Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication
The present paper is concerned with investigations of image formation properties of As₄₀S₂₀Se₄₀ thin layers. Spectral dependence of the refraction index, n, of variously treated (virgin, exposed, annealed) samples was estimated from optical transmission in the spectral region 400 -2500 nm. The n ene...
Gespeichert in:
| Datum: | 1999 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | English |
| Veröffentlicht: |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
1999
|
| Schriftenreihe: | Semiconductor Physics Quantum Electronics & Optoelectronics |
| Online Zugang: | http://dspace.nbuv.gov.ua/handle/123456789/117930 |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Zitieren: | Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication / A.V. Stronski, M. Vlcek, P.E. Shepeliavyi, A. Sklenar, S.A. Kostyukevich // Semiconductor Physics Quantum Electronics & Optoelectronics. — 1999. — Т. 2, № 1. — С. 111-114. — Бібліогр.: 7 назв. — англ. |
Institution
Digital Library of Periodicals of National Academy of Sciences of Ukraine| id |
irk-123456789-117930 |
|---|---|
| record_format |
dspace |
| spelling |
irk-123456789-1179302017-05-28T03:04:25Z Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication Stronski, A.V. Vlcek, M. Shepeliavyi, P.E. Sklenar, A. Kostyukevich, S.A. The present paper is concerned with investigations of image formation properties of As₄₀S₂₀Se₄₀ thin layers. Spectral dependence of the refraction index, n, of variously treated (virgin, exposed, annealed) samples was estimated from optical transmission in the spectral region 400 -2500 nm. The n energy dependence of variously treated samples was fitted by the Wemple-DiDomenico dispersion relationship and used to estimate the single-oscillator model parameters. It was found that exposure as well as annealing leads to the increase in n values over the all investigated spectral region. Changes of the parameters of the single-oscillator model induced by treatment are discussed on the base of photo- and thermally- induced structural changes, which were directly confirmed by Raman scattering measurements. Such photoinduced structural changes provide good etching selectivity of As₄₀S₂₀Se₄₀ layers in nonaqueous amine based solvents. The sensitivity values obtained on 488 nm wavelength consisted ~ 9 cm²/J. Surface relief patterns that were fabricated have good surface quality. Diffraction efficiency values of holographic diffraction gratings (HDG) obtained on the base of As₄₀S₂₀Se₄₀ layers consisted 60-70 %. Relief profile of HDG was close to sinusoidal one. High quality polymer HDG copies were obtained. AFM profiles of the initial replica copies were practically identical to the profile of the master grating. 1999 Article Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication / A.V. Stronski, M. Vlcek, P.E. Shepeliavyi, A. Sklenar, S.A. Kostyukevich // Semiconductor Physics Quantum Electronics & Optoelectronics. — 1999. — Т. 2, № 1. — С. 111-114. — Бібліогр.: 7 назв. — англ. 1560-8034 PACS 42.49.E; 42.70.L; 78.66; 78.30.L; 81.65.C http://dspace.nbuv.gov.ua/handle/123456789/117930 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| collection |
DSpace DC |
| language |
English |
| description |
The present paper is concerned with investigations of image formation properties of As₄₀S₂₀Se₄₀ thin layers. Spectral dependence of the refraction index, n, of variously treated (virgin, exposed, annealed) samples was estimated from optical transmission in the spectral region 400 -2500 nm. The n energy dependence of variously treated samples was fitted by the Wemple-DiDomenico dispersion relationship and used to estimate the single-oscillator model parameters. It was found that exposure as well as annealing leads to the increase in n values over the all investigated spectral region. Changes of the parameters of the single-oscillator model induced by treatment are discussed on the base of photo- and thermally- induced structural changes, which were directly confirmed by Raman scattering measurements. Such photoinduced structural changes provide good etching selectivity of As₄₀S₂₀Se₄₀ layers in nonaqueous amine based solvents. The sensitivity values obtained on 488 nm wavelength consisted ~ 9 cm²/J. Surface relief patterns that were fabricated have good surface quality. Diffraction efficiency values of holographic diffraction gratings (HDG) obtained on the base of As₄₀S₂₀Se₄₀ layers consisted 60-70 %. Relief profile of HDG was close to sinusoidal one. High quality polymer HDG copies were obtained. AFM profiles of the initial replica copies were practically identical to the profile of the master grating. |
| format |
Article |
| author |
Stronski, A.V. Vlcek, M. Shepeliavyi, P.E. Sklenar, A. Kostyukevich, S.A. |
| spellingShingle |
Stronski, A.V. Vlcek, M. Shepeliavyi, P.E. Sklenar, A. Kostyukevich, S.A. Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Stronski, A.V. Vlcek, M. Shepeliavyi, P.E. Sklenar, A. Kostyukevich, S.A. |
| author_sort |
Stronski, A.V. |
| title |
Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication |
| title_short |
Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication |
| title_full |
Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication |
| title_fullStr |
Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication |
| title_full_unstemmed |
Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication |
| title_sort |
image formation properties of as₄₀s₂₀se₄₀ thin layers in application for gratings fabrication |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
1999 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/117930 |
| citation_txt |
Image formation properties of As₄₀S₂₀Se₄₀ thin layers in application for gratings fabrication / A.V. Stronski, M. Vlcek, P.E. Shepeliavyi, A. Sklenar, S.A. Kostyukevich // Semiconductor Physics Quantum Electronics & Optoelectronics. — 1999. — Т. 2, № 1. — С. 111-114. — Бібліогр.: 7 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
| work_keys_str_mv |
AT stronskiav imageformationpropertiesofas40s20se40thinlayersinapplicationforgratingsfabrication AT vlcekm imageformationpropertiesofas40s20se40thinlayersinapplicationforgratingsfabrication AT shepeliavyipe imageformationpropertiesofas40s20se40thinlayersinapplicationforgratingsfabrication AT sklenara imageformationpropertiesofas40s20se40thinlayersinapplicationforgratingsfabrication AT kostyukevichsa imageformationpropertiesofas40s20se40thinlayersinapplicationforgratingsfabrication |
| first_indexed |
2025-07-08T13:02:11Z |
| last_indexed |
2025-07-08T13:02:11Z |
| _version_ |
1837083902066294784 |
| fulltext |
111© 1999, Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
Semiconductor Physics, Quantum Electronics & Optoelectronics. 1999. V. 2, N 1. P. 111-114.
1. Introduction
Among major areas of research in modern optical tech-
nology there are fiber-optic communications, optical im-
aging, diffractive optics. The development of novel ma-
terials is the key aspect of the above mentioned areas.
The chalcogenide glasses and systems on their base have
attracted much attention and were extensively studied
starting from the middle of 1960s. Glasses from As-S-Se
line were successfully applied in the field of diffractive
(as high resolution thin film inorganic resists) [1-2] and
fiber optics [3]. In the present paper we have studied op-
tical and chemical properties of As
40
S
20
Se
40
thin films us-
ing mainly various optical techniques and applied such
media for gratings fabrication.
PACS 42.49.E; 42.70.L; 78.66; 78.30.L; 81.65.C
Image formation properties of As
40
S
20
Se
40
thin layers in
application for gratings fabrication
A. V. Stronski a, M. Vlèek b, P. E. Shepeliavyi a , A. Sklenaø b, S. A. Kostyukevicha
a Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, Kyiv, 252028, Ukraine
b University of Pardubice, 532 10 Pardubice, Czech Republic
Abstract. The present paper is concerned with investigations of image formation properties of
As
40
S
20
Se
40
thin layers. Spectral dependence of the refraction index, n, of variously treated (virgin,
exposed, annealed) samples was estimated from optical transmission in the spectral region 400 -
2500 nm. The n energy dependence of variously treated samples was fitted by the Wemple-DiDo-
menico dispersion relationship and used to estimate the single-oscillator model parameters. It was
found that exposure as well as annealing leads to the increase in n values over the all investigated
spectral region. Changes of the parameters of the single-oscillator model induced by treatment are
discussed on the base of photo- and thermally- induced structural changes, which were directly
confirmed by Raman scattering measurements. Such photoinduced structural changes provide
good etching selectivity of As
40
S
20
Se
40
layers in nonaqueous amine based solvents. The sensitivity
values obtained on 488 nm wavelength consisted ~ 9 cm2/J. Surface relief patterns that were fabri-
cated have good surface quality. Diffraction efficiency values of holographic diffraction gratings
(HDG) obtained on the base of As
40
S
20
Se
40
layers consisted 60-70 %. Relief profile of HDG was
close to sinusoidal one. High quality polymer HDG copies were obtained. AFM profiles of the
initial replica copies were practically identical to the profile of the master grating.
Keywords: As
40
S
20
Se
40
layers, optical properties, Raman spectra, surface relief formation, diffrac-
tion gratings.
Paper received 17.02.99; revised manuscript received 01.04.99; accepted for publication 19.04.99.
2. Experiment
The bulk materials of As
40
S
20
Se
40
composition were pre-
pared by the direct synthesis according to the conven-
tional melt-quenched method from 5N purity elements.
The synthesis was performed in evacuated quartz am-
poules using rocking furnace at 700 - 750 oC for 8 - 24 hrs.
After synthesis, the ampoules were quenched in cold wa-
ter. Thin films (d = 0,4 - 5 µm) were deposited by the
vacuum thermal evaporation (P = 1 ∗10-3 Pa) from the
resistance heated quartz cruicible onto clean glass sub-
strates ( microscopic slides ) kept under room tempera-
ture. During the deposition process the substrates were
rotated by means of a planetary rotation system, which
provided the uniformity of the samples thickness. Depo-
A. V. Stronski et al.: Image formation properties of As
40
S
20
Se
40
thin layers ...
112 SQO, 2(1), 1999
sition rate was continuously measured using the quartz
microbalance technique and in the present study was
within 1 - 6,0 nm/s. Care was taken during sample prep-
aration to minimize exposure to light sources .Thin film
samples were kept in complete darkness until required.
The samples were illuminated either by the Xe-lamp (I =
=10 - 30 mW/cm2 , IR � cut-off filter) or by natural light.
Some samples were annealed in Ar atmosphere at 150 oC
during 4 hours. The optical transmittance of As
40
S
20
Se
40
films was measured in the spectral region of 0,3 to 2,5 µm
using an UV-VIS-NIR spectrophotometer (JASCO-570).
The Raman spectroscopy investigations were carried out
by using BRUKER IFS55 IR spectrophotometer with
FRA-106 accessory. All measurements were performed
at room temperature. Measurements of selective etching
in the amine based etching solutions were carried out by
using the high sensitive quartz resonance method and
with the help of MII-4 microinterferometer as described
in [2] . The holographic diffraction gratings were record-
ed in the setup close to the described in [1, 2] using the
argon laser radiation. For the production of HDG cop-
ies the �Yantar-3� photopolymer material was used. Pro-
files of the master HDG and polymer copies were mea-
sured using of scanning probe microscope �Dimension
3000� and electron microscope JSM-35.
3. Results
3.1. Optical properties
The optical constants were calculated from transmittance
data using the method suggested by Swanepoel. Typical
transmission curve of As
40
S
20
Se
40
film is shown in Fig.1.
Dependence n(λ) is presented in Fig. 2 as an example of
the unexposed sample. The energy dependencies of the
refractive index n(E) were well fitted by the Wemple - Di
Domenico dispersion relationship (Fig. 3). The depen-
dencies of n(λ), values of single oscillator energy E
o
, dis-
persion energy E
d
were obtained for the as-evaporated,
annealed and exposed samples. Exposure and annealing
lead to the increase of dielectric constant and to the de-
crease of E
o
value. It is known, that the correspondence
between E
o
and optical band gap energy E
g
for chalco-
genide glasses can be expressed as E
o
≈ 2 E
g
[4]. Using
this expression we obtain E
g
values 1.94; 1.91 and 1.85
eV for as evaporated, exposed and annealed films, cor-
respondingly. As shown in [ 5 ] , dispersion energy E
d
obeys a simple empirical relationship : E
d
= β N
c
Z
a
N
e
,
where β = 0,37 ± 0,04 eV in covalent crystalline and
amorphous materials, N
c
is coordination number of cat-
ion nearest neighbour to the anion, Z
a
is the formal chem-
ical valency of the anion, and N
e
is total number of va-
lence electrons (cores excluded) per anion. If we assume
that Z
a
= 2, N
e
= 9.33, than for as-evaporated films, where
E
d
= 18.0 we find N
c
~ 2.61 (that is lower than usually
taken for calculations value of N
c
= 3). This can be un-
derstood if we take into account that structure of evapo-
rated thin films is somewhat different from the glass one.
For example, as-deposited As
2
S
3
layers contain signifi-
cant number of defects, including dangling bonds of S
atoms, the concentration of such bonds can exceed 7 %
Fig. 1. Transmission curves: 1 � As
40
S
20
Se
40
film on the glass
substrate, 2 � substrate.
Fig. 2. Dependence of the refractive index vs wavelength, un-
exposed film.
Fig. 3. Energy dependencies of the refractive index for
As
40
S
20
Se
40
film.
500 1000 1500 2000 2500
0
20
40
60
80
100
2
1
T
ra
n
sm
is
si
o
n
,
%
λ , nm
800 1200 1600 2000
2,45
2,50
2,55
2,60
2,65
2,70
n
λ, nm
0 1 2 3 4
0,14
0,16
0,18
0,20
(
n
2 -
1
)
-1
E 2
, (eV)
2
113SQO, 2(1), 1999
A. V. Stronski et al.: Image formation properties of As
40
S
20
Se
40
thin layers ...
[6]. The structure of the evaporated As
40
S
20
Se
40
film can
be represented in the form of matrix, which consists of
pyramidal units AsS(Se)
3/2
. This matrix contain consid-
erable amounts of As
4
S(Se)
4
and S(Se)
2
fragments that
contain As-As and S(Se)-S(Se) «wrong» bonds.
Other defects, pores and hollows can be present in
the structure as well.
3.2. Raman spectra
Raman spectra of fresh evaporated As
40
S
20
Se
40
layers
(Fig. 4 , curve 1) show the presence of numerous weak
bands (118; 155,7; 171,6; 190,7 cm-1, etc.) that corre-
spond to As rich and S(Se) rich fragments . The pres-
ence of such defects, fragments leads to the lower value
of N
c
. Annealing or exposure results in polymerization
of the molecular groups in the main glass matrix, thus
the number of homopolar bonds, defects and hollows is
diminished. That is clearly seen in Raman spectra (Fig. 4,
where with the increase of exposure dose the peaks cor-
responding to the homopolar bonds are decreased and
the spectra are nearing towards the bulk ones (Fig. 4,
curve 5), where the two intensive and broad peaks near
239 and 354 cm-1 are the dominant features.This results
in the increase of the relative density of main structural
units AsS(Se)
3/2
, that provides higher values of E
d
� 21.0
and 20.75, correspondingly, and thus higher values of
N
c
� 3.04 and 3.0.
3.3. Selective etching
Such photoinduced structural changes provide good
etching selectivity of As
40
S
20
Se
40
layers in various non-
aqueous amine based solvents. The best obtained sensi-
tivity values attained ∼ 40 cm2/J [7]. The characteristic
curve of the As
40
S
20
Se
40
layers ( dependence of the h/h
0
ratio on exposure value H, where h
0
� initial thickness of
As
40
S
20
Se
40
layer, h � thickness of the exposed film after
the etching process ) is presented in Fig. 5. The lightsen-
sitivity, S, was determined as reciprocal value to the H at
which the h/h
0
= 0.5. For As
40
S
20
Se
40
layers, S
0,5
value (for
the 488 nm wavelength) reached 8.8 cm2/J , the value of a
contrast coefficient was 0.92.
3.4 . Holographic diffraction gratings
Holographic diffraction gratings with spacial frequency
1600 mm-1 were fabricated by layers exposure with an
interference pattern using the scheme described in [1,2].
After exposure the selective etching was carried out and
after that the reflective layer (Al) was deposited. Surface
relief patterns that were fabricated have good surface
quality, that can be seen from their AFM images (Fig. 6a)
Diffraction efficiency values of holographic diffraction
gratings obtained on the base of As
40
S
20
Se
40
layers were
equal to 60-70 %.
3.5. HDG replicating
The As
40
S
20
Se
40
layers are good media for HDG replicat-
ing processes. Such layers have higher mechanical and
thermal hardness that the organic resists which are tra-
ditionally used for gratings fabricating. For the fabrica-
tion of gratings copies the photopolymer material �Yan-
tar-3� was used. In Figs. 6-7 the AFM image of initial
master grating obtained on the base of As
40
S
20
Se
40
layers
(Fig. 6a) and its polymer copy (Fig. 7a) are shown. From
comparison of the AFM profiles of the master grating
and its polymer copy (Fig. 6b and Fig. 7b, respectively)
it can be concluded that they are practically identical and
close to the sinusoidal one.
Fig. 4. Raman spectra of As
40
S
20
Se
40
films: 1 � as-evaporated
film, 2 � 4 exposure by natural light, 2 � 0.5, 3 � 1, 4 � 4 hours,
respectively, 5 � bulk glass.
Fig. 5. Dependence of the h/h
0
ratio vs exposure value. Expo-
sure on 488 nm wavelength.
0,01 0,1 1
0,0
0,2
0,4
0,6
0,8
1,0
S
0.5
=1/H
0.5
=8.8 cm
2
/J
γ=tgα=0.92
α
h
/h
0
H, J/cm
2
100 200 300 400 500 600
0,0
0,4
0,8
1,2
1,6
2,0
5
4
3
2
1
In
te
n
si
ty
,
a
rb
.u
n
.
λ, cm
-1
A. V. Stronski et al.: Image formation properties of As
40
S
20
Se
40
thin layers ...
114 SQO, 2(1), 1999
4. Conclusion
The investigations carried out show that registering me-
dia based on As
40
S
20
Se
40
layers are rather promising for
the fabrication of diffractive optical elements and other
optical applications.
5. Acknowledgements
This work was partially supported by the European Com-
munity under Grant ERBCIPA CT940107 and by the
grant of Czech Ministry of Education, Youth and Sport
No. Peco Copernicus OK142 which are gratefully ac-
knowledged.
Fig. 6. Atomic force microscope image of holographic grating
obtained on the base of As
40
S
20
Se
40
films: a � 3D image, b �
grating profile.
a
b
Fig. 7. Atomic force microscope image of polymer copy of
master grating presented in Fig. 6: a � 3D image, b � grating
profile.
a
b
References
1. A. V. Stronski, P. F. Romanenko, I. I. Robur, I. Z. Indutnyi, P.
E. Shepeljavi and S. A. Kostioukevitch, Recording of holograph-
ic optical elements on As-S-Se layers // J.Inf.Rec.Mats., 20(6),
pp.541-546 (1993).
2. I. Z. Indutnyi, A. V. Stronski, S. A. Kostioukevitch, P. F. Ro-
manenko, P. E. Shepeljavi, I. I. Robur, Holographic optical ele-
ment fabrication using chalcogenide layers // Optical Engineer-
ing, 34(4), pp.1030-1039 (1995).
3. A. S. Sanghera, P. Pureza, Lynda E. Busse, I. D. Aggraval, Opti-
cal and mechanical properties of IR-transmitting chalcogenide
glass fibers, in : �Optical Network Engineering and Integrity�,
Ed. H. H. Yuce, D. K. Paul, R. A. Greenwell, SPIE Proc. 2611,
pp.2-6, (1996).
4. K. Tanaka,Optical properties and photoinduced changes in amor-
phous As-S films // Thin Solid Films, 66(3), pp.271-279 (1980).
5. S. H. Wemple, Refractive - Index Behaviour of Amorphous Semi-
conductors and Glasses // Phys. Rev, B77(8), pp.3767-3777 (1973).
6. F. Kosek, Z. Cimpl, J. Tulka and J. Chlebny, New analytic meth-
od for investigation of the distribution of bonds in As-S system /
/ J.Non-Cryst.Solids, 90(113), pp.401-404 (1987).
7. P. E. Shepeljavi, S. A. Kostioukevitch, I. Z. Indutnyi and A. V.
Stronski, Fabrication of periodical structures with the help of
chalcogenide inorganic resists, In : �Integrated Optics and Mi-
crostructures II�, SPIE Proc. 2291, pp.188-192 (1994).
µµµµµm µµµµµm
nm nm
µµµµµm µµµµµm
|