Optical spectroscopic analysis of cupric oxide doped barium phosphate glass for bandpass absorption filter

Optical spectroscopic analysis of cupric oxide doped barium phosphate glass for bandpass absorption filter

LETTER TO THE EDITOR Journal of Non-Crystalline Solids 382 (2013) 52–56 Contents lists available at ScienceDirect Journal of Non-Crystalline Solids ...

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LETTER TO THE EDITOR Journal of Non-Crystalline Solids 382 (2013) 52–56

Contents lists available at ScienceDirect

Journal of Non-Crystalline Solids journal homepage: www.elsevier.com/ locate/ jnoncrysol

Letter to the Editor

Optical spectroscopic analysis of cupric oxide doped barium phosphate glass for bandpass absorption filter D.A. Rayan a, Y.H. Elbashar b, M.M. Rashad a, A. El-Korashy c b c

Central Metallurgical Research and Development Institute, P.O. Box: 87 Helwan 11421, Cairo, Egypt Faculty of Science Al-Azhar University, Physics Department, Nasr City, Cairo, Egypt British University in Egypt (BUE), Basic Science Department, Faculty of Engineering, ElShorouk City, Cairo, Egypt

a r t i c l e

i n f o

Article history: Received 22 July 2013 Received in revised form 21 September 2013 Available online 26 October 2013 Keywords: Phosphate glass; Absorption filter; Bandpass; Optical properties; Optical band gap

a b s t r a c t CuO nanoparticles (25 nm) have been prepared by using co-precipitation method. The formed CuO powders were doped with barium phosphate glass with a series of xCuO–(20 − x)BaO–30ZnO–10Na2O–40P2O5 in molar ratio with x = 2, 4, 6, 8, 10 and 12 and were prepared by using conventional quenching melts technique. The density has been measured by using the conventional Archimedes method, the molar volume was calculated and found, and the density and molar volume are trended in the same direction by increasing the CuO contents. The investigation of the glass state has been measured using XRD technique. The results show that no natural broadening peaks that form crystals, which proofed the systems, are completely in glass state. Some optical spectroscopic analysis was calculated from the absorbance and transmittance measurement like absorption coefficient, refractive index, extension coefficient, the optical energy gap, the cut off in UV and IR bands to the bandpass filter, which confirmed the optical properties of this type of filter. © 2013 Elsevier B.V. All rights reserved.

1. Introduction The word glass is usually used throughout history based on silica. It is possible to form an almost limitless number of inorganic glasses which do not contain silica, so silica is not a required component of a glass. Glasses are traditionally formed by cooling from a melt. However it can be prepared by using different methods such as vapor deposition, sol-gel processing of solutions, and neutron irradiation of crystalline materials. Most traditional glasses are inorganic and non-metallic [1]. The most important commercial glass former is based on oxides, for example, silicate, borate, tellurite and phosphate [2]. The phosphate glass has marvelous properties such as low dispersion, high refractive index and low melting temperature compared to silicate glass [3]. The poor chemical durability of the phosphate glass is one of the main disadvantages of using this type of glass former. However, adding a good modifier like transition metals oxide leads to increase the benefits of the glass with decreasing its chemical durability. The fabrication of optical glass filter using BaO alkaline earth metal oxide has an effect on the improvement of devitrification resistance when it doped in small amount. However, if the amount of BaO in the glass is increased, it shows poor melting properties [4]. Additionally, ZnO improves the chemical durability, melting properties, and opacity of glass, which is very important for the optical properties for glass filter [5]. The oxide metals like zinc oxide play a good role for changing the properties of phosphate glass when it adds as a modifier. The zinc phosphate glass has a significant interest because it exhibits a high durability, low melting temperature with a lower glass transition temperature, and glass forming ability. Zinc phosphate glass doped with copper ion's 0022-3093/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jnoncrysol.2013.10.002

structure was studied by using many techniques like XRD, NMR, XPS, EXAFS, FTIR, XRF, Raman spectroscopy, hardness, thermal analysis, and electrical conductivity [6–18]. The competition between the interference filters and absorption filters was increased, but the technology of fabricating the absorption bandpass filters is still very expensive and needs to have more development in chemical composition to reach the optimum practical applications [19,20].

* CuO, Monoclinic *

*

Intensity (Count/Sec)

a

* **

*

20

30

40

50

2θ degree Fig. 1. XRD pattern for the copper oxide.

*

*

60

* *

70

LETTER TO THE EDITOR D.A. Rayan et al. / Journal of Non-Crystalline Solids 382 (2013) 52–56

53 CuO 2% CuO 4% CuO 6% CuO 8% CuO 10% CuO 12%

Intensity count / sec

5

CuO 12%

CuO 8% CuO 6%

4

Absorbance

CuO 10%

3 2 1 0

CuO 2%

200 0

10

20

30

40

50

60

70

400

80

600

800

1000

1200

Wavelength λ (nm)

2θ Fig. 4. The absorbance verses wavelength of the glass samples. Fig. 2. XRD pattern for the prepared glass.

In the present study, the physical properties such as density, molar volume, structure XRD, transmission, absorption, and refractive index were studied to examine the effect of copper oxide and barium oxide molar ratio on zinc phosphate glass for glass absorption filter applications.

2. Experimental The glass samples were prepared by using copper oxide doped phosphate glass with a chemical composition xCuO–(20 − x)BaO– 30ZnO–10Na2O–40P2O5 in molar ratio with x = 2, 4, 6, 8, 10 and 12 and applying the conventional melt and quenching technique. The starting materials were used as NaCO3, ZnO, (NH4) H2PO4, and CuO. The chemical compositions were mixed and grinded using mortar for 30 min for each sample, and then calcinated in porcelain crucible using muffle furnace for 1 hour in 290 °C to release the gases from the chemicals like CO2 and NH3. After that the sample in the porcelain crucible was placed into a melting furnace for 30 min in 1100 °C, then shaken clockwise to ensure that the material is in high homogeneity. Finally, the casting was quenched and annealed in copper mould with pressing plate to have a thin disk in a temperature of 300°C for studying the optical properties. The thin disk samples were transparent and green. The annealing technique is required because of the internal stress that remained in the glass during the quenching. The samples were investigated by using polarizer technique before optical and density measurement and all samples were found free from the thermal stresses.

The optical microscope was also used to investigate the samples from the porosity, which indicated the presence of the porosity in some samples which happens during the pouring of the molten glass. In this study we have some measurement to characterize the glass samples, stable as density measured, XRD, absorbance, and transmission. The density was measured by using simple Archimedes method for all the glass samples using ethanol as an immersion liquid at room temperature. Molar volume was calculated from the density obtained. The crystallite phases present in the different annealed samples were identified by using X-ray diffraction (XRD) on a Brucker axis D8 diffractometer with crystallographic data software Topas 2, using CuKα (λ = 1.5406 Å) radiation operating at 40 kV and 30 mA at a rate of 2°/min. The diffraction data were recorded for 2θ values between 4° and 70°. The optical absorption and transmission spectra were recorded at room temperature using UV/vis absorption (JASCO V570) spectrophotometer in the wavelength range 190–1200 nm. 3. Results and discussion The XRD measurement for glass powder was recorded with a 2θ range (10°–70°) by using a computer for controlling the diffractometer with Cu Kα. Fig. 1 depicts tenorite monoclinic copper oxide CuO (JCPDS no. 72-0629) with crystallite size 25nm that is used for glass fabrication with a pattern for nanocrystalline structure. Fig. 2 shows the glass powder with no indication to any peaks for crystals as the formed particles were amorphous.

33.90 3.40 33.85 3.35

33.80 33.75

3.30

33.70 3.25

Density ρ (g/cm3)

Molar Volume (cm3/mol)

3.45

absorption coefficient α (cm-1)

10 Density Molar Volume

33.95

CuO 2% CuO 4% CuO 6% CuO 8% CuO 10% CuO 12%

9 8 7 6 5 4 3 2 1 0

33.65 2

4

6

8

10

12

Concentration CuO (%mol) Fig. 3. Molar volume and density as a function of CuO contents.

200

400

600

800

1000

Wavelength λ (nm) Fig. 5. The absorption coefficient verses wavelength of the glass samples.

1200

LETTER TO THE EDITOR D.A. Rayan et al. / Journal of Non-Crystalline Solids 382 (2013) 52–56

50 40

Transmittance

30 20 10 0

CuO 2%

6

CuO 4%

5

CuO 6%

4

CuO 8%

3

CuO 10%

2

CuO 12%

1 0 -1

294

400

600

800

1000

1200

-3

λ (nm)

-4

322

200

312

-2

-10

320

Transmittance

60

7

318

CuO 2% CuO 4% CuO 6% CuO 8% CuO 10% CuO 12%

70

304

54

-5

Fig. 6. The transmission verses wavelength of the glass samples.

180

200

220

240

260

280

300

320

340

λ(nm) The density and molar volume VM were calculated according to relations [1]:  ρ¼

 W air ρ ðW air −W l Þ 0

Fig. 7. The UV cut off verses wavelength of the glass samples.

VM ¼

ð1Þ

MWðglassÞ ρglass

ð2Þ

where ρ is the sample density; ρ0, the liquid density; Wair, the weight in the air; Wl, the weight in the liquid; VM, the molar volume; and Mw, the molar mass. The density of the glass samples decreases as the barium contents decreases. Moreover, the molar volume and density decrease proportionally to the barium content as shown in Fig. 3. The molar mass of barium oxide is heavier than the molar mass of copper oxide. So, the glass matrix with higher contents with barium oxide Ba2+ is more dense. In addition, the decrease of molar volume is due to the atomic radius of Ba2+ higher than Cu+. As usual, the molar volume and density were changed with inverse direction of each other's direction, but these are unusual results. BaO has high relative molecular mass which opens the structure of the glass network and introduces excess structure volume. CuO plays as a modifier, and by replacement of CuO by BaO causing the decrease of overall molar volume [21–24]. The absorbance spectra of the glass samples shown in Fig. 4 vary due to the different form of the CuO contents. Furthermore, the absorbance (A) increasing with contents of CuO increased in the UV and infrared bands. The absorption coefficient α(ν) as shown in Fig. 5 for the glass samples can be determined using the relation [25]:

The variation of optical transmission of the glass samples is shown in Fig. 6, and the variation of the cut off for the UV and infrared is produced in Table 1. The effect of copper oxide contents of the cutting bands in UV and IR due to the copper has two absorption bands, one in the UV and the other in infrared. Moreover, the copper oxide increases, the band shifts and the absorption UV band increases, until threshold contents of copper oxide begins to have a cut off in infrared region. These absorption bands in the range of 600 and 1200 nm were used to resolve the absorption band in cupric phosphate glass, and these bands were assigned to the energy transitions 2B2g → 2B1g, 2A1g → 2B1g and 2 Eg → 2B1g [26,27]. The UV cut off and UV bandstop filter is shown in Fig. 7. The bandstop in optics is a technique that is able to reject a band of spectral lines. This filter, the UV bandstop, begins with 190 nm and increases with increasing the CuO doping; the UV cut off, the end of the bandstop filter which starts from 294 nm to 322 nm, depends on the CuO concentration from 2% to 12%. The IR cut off and IR bandstop filter is shown in Fig. 8. The bandstop in the IR band is different from the UV cut off and UV bandstop. Such this filter the IR bandstop begins with 700 nm, 705 nm, and 708 nm and ends to 1100 nm which is the end of

6 5 CuO 8%

4

where ln(Io/I) is the absorbance (A), and d is the thickness of the sample.

Table 1 Shows the cut off for UV, Infrared, and the bandstop.

3

CuO 12%

2 1

CuO 2%

CuO 4%

CuO 6%

CuO 8%

CuO 10%

CuO 12%

294

304

312

318

320

322

190–294

190–304

190–312

190–318

190–320

190–322







700

705

708







700–1100

705–1100

708–1100

700

0 -1

705 708

UV-cut off λ (nm) UV bandstop λ (nm) IR-cut off λ (nm) IR bandstop λ (nm)

CuO 10%

ð3Þ

Transmittance

α ðvÞ¼ð1=dÞlnðI o =IÞ¼2:303ðA=dÞ

-2 -3 620

640

660

680

700

720

λ(nm) Fig. 8. The IR cut off verses wavelength of the glass samples.

740

LETTER TO THE EDITOR D.A. Rayan et al. / Journal of Non-Crystalline Solids 382 (2013) 52–56

3.0

5.5

CuO 2%

CuO 2%

5.0

CuO 4%

CuO 4%

4.5

CuO 6%

CuO 6% 2.5

CuO 8%

4.0

Refractive index n

(αhν)0.5 (cm-1ev)0.5

6.0

55

CuO 10%

3.5

CuO 12%

3.0 2.5 2.0 1.5

CuO 8% CuO 10% CuO 12%

2.0

1.0

1.5

0.5 0.0 3.2

3.3

3.4

3.5

3.6

3.7

3.8

3.9

4.0

4.1

4.2

4.3 1.0 300

Photon Energy hν (ev)

350

400

450

500

550

600

650

700

Wavelength λ (nm)

Fig. 9. The optical energy gap.

Fig. 11. The refractive index for the glass samples.

The extinction coefficient as shown in Fig. 12 is usually calculated using a well known relation [28]:

Table. 2 Shows the optical energy gap copaired to the CuO concentration. Energy gap

CuO 2%

CuO 4%

CuO 6%

CuO 8%

CuO 10%

CuO 12%

Egi (eV)

3.6

3.56

3.4

3.37

3.35

3.32



the measurement of the transmission. This IR cut off is for the only CuO with 8%, 10%, and 12% respectively; the bandstop rises in these samples only. Table 1 shows the UV, IR cut off, and bandstop for both. The optical energy gap decreases by increasing the CuO concentration as shown in Fig. 9. The variation begins with 3.60 to 3.32 eV; the listed results are shown in Table 2. It is observed that the trend of the UV cut off is reversible to the optical energy gap as shown in Fig. 10. The refractive index has been calculated by using the following equation: AþRþT ¼1

ð4Þ

where A is the absorbance, T is the transmittance, and the R is the reflectance. With the calculation of the reflectance we can calculate the refractive index as shown in Fig. 11 from the following equation [28]: R¼

ðn−1Þ2 ðn þ 1Þ2

αλ 4π

ð6Þ

where α is the absorption coefficient and λ is the wavelength The dielectric constants as shown in Figs. 13–14 were calculated by using the relations [28]: ′

2

ε ¼n −k

2

ð7Þ



ε ¼2nk

ð8Þ

where n is the refractive index, k is the extinction coefficient, ε′ the real part and ε″ is the imaginary part. It is found that for some optical properties like refractive index, extinction coefficient and dielectric constants there is no high remarkable change with changing wavelength. The second important step for that filter after the bandstop is bandpass. The bandpass in optics is a technique that is able to pass a band of spectral lines. Such these filters have a single bandpass with double bandstop in UV and IR as shown in Fig. 15. The area,

ð5Þ 100

3.60 320 UV Cut off Optical gap

3.50

315 310

3.45 305 3.40 300

UV Cut off (nm)

Optical gap (ev)

3.55

3.35

extinction coefficient, k (cm-1)

90 325

CuO 2%

80

CuO 4%

70

CuO 6% CuO 8%

60

CuO 10%

50

CuO 12%

40 30 20

295

10

290

0

3.30 2

4

6

8

10

12

CuO mol% Fig. 10. The variation of optical band gap and the UV cut off comparing to CuO%.

350

400

450

500

550

600

Wavelength λ (nm) Fig. 12. The extinction coefficient for the glass samples.

650

700

LETTER TO THE EDITOR D.A. Rayan et al. / Journal of Non-Crystalline Solids 382 (2013) 52–56

CuO 2%

4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4

50

CuO 4% CuO 6%

40

CuO 8%

Transmittance

ε'

56

CuO 10% CuO 12%

30 20 10 0

350

400

450

500

550

600

650

100

200

300

400

center of the bandpass, and full wave half maximum (FWHM) were calculated as shown in Table 3. The technique used in this reference is too much expensive compared to the present work, and the final finishing does not affect too much to the product especially in laser protection glass. The center of the peaks in the present work shows these filters in the green band nearly attached to the blue band. Even if the width of the bandpass filter is too much wide, the bandstop in the infrared covers the region that is used in some laser goggle applications like semiconductor laser that operates at 808 nm and Nd:YAG or Nd:Glass that operates from 1050 nm to 1060 nm, which can be used as a laser protection goggle with any wavelength that covers from 800 nm to 1100 nm (the bandstop region). 4. Conclusion The present study shows the effect of Cu2+ ion of the glass phosphate, the molar volume and density are studied to describe the effect of the Ba2+ ion of the phosphate glass and the unusual increasing between the density and molar volume. The density of the glass samples decreases as the barium contents decreases. The optical transmission is also studied and presents the effect of Cu ions of the cut off for UV and infrared bands. The optical energy gap decreases by increasing the CuO concentration. It varies from 3.60 to3.32 eV. The practicality of using this type of glass as bandpass filters indicated that all glass

CuO2% CuO4% CuO6% CuO8% CuO10% CuO12%

3.0x10-7 2.5x10-7

ε'

2.0x10-7 1.5x10-7 1.0x10-7 5.0x10-8 0.0 350

400

450

500

600

700

800

900

1000

Fig. 15. The integration and the peak analysis of CuO 8%.

Fig. 13. The ε′ vs. the wavelength for the glass samples.

3.5x10-7

500

λ(nm)

λ(nm)

550

600

λ(nm) Fig. 14. The ε″ vs. the wavelength for the glass samples.

650

Table. 3 The area, center, width, and FWHM of the bandpass filter.

Area Center (nm) Width (nm) FWHM (nm)

CuO 8%

CuO 10%

CuO 12%

10710 501.88 164.87 194.12

11212 497.75 172.8 203.46

13436 501.95 162.09 190.85

samples show a bandstop in UV bandstop, and some of them exhibit phenomenon of bandstop in UV and infrared bands. The refractive index and extinction coefficient and some optical properties are studied and the results clear that there are no high remarkable change with changing wavelength. References [1] J.E. Shelby, Introduction to Glass Science and Technology, 2nd ed. The Royal Society of Chemistry, 2005. [2] R.H. Doremus, Glass Science, 2nd ed. John Wiley & Sons, Inc., 1994. [3] R.K. Brow, J. Non-Cryst. Solids 263&264 (2000) 1–28. [4] M. Catauro, G. Laudisio, J. Therm. Anal. Calorim. 58 (1999) 617–623. [5] G. Buxbaum, G. Pfaff, Wiley-VCH, 1998. [6] E. Metwalli, J. Non-Cryst. Solids 317 (2003) 221–230. [7] R.J. Barczynski, M. Gazda, L. Murawski, Solid State Ionics 157 (2003) 299–303. [8] E. Metwalli, M. Karabulut, D.L. Sidebottom, M.M. Morsi, R.K. Brow, J. Non-Cryst. Solids 344 (2004) 128–134. [9] T. Miura, Y. Benino, R. Sato, T. Komatsu, J. Eur. Ceram. Soc. 23 (2003) 409–416. [10] S. Bruni, F. Cariati, D. Narducci, Vib. Spectrosc. 7 (1994) 169–173. [11] N. Vedeanu, O. Cozar, I. Ardelean, B. Lendl, J. Optoelectron. Adv. Mater. 8 (2006) 78–81. [12] N. Vedeanu, D.A. Magdas, R. Stefan, J. Non-Cryst. Solids 358 (2012) 3170–3174. [13] J. Koo, B. Bae, H. Na, J. Non-Cryst. Solids 212 (1997) 173–179. [14] G. Walter, J. Vogel, U. Hoppe, P. Hartmann, J. Non-Cryst. Solids 320 (2003) 210–222. [15] B. Tischendorf, J.U. Otaigbe, J.W. Wiench, M. Pruski, B.C. Sales, J. Non-Cryst. Solids 282 (2001) 147–158. [16] M. Nocun, J. Non-Cryst. Solids 333 (2004) 90–94. [17] J. Sułowska, I. Wacławska, Z. Olejniczak, J. Vib. Spectrosc. 65 (2013) 44–49. [18] W. Leenakul, P. Kantha, N. Pisitpipathsin, G. Rujijanagul, S. Eitssayeam, K. Pengpat, J. Magn. Magn. Mater. 325 (2013) 102–106. [19] M.H. Asghar, M. Shoaib, F. Placido, S. Naseem, Curr. Appl. Phys. 9 (2009) 1046–1053. [20] M. Bessell, Encyclopedia of Astronomy and Astrophysics, Nature Publishing Group and Institute of Physics Publishing, UK, 2001. [21] H.M. Oo, H.M. Kamari, W.M.D. Wan-Yusoff, Int. J. Mol. Sci. 13 (2012) 4623–4631. [22] S. Kaewjaeng, J. Kaewkhao, P. Limsuwan, U. Maghanemi, Procedia Eng. 32 (2012) 1080–1086. [23] P. Limkitjaroenporn, J. Phys. Chem. Solids 72 (2011) 245–251. [24] A. Dutta, A. Ghosh, J. Non-Cryst. Solids 353 (2007) 1333–1336. [25] R. Punia, R.S. Kundu, J. Hooda, S. Dhankhar, S. Dahiya, N. Kishore, J. Appl. Phys. 110 (2011)(Article ID 033527). [26] B.S. Bae, M.C. Weinberg, J. Non-Cryst. Solids 168 (1994) 223–231. [27] H. Takebe, S. Nishimoto, M. Kuwabara, J. Non-Cryst. Solids 353 (2007) 1354–1357. [28] M.Y. Nadeem, W. Ahmed, Turk. J. Phys. 24 (2000) 651–659.