AD-A266 293

Technical Document 2461

March 1993

Porous Silicon For

Pumping Solid-State
Lasers

S. D. Russell
W. B. Dubbelday
R. L. Shimabukuro

2,9993

Approved for public release: distribution Is unlimited.

I 93-14885
Ii•lc>l~lllllllll
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QUALITY AVAILABLE. THE COPY
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 Technical Document 2461
March 1993

Porous Silicon For Pumping

Solid-State Lasers

S. D. Russell
W. B. Dubbelday
R. L. Shimabukuro
 NAVAL COMMAND, CONTROL AND
OCEAN SURVEILLANCE CENTER
RDT&E DIVISION
San Diego, California 92152-5001
J. D. FONTANA, CAPT, USN R.-T. SHIEARER
Commanding Officer Executive Director

ADMINISTRATIVE INFORMATION
The research presented in this work was funded by the Office of Naval Rescarch.
Solid-State Laser (6.1.5) block program and in part by the NCCOSC. RDT&E Division
Independent Research (IR) program.

Released by Under authority of

G. A. Garcia, Head H. E. Rast
Research and Technology Solid State Electronics
Branch Division

ACKNOWLEDGMENTS
The authors thank Dr. E Hanson (NRaD. Code 843) and Dr. M. Sailor (Dept. of
Chemistry, UCSD) for making their labs available for the collection of photoemission
spectra, and S. Pappert (NRaD, Code 555) foi supplying the multiple quantum well Al-
GaAs/GaAs sample used in this investigation. The authors also thank
D. Gookin (NRaD, Code 843) for exchanging information concerning a novel applica-
tion for porous silicon, and Dr. V. Smiley (NRaD, Code 804) and Dr. A. Gordon
(NRaD, Code 0014) for funding this research. Finally, the authors thank Dr.
D. Szaflarski (ONT/ASEE postdoctoral fellow, now at Molecular Biosystems) and
P. Georgief (SDSU Foundation Student) for preparing some of the samples used
in this work.

SM
 CONTENTS

BACKGROUND ..................................................
DIODE-PUMPED SOLID-STATE LASERS ................... .
POROUS SILICON .............................................. 3
O BJE CT IV E ................................................... ........ 4
APPROACH .................................................... ... 4
D E LIV E RA BLES ..................................................... 4
PERIOD OF PERFORMANCE ....................................... 4
EXPERIM ENTAL RESULTS .............................................. 4
POROUS SILICON FABRICATION PROCESS ........................... 4
POROUS SILICON ON SAPPHIRE ..................................
QUANTUM EFFICIENCY OF POROUS SILICON ....................... 7
RECENT RESU LTS .................................................. If
FUTURE DEVELOPMENTS ........ ................................ 0

CO N C LU SIO N S ........................................................ I

R E FE R E N C E S ......................................................... I

FIGURES
1. Common energy levels for solid-state lasers . ............................... 2

2. Silicon band structure ................................................... 3

3 Photoluminescence spectra of porous SOS ................................. 6
4. SEM cross section of porous SOS ......................................... 7
5. Diode laser and porous silicon emission spectra ............................. 8
6. MQW and porous silicon emission spectra ....................... 9
A-oession For

NT:, FPO

-u:,t'......

I -

iii
 BACKGROUND

DIODE-PUMPED SOLID-STATE LASERS

Solid-state lasers have military, scientific, and commercial applications in. for example.
ranging, imaging, spectroscopy, nonlinear optics, and materials processing. Diode laser pump-
ing offers an all-solid-state laser with high efficiency in a simpler. more reliable, and compacl
system. These systems offer many improvements over the use of diode lasers themselves, in-
cluding narrower frequency linewidth. better beam quality. higher peak powers, and different
wavelengths. Diode lasers are attractive as pumps because they are compact, efficient, and re-
liable. However, since they are fabricated from III-V compound semiconductors. they are ex-
pensive. The emission wavelengths of diode lasers may be adjusted by varying the material
composition during wafer growth and precisely matched to coincide to peak absorption lines
by controlling the operating temperature. Therefore, diode pumps cause less undesirable
heating and produce no damage such as may occur when high-energy photons from flashlamps
are present in the pump light. In addition, because the diode pumps are partially coherent de-
vices, the output beams may be efficiently focused and optically coupled to spatially match the
solid-state laser mode.
Solid-state lasers operate in various manners and configurations, and virtually all of these
lend themselves to the use of diode pumps. The geometrical configurations include a rigid
cylindrical rod, a slab, and a flexible optical fiber. Solid-state lasers operate in CW, long-pulse
(jts time frame) and short-pulse (0-switched) forms. The emission may contain single or multi-
ple spatial or longitudinal modes. The use of diode pumps provides for several new pump-
resonator configurations; for example, transversely pumped rod or slab systems for pulsed
high-power multimode output, analogous to flashlamp-pumped systems, longitudinally CW
end-pumped rod systems for low-power output with high efficiency because of the ability for
optical mode matching in the lasing volume; and longitudinally pumped scalable slab or disc
systems for high CW power in the fundamental (TEM 0 0) mode by increasing both the radial
and longitudinal component of the pumped volume [1].
Diodes fabricated from AIGaAs with different concentrations of Al and Ga emit at wave-
lengths of about 800 nm, ranging from about 700 to 900 nm. These emission wavelengths coin-
cide well with the strong absorption bands of several currently important solid-state lasing
ions, including, for example, neodymium, holmium, erbium, and promethium. Typical pump-
ing requirements at the desired wavelength are tens of milliwatts to hundreds of milliwatts.
Threshold pumping values of 6-12 mW for Nd:NPP (Nd:P 5 0 14) and LNP (LiNdP 4 O; 2) with
reasonable efficiency have been reported [2]. Laser emission has also been reported from
Ho:YAG at 2.1 Rm, Er3+ : YLFat 2.8 Rtm, Nd:YAG at 0.946 Um, Nd : YVO 4 -at 1.06 .am. and
Nd:glass at 1.06 rim; these and others have been thoroughly reviewed in the scientific literature
[I -41. Figure 1 describes some common energy level schemes for solid-state lasing, and the
desired pump wavelengths [2]. This shows that pump sources emitting between 700 and 900 nm
may be employed to pump a large variety of laser hosts. Additional information can be ob-
t-i '7ed from,! KammsKHi [4J. I he host crystal tor these lasing ions plays a iole in Jie ime structure
of the absorption bands due to the Stark splitting by the crystal field, but does not substantially
change the required spectral region required for the efficient pumping of the ions into the
excited states desired for laser emission. For reference, the best optical efficiency in dil)de-
pumped solid-state lasers is 197' (Nd:YAG) [3] compared to 8t7,4 efficiency in a flashlamp-
pumped coaxially cylindrical Nd:glass rod, although more typically it is 51'4 with a flashlamp
with Nd,Cr:GSGG or Er, Tm, Ho:YAG [2]. Therefore, research into high-cfficiency pumping
schemes is ongoing.

112

Encrgy lee d~iagramof Nd' The lasw, ran,tii'fl a,, 5 h,,-i.f

ne-v irinc, diode pump tasmti, is light lines and in "elaxatmn
lines The fitestproposed diode pumped lasr transition ýaiasb .
nea- 06 pmn pumped at 880 nm o'3.1Repreventavive Stark splittinps oflthe
"viavirldsare showr on the right rand dier The, ac.ua lase in- ; iiV
Ocurtct weci these individual Stark splittinigs The open,box for the 11neipg 1-6ne j:o heeveS 2 W Pri1 ' "AidIrat W,
geo~und-startmanifold indicates that tie laser tranitwtonInthis manifiold Yb'* YAG, NIhTin. Wi 1 i
5ýd sie in O
to-' ' i',
5sto an energy lenl above the groundsltet It-nislet

i: 5
j _,j I
ci • •,.--÷ at

hnes TheI'irst
popo,,ed ioep ' pd
a .. lkn)lo i•"'¢:4. :[•S2•

ner
0 ,rnpur~e n Er8g tr •pllp•;O h ,r.natv

Pinn e .rom levelsonenrg rn.t~; r h•f ! for~ra - soidstt

. I
lasers (Fro ['2

OW
l n2 is

aa
in

5- a1 •"
it + i ,

E-nergylevel schcnmes itnEr)' rat '11.'1 'l,, 0)1 lll •1%/

~a
D she d Ilines Sn {I) in 'd tca le i pi i{n
nee n ~io |-ni') if
siilid s tat eI at'-
ve-I vi hei)e
,tat)[
Wv
ti m t" i
ii - 'rc
"A- -
-•'
d-rirsrn-ieiraied
a nlrt (h )iiii • YA
. . ,D,
, a 2y•
' I •
r•t aIpeivvi'+,hte
i antoi-in ai +•, : l u'lr el~
d
•i~gure 1. Common energy levels for solid-state lasers. (From [2].)

2
POROUS SILICON

Figure 2 shows the band structure for sing,c crystal sili- .

con [5]. Since the conduction band minimum does not have
the same crystal momentum (k) as the valence band maxi-
mum, the band gap (denoted byEg ) is an indirect gap. In
silicon, radiative recombination can only take place with the ,
V---
L
assistance of a phonon, making such transitions inefficient. ,
This has prevented silicon from being used as a solid-state -

source of light, unlike group III-V semiconductors, which , .

have a direct gap at the center of the Brillouin zone (F = 0).
° - --------
The discovery of photoluminescence in porous silicon has
therefore generated a new optoelectronic material for study
[6]. The typical emission spectrum of electrochemically
.,
-Z
I K
etched porous silicon is in the red, orange, and yellow region
(nominally 500 to 750 nm), although green and blue emis- 1
sions have also been demonstrated. A blue shift of the peak
emission wavelength has been shown by increased oxida- L fl,,
tion and etching of porous silicon [7] and by photochemical WA "frq
etching under illumination with high-energy photons*. At
this time, the light-emitting mechanism is not well under- Figure .Silicon band
stood, with three competing theories existing: quantum size structure.
effects [6,7], amorphous silicon radiative emission [81, and surface passivation species that
allow molecular radiative species that allow molecular radiative emission [9.10]. The fabri-
cation processes must be examined to elucidate the mechanism with a view toward engineering
the desired emission wavelength for solid-state laser pumping applications.
Recent research has suggested the potential of devices fabricated from porous silicon. The
photoemi ion from porous silicon was reported to exhibit an integrated intensity three times
greater than that of a commercial (AIGa)As LED [11]. This offers hope for an efficient light-
emitting device that is competitive with I11-V compound semiconductor devices. The demon-
stration of electroluminescence from porous silicon [12] was a key step in obtaining useful
optoelectronic devices. The implication of this milestone is that the scalability and large-scale
integration achievable in silicon microelectronics may be exploited in the fabrication of arrays
of light-emitting structures. This may lead to practical devices such as LEDs, superluminescent
diodes, or even silicon-based lasers (which may be achievable with further development).
Preliminary experiments at NRaD's Microelectronics Laboratory have demonstrated pho-
toluminescence in both bulk silicon and silicon-on-sapphire (SOS) prepared by chemical, pho-
tochemical, and electrochemical techniques [131. Porous silicon on a transparent substrate
(sapphire) presents advantages both for materials studies and possible device applications.
since the emission can be observed through the substrate, which may enable more efficient
pumping of solid-state laser host materials.

* Private communication from M. J. Sailor. Dept. of Chemistry, University of California. San Diego (UCSI)).

3
 OBJECTIVE
The objective of this research is to perform pre'iminarv experiments to examine the feasi-
bility of using porous silicon and related devices for pumping solid-state lasers.

APPROACH
The controlled fabrication of light-emitting silicon structures will be developed using
chemical, electrochemical, or photochemical techniques. Emphasis will be placed on tech-
niques compatible with the requirements for the VLSI device processing of wafer size and
etching uniformity. The optical and microstructural properties will be characterized using in-
house facilities. This will elucidate the emission mechanism, which may allow the required
engineering of the emission wavelength peak. In addition, variations in processing conditions
and in silicon film thickness on sapphire will be examined for more precise control of the
porous silicon thickpess. These methods may provide the means to control the peak wave-
length of the emission and may also allow control of the emitted linewidth. The photolumincs-
cence intensity from porous silicon will be quantitatively measured for comparison with com-
peting semiconductor pump sources.

DELIVERABLES
A preliminary report summarizing the experiments performed and conclusions was sub-
mitted 30 September 1992. The current technical document is the final deliverable and will
complete this preliminary study of the feasibility of using porous silicon as a solid-state laser
pump source.

PERIOD OF PERFORMANCE
The period of performance for this work was 1 June 1992 to 30 September 1992.

EXPERIMENTAL RESULTS

POROUS SILICON FABRICATION PROCESS

Porous silicon is commonly fabricated by the anodic oxidation of silicon in hydrofluoric
acid (HF) solutions [6,7,8-11]. A solution of equal parts of HF and ethanol is typically used in
a conventional electrochemical cell, with a platinum cathode and the silicon forming the
anode. Current densities from about 1 to 100 mA are passed through the solution, causing the
dissolution of the silicon and the creation of a physically porous structure with a reduction in
density. This technique was used in this work to fabricate thick porous silicon films on bulk
silicon, where it is simple to apply electrical contact to the backside of the sample (wafer). But
this technique is less valuable in the fabrication of porous silicon films on sapphire due to the
electrical insulation (> 106 £ - cmresistivity) of the substrate. In addition, the requirement of
obtaining highly uniform porous regions for future device applications suggests that an

4
investigation be conducted of fabrication techniquleS more compatible wiih conmentioln:l
VLSI processing. In this work, we demonstrated the first photochcmical fa rlcattion of porous
silicon, and also investigated chemical stain etches rpeportcd in the literature [14.151 as requir-
ing no electrical current.
The chemical stain etch used a solution of HF:FINO 3 :dcionized ft1O (1:5: P(1). Bulk silic0n
and SOS wafers were similarly processed. The bulk wafers were (100)-oriented B-doped ,i1i-
con with 3-5 Q-cm resistivity. The SOS samples were cpitaxially deposited silicon, boron-
doped in situ to 4 x 10 15 cm-, on 270-nm-thick SOS (1 X lt0I' cm-3) to a total silicorn
thickness of 10 lim. The etch solutions were prepared by reacting a square centimeter of silicon
with the HF:HNO 3 mixture for 2 minutes, causing an accumulation of tItNO,. the activc
oxidizer in the reaction [171. The chemical etch is a result of hole injection from the tNO(
oxidant into the silicon substrate via the following net reaction ! 161:
Si + HNO 3 + 6 HF --- H 2 SiFe + HNO 2 + H2 0 + H';
The reaction is catalyzed by the presence of NO 2 ions, and so there is usually an induction
period observed for the etching process. Deionized H_,O was subsequently added to the solu-
tion before the sample to be etched was immersed. Typical etch times ranged from I to 15 min-
utes. The samples were rinsed with deionized water, dried with nitrogen, and examined with a
hand-held ultraviolet lamp (Mineralight Model #S52). Generally, samples etched for less
than 1 minute did not luminesce, whereas SOS samples that are etched longer than - 15 min-
utes resulted in the complete dissolution of the silicon off the sapphire substrate.
We also demonstrated for the first time that photoluminescent porous sillcon is produced
via a photoinitiated chemical stain etch. For these experiments, (10())-oriented bulk silicon.
75As-doped to 1-1.8 Q -cm, were used. The n-type SOS samples were epitaxially deposited

silicon, phosphorous-doped in situ (1(0'cm-3), on 270-nm-thick SOS ('As-doped to

10 cm -3) to a total silicon thickness of 10 jim. The acid mixture of HF:FHNO, was diluted with
distilled H 20 (same ratios as above) and placed in optical quality cuvettes. The samples were
immersed in solution and illuminated for 2- 10 minutes using a 5-mW HeNe laser. For short
times, typically 1-minute etching occurs only in the regions where the sample is illuminated.
Patterns generated by double-slit diffraction produced distinguishable etched features of
about 30 ltm with both the bulk and SOS materials. As the illumination time increased. the
etching spread out to regions of the silicon which were not illuminated and small etched fea-
tures became washed out, which is consistent with the generation of holes required for the ca-
talysis of the etching mechanism described above. After the samples were rinsed with deion-
ized H2 0 and dried with nitrogen, they displayed visible orange photoluminescence upon UV
illumination. The porous silicon layer thickness was found by using scanning elector microcopy
(SEM) to be - 300 nm for samples irradiated 8 minutes.

POROUS SILICON ON SAPPHIRE

The photoluminescence spectra of etched samples were obtained using a defocussed (5
mW/cm ) 442-nm HeCd laser for excitation, and the emission was collected by a 0.25-mi
monochrometer with CCD detector. The collection spot size was about 1 mm in diameter.

5
Care was taken to record the emission spectra within fivc minutes of samnple pr.pairatIoM in
order to minimize the degradation of the luminescence, which in some cas,,e is ohsecrx.d %%tth
exposure to air. The porous SOS samples show photoluminescence signals comparable to
those published for p-type bulk silicon [14.15]. The photoluminescence spectra of 1(I-rm-thick
SOS etched for 9 minutes are shown in figure 3. The two curves shown arc the emission ,pctra
obtained when the sample was illuminated and emission ,as collected at the silicor ',ide
(dotted line) and at the sapphire side (solid line) of the wafer. The photoluminc,cenc_ maxi-
mizes in intensity at - 700 nm with a width of -10oo nm. The luminescence from the
Cr+ 3 impurity (695 nm) is pronounced in the sapphire-side illumination spectrum. The
similarity in the front and backside spectra suggests that there is uniformity in the porou,
structure with depth and that strain effects due to the lattice mismatch between the silicoon and
the sapphire are minimal.
I I II

SILICON SIDE

(,-" .' .9
I*
" "/
,
1 %

_ SAPPHIRE SIDE
U)
z
Z.

I I I I ,I ..
550 600 650 700 750 800 850
WAVELENGTH (nm)

Figure 3. Photoluminescence spectra of porous SOS.

Fabricating porous SOS allows for the accurate control of the depth of the porous laver.
Etching completely through the silicon layer to the silicon-sapphire interface allows control
of the porous layer thickness by controlling the thickness of the silicon. The latter is controlled
via either deposition techniques or oxidation/etch thinning processes, which are well-estab-
lished VLSI techniques. Experiments on 0.3-[rm-thick and 10-Ltm-thick SOS showed no signifi-
cant difference in the photoluminescence characteristics of peak emission wavelength or line-
width. The thicker porous layer did exhibit an increased luminescence intensity relative to the
thinner porous layer, which is attributed to the volumetric increase in the number of silicon
emitters.
Identically processed bulk porous silicon and porous SOS exhibit qualitatively different
emission when illuminated with a UV lamp. Bulk porous silicon, chemically etched as de-
scribed above, emits a vivid luminescence, whereas the I0-pm-thick porous SOS sample exhib-
its a hazy, diffuse luminescence emission. In order to understand these differences, the

6
morphology of the samples was analyzed by using SEM. l hc thickness of the porous lavcr i]
the bulk porous silicon is about 100 nm. Aith a surface roughnes.s of 10-20I nm. The poros
layer on the SOS sample is less discernible, but shows a comparable surface roughnes, as
shown in the SEM cross section in figure 4. Read"iy observable arc additional crevices and
cracks extending through the entire 10-gtm silicon lavcr on sapphire. 'Fhcse cracks ;'re attrib-
uted to preferential etching along threading dislocations and presumably cause diffuse §,tatter-
ing of the emitted photoluminescence. The dislocations arise from the thermal mismatch be-
tween silicon and the sapphire substratc which produces compressive stress in ihc silicron ,atvcr
during the deposition at high temperature and subsequent cooling. This stress is partiallk
relieved by the generation of threading dislocations. This hypothesis was examined by usin-g
Raman spectroscopy to measure the strain-induced splitting and shift in the O(IV) phonon. Tlhc
resulting spectra from thick and thin film porous SOS exhibit a peak at 522.2 + 0(.7 cmi
which is consistent with the relaxation of stress in the etched porous silicon film [131.

Figure 4. SEM cross section

7' of porous SOS.

QUANTUM EFFICIENCY OF POROUS SILICON

Initial experiments into the quantum efficiency of porous silicon with respect to 1Ill-V corn-
pound semiconductors were performed by comparing the photoluminescence of undoped
bulk-GaAs and 100-A-period multiple quantum well (MQW) AIGaAsiCaAs samples to an
electrochemically prepared porous silicon sample. The electrochemically prep~ared porous
layers could he fabricated several microns in depth in bulk silicon, and did not exhibit the dif-
fuse scattering observed in the thick film porous SOS samples. Experiments were performed
under 5-mW excitation, with the 457.9-nm line of an argzon ion laser, and emission was
detected by an Aires FF5()(MS monochrometer with a silicon photodetector. No room
temperature photoluminescence was observed from the Undoped bulk-GaAs sample. while
the MQW-AIGaAsiGaAs sample exhibited a very weak room temperature photoluminc,,-
cence, with some structure barely observable in thle spectra. Under identical conditions, an
electrochemically etched porous silicon sample exhibited strong photoluminescence at room
temperature. with the peak wavelength at about 720 nm. The significant in,.-rease in li.ht emis-
sion from the porous silicon sample compared to the MQW-AIGaAs 'GaAs sample was clearl\
obser'able with the naked eve: however, in this experiment a quantitative comparison wAas not
possible due to our inability to substantially detect photoluminescence from the 11 I-V semicon-
ductors at room temperature.

* LASER
a PS X10

z 5s e o

•.:, -,

500 550 600 650 700 750 800 85C 900 950
WAVELENGTH (nrmi

Figure 5. Diode laser and porous silicon emission spectra.

The emission spectra obtained for the porous silicon above were then compared to tne
emission from a commercial AIGaAs semiconductor laser (D.O. Industries GAL[A laser.
model 975-04-8) under an identical light-collection arrangement. The intensity of the semi-
conductor laser was specified as 5 mW, with ý,peak wavelength about 755 nm. The integrated
area wa calculated for the two spectra, shown in figure 5, and corrected ior geometrical fac-
tors. The integrated area for the semiconductor laser was 20 times that of our porous silicon
sample, implying an emission of 0.25 mW. From these results, an external quantum efficiency
of 5% was obtained.
Subsequent experiments were performed using a 10-mW IleCd laser (Liconix model
421 ONB) at 442 nm. Emission spectra were collected by using a 0.2"-m monochromenter (Acton
model 275, 150 grooves/mm grating) and a liquid-nitrogen-cooled CCD detector (Princeton
Instruments). This experimental arrangement allowed for a substantially improved detection

8
of low light level due to the multichannel collection ability and the loA dark current detector.
Typically, 5 accumulations of 1-second exposures were used to ohlain the emission Spcctra.
Several of the electrochemically etched porous silicon samples were measured, with peak
wavelengths ranging from 706 nm to 735 nm. All showed the characteristic broadhlmnd cmlis-
sion ( - 150 nm full width, half maximum) and had comparable relative intensiti-,. lThc laser
intensity was monitored during collection and the spectra were normalized to the maximum
laser intensity when appropriate. The undoped GaAs sample was reexamined for room tem-
perature photoluminescence. As many as 10 accumulations of 10 second exposue-"es \crc
acquired without evidence of photoemission. The MQW-AlGaAs'GaAs sample was also rein-
vestigated. The emission spectra were easily detected, with a peak about 843 nm. Figurc 6
compares the photoluminescence emission spectra of the MOW and porous silicon. The con-
mercial semiconductor laser was again used to quantify the magnitude of the phololumines-
cence. Correcting the data for geometrical aspects, we find that the integrated intensit\ of the
porous silicon is greater than 103 times that of the MQW structure. In one region of interest.
750 nm to 900 nm, the room temperature photoluminescence of porous silicon exceeds that of
the MQW sample by a factor of - 200. Of course, the MQW has a much smaller linewidth and
can be made to lase but for pumping applications the additional emission would be readily
traded for linewidth. The emitted intensity from the "brightest- porous silicon sample was cal-
culated to be 2.6 uW This corresponds to an external quantum efficiency of about ().L04",. sub-
stantially below that measured previously.

•MOW X 50 1

-. A%
5
uC x
z z.. ,*

I.-- .

500 550 600 650 700 750 800 850 900 950
WAVELENGTH (nm)

Figure 6. MQW and porous silicon emission spectra.

9
 The shift to a shorter wavelength to photoexcite the samplesC xould not be expected to
cause the lower measurement for the quantum efticienc%. In fact, the increased photon ener'y
should photoexcite a larger population of states in the porous silicon, resulting in increased
photoluminescence. Fhe lower emission observed in this work from samples analyzed roughly
I month apart is attributed to an aging effect observed in porous silicon. It has been reported
[17,18] and has been observed here that oxidation of tle samples occurs with prolonged expo-
sure to air, which can be accelerated by illumination. This is evident by an increase in the Si-()
peak in the FTIR spectravwith time. We hypothesize that the oxidation process replaces surface
hydrogens with oxygens and subsequently quenches the radiative emission. ln1\c[,,Ivation of
this theory is ongoing.

RECENT RESULTS

Namavar et al. [ 19] of Spire Corporation report that the photolumincscence of their elec-
trochermically prepared porous silicon samples emit intensities "essentially equal to those rou-
tinely found at Spire for MOCVD-grown AI0 .3 Gal- As" and that the emission wavelength can
be red-shifted by increasing the concentration of germanium in porous SiI xGe alloys. Flec- -

troluminescence was obtained from an n-ITO/p-PS-junction diode when forward biased. Cor-
recting for series resistance, Namavar et al. project that the device would emit light with less
than 3 volts applied.
At the fall 1992 Materials Research Society (MRS) conference,* there were several
presentations of interest. Liu et al. (Stanford) reported on lithographically defined quantum
pillars fabricated in bulk Si. This group has reported light emission from these pillars when
substantial laser pumping (several W/cm ) is used. and attempts are now underway to make
contact with these nanostructures to investigate electroluminescence. Kozlowski et al. (Inst.
Solid State Tech., Germany) reported electroluminescence at 5 volts in photoelectrochemical-
ly etched porous pn-junctions. Light emission from the blue to the red region of the spectrum
was observed and could be tuned by varying the wavelength of incident light during the etching
process. Maruska et al. (Spire Corp.) reported red electroluminescence and the first monolith-
ic fabrication of a silicon light source (ITO/porous Si) and a silicon detector (ITO/Si). Peng et
al. (Rochester) reported a means to passivate the porous silicon surface to prevent the degra-
dation of photoluminescence by postfabrication etching in a nitric acid solution.

FUTURE DEVELOPMENTS
The investigation of the fundamental light emission mechanism in porous silicon and
porous SOS and the development of fabrication techniques that are reproducible and compat-
ible with microelectronic (VLSI) processing will be continued under the OCNR Independent
Research (IR) program at N,'COSC, RDT&E Division during FY93. Advances from this pro-
gram will be applicable to Jectroluminescent silicon and the further development of an
efficient light-emitting silicon source.

"Thtpresentations mentioned in this paragraph and related articles arc published in the Alicroclstaiinc Sen'i(ondwdror.r Aatclwnl
Science & Devices. Vol- 283. Material, Research Society Symposmim Proceedings, 1993.

10
 CONCLUSIONS

Photoluminescent porous silicon and porous SOS have been fabricated by using chemical.
electrochemical, and photochemical techniques. An electrochemically fabricated porous sili-
con sample exhibited 5% quantum efficiency when pumped with 5 mW of 457.9-nm argon ion
laser light with a peak emission wavelength of 720 nm. This is consistent with other reports that
efficiencies between 1 and 10'4, have been observed. This room temperature performance
exceeds the early development of light emission from 111-V semiconductors and suggests that
continued research and development of the emission mechanism and optimization of the fab-
rication process can produce at least functionally equivalent results in a less expensive material
which is amenable to large-scale integration.
In 1966, the external quantum efficiency of direct-band gap GaAs light-emitting diodes was
reported greater than 17 [2201. The first diode lasei-pumped solid-state (CaF-':U 3- j laser
demonstrated in 1962 required the entire assembly to be placed in a liquid helium dewar due to
the requirements for the GaAs diode laser operation. Since then. a 100-mW AIGaAs diode
array was commercially produced in 1984, and subsequently the output power has increased
two orders of magnitude to 10 watts in multistripe bar arrays commercially available [2.31.
Extrapolation of similar rapid development can be made for porous silicon due to the mature
silicon processing infrastructure in-place worldwide. This is evident by the monolithically inte-
grated silicon-based source and detector and the rapid advances in silicon LEDs. Improve-
ments in fabrication techniques, particularly to tune the emission spectra and increase
emission, have already begun and offer significant promise as an alternative solid-state laser
pump source.

REFERENCES

1. W. Streifer, D. R. Scifres, G. L. Harnagel. D. E Welch, J. Berger, M. Sakamoto, 'Advances

in Diode Laser Pumps," IEEE J. Quantum Elect., 24 (6), June 1988. pp. 883-894.
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24 (6), June 1988, pp. 895-912.
3. P Albers, "Diode Pumped Neodymium Lasers," High-Power Solid-State Lasers and
Applications, C. L. M. Ireland, editor, SPIE Vol. 1277, pp. 48-51, (1990).
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1981).
5. S. M. Sze, Physics of Semiconductor Devices, 2nd. Edition (New York: John Wiley & Sons,
1981), p. 13.
6. L. T Canham, "Silicon Quantum Wire Array Fabrication by Electrochemical and Chemi-
cal Dissolution of Wafers," Appl. Phys. Lett., 57 (10). Sept. 1990, pp. 1046-1048.
7. S. Shih, C. Tsai, K.-H. Li, K. H. Jung, J. C. Campbell, D. L. Kwong. "Control of Porous Si
Photoluminescence Through Dry Oxidation," Appl. Phys. Lett., 60 (2), Feb. 1992, pp.
833-835.

11
S. R. P.Vasquez, R. WV. Fathauer.T Ge(org~e. A. Ksendzov T1.L. L.in. "Electronilc Slruciure: of
Light-Emitting Porous Si." App!. Phys. Lett.. 60 (8). F'eb). 199)2. pp. 10014- 10016,
9. N. L. Zheng, WV. Wang. H. C. Chen, 'Tomlus minperature Dependencies of Phoro(,lu-
minescence for Visible-Light -Emitting Porous Si." Appi. Phys. Leitt- 60 (2). Vebh, 1992, pp.
986-988.
10. M. S. Brandt, H. D. Fuchs, MI. Stutzmann. J. Weber. ),I.(iardo)na. "The (.ricinofVil
Luminescence From 'Porous Silicon': A Niewx Interpretation. Solid Stiate (oninun.. X1
(4), 19921, pp. 307 -3 )12.
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Silicon Transparent Surface Light-Emitting Diodes." Appi. Phys. Lett_. 61 (11 ). 14 Sept.
1992, 1338- 1340.
13. W B. Dubbelday. D. M. Szaflarski, R. Shimahukuro, S. 1.. Russell. MI. J. Sailor. "Photoln-
minescent Thin Film Porous Silicon on Sapphire." Appi. Phvs. Lett.. 621 (141). Apr. 1993,
pp. 1694 -1696.
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Bard, "Demonstration of Photoluminescence in Nonanodized Silicon," AppI. Phys. Lett.,
60 (13), Mar 1992, pp. 1532-1534.
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19. E Namavar, H. P.Maruska. N. M. Kalkhoran, "Visible Electroluminescence From Porous
Silicon np}-leterojunction Diodes," App!. Phys. Lett., 60 (20), May 1992. pp. 2514 -2516.
20. H. Rupprecht, J. M. Woodall, K. Konnerth, D. G. Pettit, "Efficient Electroluminescence
From GaAs Diodes at 3(00K," AppI. Phys. Lett., 9 (6) Sept. 1966, pp. 221- 223.
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4 TITLE AND SUBTITLE L F N%:!G %UMBERRS

POROUS SILICON FOR PUMPING SOLID-STATE LASERS 0601153N

84 - CH4 I
0601 152N
6 AUTHOR(S) 953 - 2W70
S. D. Russell, W B. Dubbelday, R. L. Shimabukuro
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Z.,
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13. ABSTRACT (Maximum 200 words)

Preliminary experiments were performed to investigate the feasibility of using silicon-based sources to pump solid-state
lasers. Photoluminescent porous silicon and porous silicon-on-sapphire (SOS) have been fabricated using chemical, electrochemi-
cal, and photochemical techniques. An electrochemically fabricated porous silicon sample exhibited 5Y quantum efficiency when
pumped with 5 mW of 457.9 nm argon ion laser light with a peak emission wavelength of 720 nm. This is consistent with other
reports that efficiencies between 1 and 10'7 have been observed. This room temperature performance exceeds the early develop-
ment of light emission from III-V semiconductors and suggests that continued research and development of the em .oi-on- rn.ecnt,
nism and optimization of the fabrication process can produce, at the very least, functionally equivalent results in a lhss expensive
material which is amenable to large-scale integration.

14 SUBJECT TERMS i5 NUMBER OF PAGES

porous silicon photoluminescence 20
solid-state lasers laser pumping PRICE CODE
silicon-on-sapphire
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