bands
~solid curves in Fig. 5!: one luminescence band with a peak
at 596.3 nm ~2.079 eV!; another luminescence band with a
peak at 712.2 nm ~1.741 eV!. These results can also be ex-
plained in a similar way. Compared to Fig. 1, it is obvious
that, by blueshifting the PL peak energy, the Cu-related peak
is also shifted systematically. In Fig. 1, the size of the copper
related PL peak relative to the band-to-band peak, is much
smaller than in Fig. 5. This is because the detector response
is dropping off rapidly by 800 nm in Fig. 1.
In summary, we have observed two luminescence bands
in the Cu-doped PS sample, one red luminescence band, an-
other near infrared luminescence band. Our experimental re-
sults indicate the near infrared luminescence band is caused
by copper impurity in PS. The red luminescence band is
assigned to a band-to-band transition, and the near infrared
FIG. 5. Photoluminescence spectra of another pair of ~a!: a control porous luminescence band to a band-to-acceptor transition. Blue-
silicon sample; and ~b!: a Cu-doped porous silicon.
shifting the PL peak energy can also shift the Cu-related
peak systematically. We believe the present result will con-
der our assumptions of ~1!: the band gap of Cu-doped PS is tribute to the fundamental understanding of the complicated
1.877 eV, and ~2!: one of the deep levels is 0.366 eV above properties of PS.
the valence band, the peak energy of the near infrared lumi- The author would like to thank Dr. K. P. Chik, Dr. S. K.
nescence band should be 1.511 eV. Our measured peak en- Hark, and K. W. Tong for their support and assistance in this
ergy of the near infrared luminescence band is 1.546 eV. work.
Three causes may be responsible for the 0.035 eV discrep-
ancy: ~1! our experimental error; ~2! the precise nature of
copper impurity in PS is not fully understood yet; and ~3! 1
L. T. Canham, Appl. Phys. Lett. 57, 1046 ~1990!.
other recombination processes ~i.e., via shallow levels! may 2
F. Koch, V. P. Koch, and T. Muschik, J. Lumin. 57, 271 ~1993!.
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exist, too.
Phys. Lett. 64, 3282 ~1994!.
To check our explanation, we fabricated PS samples that 4
J.-W. Chen and A. G. Milnes, Annu. Rev. Mater. Sci. 10, 157 ~1980!.
had a higher peak luminescence energy, and then doped 5
L. A. Hemstreet, Phys. Rev. B 15, 834 ~1977!.
these samples with copper. Figure 5 shows the PL spectra of M. M. Akhmedova, L. S. Berman, L. S. Kostina, and A. A. Lebedev, Sov.
Phys. Semicond. 10, 1400 ~1976!.
another pair of the control PS sample and Cu-doped PS 7
C. Delerue, M. Lannoo, G. Allan, and E. Martin, Thin Solid Films 255, 27
sample. Curve ~a! is the PL spectrum of the control PS ~1995!.
sample with a single peak at 628.7 nm ~1.972 eV!. Curve ~b! 8
Y. M. Huang, Solid State Commun. 97, 33 ~1996!.

Appl. Phys. Lett., Vol. 69, No. 19, 4 November 1996 Y. M. Huang 2857