Etching kinetics of virgin photo-thermo-refractive glass and glassceramics (after photo-thermo-induced
crystallization process at various terms) in aqueous hydrofluoric acid based solution has been investigated
for the first time. It has been shown that the etching rate of the glassceramic is increasing with increasing
of nanocrystalls number and size.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3540

Bocharova, I.V.

Ignatiev, A.I.

Nikonorov, N.V.

Sorokina, M.G.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 4, 04NAESP20(2pp) (2013)   2304-1862/2013/2(4)04NAESP20(2) 04NAESP20-1  2013 Sumy State University Dependence of Chemical Etching rate of PTR-glasses on Terms of  Photo-thermo-induced Crystallization   M.G. Sorokina*, I.V. Bocharova†, N.V. Nikonorov‡, A.I. Ignatiev§   St. Petersburg National Research University of Information Technologies, Mechanics and Optics,  49, Kronverkskiy pr., 197101 Saint-Petersburg, Russia  (Received 11 July 2013; published online 01 September 2013)  Etching kinetics of virgin photo-thermo-refractive glass and glassceramics (after photo-thermo-induced crystallization process at various terms) in aqueous hydrofluoric acid based solution has been investigated for the first time. It has been shown that the etching rate of the glassceramic is increasing with increasing of nanocrystalls number and size.   Keywords: Photo-thermo-refractive glass, Chemical etching, photo-thermo-induced crystallization   PACS number: 81.65.Cf, 42.70.Ce                                                           * Ovenka100@mail.ru † Carabanga@list.ru ‡ Nikonorov@oi.ifmo.ru § Ignatiev@oi.ifmo.ru 1. INTRODUCTION  Photo-thermo-refractive(PTR) glasses have attract-ed considerable attention as a material for volume hol-ogram recording. It is a sodium-zinc-aluminum-silicate glass doped with cerium, silver and antimony[1]. The process of ultraviolet exposure followed by heat treat-ment leads to precipitation of crystalline phase. It pro-duces refractive index modulation and this phenome-non is used for phase volume hologram recording. One of the advantages of the material is a low level of scat-tering on the boundary between crystalline and glassy phases. Photo-thermo-refractive glass has small size of nanocrystalls (NaF-AgBr) that allows to record highly efficient volume Bragg gratings[2]. But the technical and industrial uses of PTR glass have increased in re-cent years. It has been found that the local nanocrys-talline phase of PTR glass etches about ten times faster than the glassy one[3]. For that reason this materials can be used for fabrication of photonics and mechatron-ics elements.  The purpose of this paper is to describe a new PTR glass capable of being etched by an aqueous hydrofluor-ic acid based solution depending on characteristics of photo-thermo-induced crystallization process.   2. TECHNOLOGY AND EXPERIMENTS  Several photo-thermo-refractive glasses of approxi-mate composition Na2O-ZnO-Al2O3-SiO2-NaF-KBr doped CeO2, Sb2O3 and Ag2O and based-on-it glass-ceramics were studied in this work. Polished samples of 1 mm thick and 7  7 mm lateral size were prepared for photo-thermo-induced crystallisation. Glass samples were ultraviolet exposed and heat treated. Nanocrys-talls NaF were forming within UV-exposed area during the process of photo-thermo-induced crystallization. Ultraviolet exposure and heat treatment properties were varying depending on the aim of the experiment.  Samples were placed in 3N aqueous hydrofluoric  acid based solution. During the measurement tempera-ture and hydrodynamic were constant. Constant condi-tions were provided by magnetic churn with warm up and were controlled by mercury thermometer. The step heights between unexposed and exposed areas were measured using electronic micrometer. Sensitivity of the measurements was in the range of 1 μm.    3. RESULT AND DISCUSSION   The first set of samples were exposed to ultraviolet radiation with various durations. With increasing du-ration of ultraviolet exposure increases the number of nucleation centers. It leads to number of nanocrystals growth. Heat treatment was held within 10 hours at 489 C. The dependence of etched layer thickness of glassceramics with various ultraviolet exposure dura-tion on etching time in hydrofluoric acid based solution is shown in Fig. 1.   Fig. 1 – The dependence of etched layer thickness on etching time. Glassceramics with various ultraviolet exposure dura-tions. 3N concentration. T  C    M.G. SOROKINA, I.V. BOCHAROVA, ET AL. PROC. NAP 2, 04NAESP20 (2013)   04NAESP20-2 According to obtained curves, chemical etching rate rises with the increase of ultraviolet exposure duration and therefore the increase of nucleation cen-ters number.  The second set of samples were exposed to ultravio-let radiation within 50 seconds each. Heat treatment temperature was 489 C. Heat treatment durations were 3h, 5h, 10h and 20h. With increasing duration of heat treatment increases NaF-AgBr size. The depend-ence of etched layer thickness of samples with various heat treatment duration on etching time in HF solution is shown in Fig. 2.    Fig. 2 – The dependence of etched layer thickness on etching time. Glassceramics with various heat treatment durations. 3N concentration. T  C    The experiment showed that chemical etching rate increases with nanocrystall size growth. The third set of samples were exposed to ultraviolet radiation as well within 50 seconds each.  Heat treat-ment was held within 10 hours. With increasing tem-perature of heat treatment also increase nanocrystalls sizes. The dependence of etched layer thickness of samples with various heat treatment temperatures on etching time in HF solution is shown in Fig. 3. The curves in Fig. 3 show the etching rate rising with increase of heat treatment temperature around 507 C and following decreasing around 540 C. The relation-ship between chemical etching rate and temperature of heat treatment is nonlinear.    Fig. 3 – The dependence of etched layer thickness on etching time. Glassceramics with various heat treatment tempera-tures. 3N concentration. T  C   4. CONCLUSIONS  The dependence or chemical etching rate on charac-teristics of photo-thermo-induced crystallization pro-cess has been investigated for the first time. It has been shown that number and sizes of nanocrystals in-fluence on chemical resistance of the material.  According to the results of work, it was concluded that this materials are suitable for making elements and devices using the combination of chemical etching technology and photo-thermo-induced crystallization process.  AKNOWLEDGEMENTS  This work was supported by the federal targeted program “Scientific and Pedagogical Personnel of Inno-vative Russia (2009–2013)” (agreement no. 14.B37.21.0169 of the Ministry of Education and Sci-ence of the Russian Federation).  REFERENCES  1. L. Glebova, K. Chamma, J. Lumeau, L. Glebov Advances in Optical Materials, Conference paper 1 (2011). 2. O.M.Efimov, L.B. Glebov, L.N. Glebova, K.C. Richardson, V.I. Smirnov Appl. Opt. 38, 2 (1999). 3. A.I. Ignatiev, N.V. Nikonorov, M.G. Sorokina, Scientific and technical journal of Information technologies, mechan-ics and optic. 3 (73) (2011).  

Dependence of Chemical Etching rate of PTR-glasses on Terms of Photo-thermo-induced Crystallization

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 4, 04NAESP20(2pp) (2013) 
 
 
2304-1862/2013/2(4)04NAESP20(2) 04NAESP20-1  2013 Sumy State University 
Dependence of Chemical Etching rate of PTR-glasses on Terms of  
Photo-thermo-induced Crystallization  
 
M.G. Sorokina*, I.V. Bocharova†, N.V. Nikonorov‡, A.I. Ignatiev§ 
 
 St. Petersburg National Research University of Information Technologies, Mechanics and Optics,  
49, Kronverkskiy pr., 197101 Saint-Petersburg, Russia 
 
(Received 11 July 2013; published online 01 September 2013) 
 
Etching kinetics of virgin photo-thermo-refractive glass and glassceramics (after photo-thermo-induced 
crystallization process at various terms) in aqueous hydrofluoric acid based solution has been investigated 
for the first time. It has been shown that the etching rate of the glassceramic is increasing with increasing 
of nanocrystalls number and size.  
 
Keywords: Photo-thermo-refractive glass, Chemical etching, photo-thermo-induced crystallization 
 
 PACS number: 81.65.Cf, 42.70.Ce 
 
 
                                                        
* Ovenka100@mail.ru 
† Carabanga@list.ru 
‡ Nikonorov@oi.ifmo.ru 
§ Ignatiev@oi.ifmo.ru 
1. INTRODUCTION 
 
Photo-thermo-refractive(PTR) glasses have attract-
ed considerable attention as a material for volume hol-
ogram recording. It is a sodium-zinc-aluminum-silicate 
glass doped with cerium, silver and antimony[1]. The 
process of ultraviolet exposure followed by heat treat-
ment leads to precipitation of crystalline phase. It pro-
duces refractive index modulation and this phenome-
non is used for phase volume hologram recording. One 
of the advantages of the material is a low level of scat-
tering on the boundary between crystalline and glassy 
phases. Photo-thermo-refractive glass has small size of 
nanocrystalls (NaF-AgBr) that allows to record highly 
efficient volume Bragg gratings[2]. But the technical 
and industrial uses of PTR glass have increased in re-
cent years. It has been found that the local nanocrys-
talline phase of PTR glass etches about ten times faster 
than the glassy one[3]. For that reason this materials 
can be used for fabrication of photonics and mechatron-
ics elements.  
The purpose of this paper is to describe a new PTR 
glass capable of being etched by an aqueous hydrofluor-
ic acid based solution depending on characteristics of 
photo-thermo-induced crystallization process. 
  
2. TECHNOLOGY AND EXPERIMENTS 
 
Several photo-thermo-refractive glasses of approxi-
mate composition Na2O-ZnO-Al2O3-SiO2-NaF-KBr 
doped CeO2, Sb2O3 and Ag2O and based-on-it glass-
ceramics were studied in this work. Polished samples of 
1 mm thick and 7  7 mm lateral size were prepared for 
photo-thermo-induced crystallisation. Glass samples 
were ultraviolet exposed and heat treated. Nanocrys-
talls NaF were forming within UV-exposed area during 
the process of photo-thermo-induced crystallization. 
Ultraviolet exposure and heat treatment properties 
were varying depending on the aim of the experiment.  
Samples were placed in 3N aqueous hydrofluoric  
acid based solution. During the measurement tempera-
ture and hydrodynamic were constant. Constant condi-
tions were provided by magnetic churn with warm up 
and were controlled by mercury thermometer. The step 
heights between unexposed and exposed areas were 
measured using electronic micrometer. Sensitivity of 
the measurements was in the range of 1 μm. 
   
3. RESULT AND DISCUSSION  
 
The first set of samples were exposed to ultraviolet 
radiation with various durations. With increasing du-
ration of ultraviolet exposure increases the number of 
nucleation centers. It leads to number of nanocrystals 
growth. Heat treatment was held within 10 hours at 
489 C. The dependence of etched layer thickness of 
glassceramics with various ultraviolet exposure dura-
tion on etching time in hydrofluoric acid based solution 
is shown in Fig. 1. 
 
 
Fig. 1 – The dependence of etched layer thickness on etching 
time. Glassceramics with various ultraviolet exposure dura-
tions. 3N concentration. T  C  
 
 M.G. SOROKINA, I.V. BOCHAROVA, ET AL. PROC. NAP 2, 04NAESP20 (2013) 
 
 
04NAESP20-2 
According to obtained curves, chemical etching 
rate rises with the increase of ultraviolet exposure 
duration and therefore the increase of nucleation cen-
ters number.  
The second set of samples were exposed to ultravio-
let radiation within 50 seconds each. Heat treatment 
temperature was 489 C. Heat treatment durations 
were 3h, 5h, 10h and 20h. With increasing duration of 
heat treatment increases NaF-AgBr size. The depend-
ence of etched layer thickness of samples with various 
heat treatment duration on etching time in HF solution 
is shown in Fig. 2. 
 
 
 
Fig. 2 – The dependence of etched layer thickness on etching 
time. Glassceramics with various heat treatment durations. 
3N concentration. T  C   
 
The experiment showed that chemical etching rate 
increases with nanocrystall size growth. 
The third set of samples were exposed to ultraviolet 
radiation as well within 50 seconds each.  Heat treat-
ment was held within 10 hours. With increasing tem-
perature of heat treatment also increase nanocrystalls 
sizes. The dependence of etched layer thickness of 
samples with various heat treatment temperatures on 
etching time in HF solution is shown in Fig. 3. 
The curves in Fig. 3 show the etching rate rising with 
increase of heat treatment temperature around 507 C 
and following decreasing around 540 C. The relation-
ship between chemical etching rate and temperature of 
heat treatment is nonlinear. 
 
 
 
Fig. 3 – The dependence of etched layer thickness on etching 
time. Glassceramics with various heat treatment tempera-
tures. 3N concentration. T  C  
 
4. CONCLUSIONS 
 
The dependence or chemical etching rate on charac-
teristics of photo-thermo-induced crystallization pro-
cess has been investigated for the first time. It has 
been shown that number and sizes of nanocrystals in-
fluence on chemical resistance of the material.  
According to the results of work, it was concluded 
that this materials are suitable for making elements 
and devices using the combination of chemical etching 
technology and photo-thermo-induced crystallization 
process. 
 
AKNOWLEDGEMENTS 
 
This work was supported by the federal targeted 
program “Scientific and Pedagogical Personnel of Inno-
vative Russia (2009–2013)” (agreement no. 
14.B37.21.0169 of the Ministry of Education and Sci-
ence of the Russian Federation). 
 
REFERENCES 
 
1. L. Glebova, K. Chamma, J. Lumeau, L. Glebov Advances 
in Optical Materials, Conference paper 1 (2011). 
2. O.M.Efimov, L.B. Glebov, L.N. Glebova, K.C. Richardson, 
V.I. Smirnov Appl. Opt. 38, 2 (1999). 
3. A.I. Ignatiev, N.V. Nikonorov, M.G. Sorokina, Scientific 
and technical journal of Information technologies, mechan-
ics and optic. 3 (73) (2011). 
 


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Dependence of Chemical Etching rate of PTR-glasses on Terms of Photo-thermo-induced Crystallization

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