CW LASER AT ROOM TEMPERATURE USING VITREOUS SUBSTANCES

BY

0. K. DEUTSCHBEIN
AND C.

C. PAUTRAT

Reprinted from IEEE JOURNAL OF QUANTUM ELECTRONICS Vol. QE-4, Number 2, February 1968 Pp. 48-51
Copyright 1968, and reprinted by permission of the copyright owner PRINTED IN THE U.S.A.

CW Laser at Room Temperature Using Vitreous Substances

0. K. DEUTSCHBEIN AND C. C. PAUTRAT

AbstractWith the aim of finding laser glasses operating in CW at room temperature, a comparative study was made of various neodymium-doped vitreous substances : silicate, borate, germanate, phosphate, and fluoride glasses. About 500 samples of phosphate glasses, doped with neodymium, were prepared and their optical properties studied. The phosphate glasses have three main advantages for laser action.

X. A

E.10-3 cm l

2 05/2 2 P1/2

4 G1112 2G 9/2
2 03/2 2 1(15/2

4G 3/2_
20 5 200
4G 2

5800 6 300 6800 7 8000 8800

-10

7/2 K13/2 4G 5

1) The fluorescence band is narrower than in silicate glasses and can be as sharp as 153 A. 2) The optical pumping is more efficient in phosphate glasses. 3) The lifetime of the 4F312 level is about 300 tiS. The phosphate glasses have very interesting laser characteristics, i.e., in pulsed operation the threshold is 1 joule. Such a rod exhibits semicontinuous operation at room temperature pumped by a krypton arc lamp; when excited in ac, the threshold is about 1 kW. It was found that the fluoride glasses have even more promising laser properties.

<ilaser

transition X.1.13611 ._

17 000 24 000 49 000

V

INTRODUCTION MONG the different types of lasers, the solid fluorescent lasers have the advantage of having a relatively high concentration of active atoms, e.g., 1.6 X 1020 atoms/cm for Nd-doped YAG, and 4.5X 1020 atoms/cm for LG55 glass of the Schott
Manuscript received June 9, 1967; revised October 21, 1967. This research was partially supported, at its first stage, by the U. S. Department of Army, through its European Research Office. This paper was presented at the Conference on Laser Engineering and Applications, Washington, D. C., June 6-9, 1967. The authors are with Centre National d'Etudes des Telecommunications, 92 Issy-lea-Moulineaux, France.

Fig. 1. Energy levels of free Nda+ ion.

Company. For this reason powerful and compact lasers are feasible. From the various rare earths, neodymium is the most attractive dopant because it has several advantages (as seen in Fig. 1). 1) It has a four-level energy scheme at room temperature, because the final level of laser transition is essentially unoccupied. 2) It has several absorption bands, stronger than the other trivalent rare earths, in the visible and near

DEUTCHBEIN AND PAUTRAT: CW LASER USING VITREOUS SUBSTANCES

infrared region where powerful radiation sources are available. 3) The wavelength of emission is in the 1-micron region, where fast detectors exist. Neodymium-doped silicate glasses are valuable laser materials for powerful emission in pulse operation,' but CW operation at room temperature seems practically impossible' ' I because the threshold power is relatively high. This is due essentially to two reasons: 1) the emission bands are broad, and 2) the different absorption bands have unequal intensities. GENERALITIES In laser action, the optical gain coefficient is inversely proportional to the half width of the emission band, for a given pumping power, and so materials with sharper emission bands will have lower threshold values. In solid fluorescent lasers, the emission spectra are not formed by several isolated lines as in gases but by a more or less complex band whose origin is the splitting up of the energy levels of the atoms by the interionic Stark effect and the dynamic interaction of phonons. In glasses, the inherent fluctuations of composition produce inhomogeneously broadened bands which are markedly wider than in crystals. In order to find glasses having lower thresholds than silicate glasses, comparative study was made of various neodymium-doped vitreous substances: silicate, borate, gerraanate, phosphate, and fluoride. As far back as 1938, Tomaschek and Deutschbein" had observed that the fluorescence spectra of Eu 3+ are sharper in phosphate and fluoride glasses than in silicate and borate glasses, and for this reason a systematic study on neodymium-doped phosphate glasses has been carried out. PHOSPHATE GLASSES About 500 samples of phosphate glasses of various compositions have been prepared and their optical properties studied.'" The volume of each sample was about 25 cre, sufficient for optical and physical measurements but not enough for casting laser ingots of good optical homogeneity. With the aim of determining the influence of the different components on the width of the emission band, simple series of monovalent, divalent, and trivalent cations in glasses of metaphosphate type have been studied, as well as mixed glasses with several cations. Furthermore, the rates P 205/metal oxide have been varied within the limits of the vitreous phase.
Fluorescence Spectra

b) For a given valency, heavier ions have smaller bandwidths than do lighter ones. c) Mixed glasses of a monovalent and a divalent cations [e.g., of the formula Cd K4 (P03) 6] have a smaller bandwidth (166 A) than glasses with only one cation [185 A for KPO 5 and 232 A for Cd (P03)2]. d) Phosphate glasses of rather complex compositions, as described in several patents" ' 81 , have bandwidths of more than 300 A. Consequently, it is possible to prepare Nd-doped glasses having much smaller fluorescent bandwidths (153 A) than silicate glasses (240 A) as compared in Fig. 2.
Absorption Spectra

As seen from Fig. 1, the Nd' ion has several absorption bands in the visible and near infrared region, which are generally of different intensities. In the case of silicate glasses, the band at 5800 A is very strong, about three times more intense than the other bands in the near infrared region, Fig. 3. These features are advantageous for the excitation of thick rods because the pumping light is absorbed in different depths of the section of the rod, but on the other side the threshold values are higher. In phosphate glasses, the bands at 5800 A, 7500 A and 8000 A have approximately the same intensities, and thus the pumping light is absorbed by the three bands in the same way, and so lower thresholds can be obtained, especially for thin rods (of 3 mm diameter).
,

Lifetime

The lifetime of the 4F 312 level is about 300 /is for neodymium concentration of 0.25 gram-atom per liter. This value corresponds to a natural linewidth of 2 X 10' A.
Laser Effect

The measurements of the fluorescence spectrum in the 1.05-micron region gave the following results. a) The fluorescent bandwidth is relatively small for monovalent cations (about 190 A.), broader for divalent cations, and even broader (up to 400 A.) for trivalent cations (Al).

In order to test the laser potentiality of phosphate glasses, one melt of a volume of one liter was prepared of the composition Zn Li, (P0 3) 6 which does not have a very small fluorescence bandwidth (190 A.), but which is relatively easy to prepare. Cylindrical rods of 50 mm length and 3 nun diameter have been cut from this ingot, with confocal ends coated with multidielectric mirrors. These rods have been tested in pulsed operation at room temperature by wrapping a silver foil around the rod and a straight xenon flash lamp PEK X E 1-2. Under these conditions typical thresholds had been of 1 joule. Under the same condition very good Ca W0 4 rods of the same dimensions have thresholds of 0.5 joule, and commercial silicate glass rods of the same dimensions, 4 joules. It should be mentioned that our phosphate glass rods have poorer optical quality than the commercial silicate glass rods, as can be seen from the mode patterns shown in Fig. 4. This can be explained by the small quantity of our melt, as compared to the much higher volumes of commercial laser glasses. Semicontinuous laser operation at room temperature has been obtained with an apparatus already used for crystals.'" The pump reflector is an elliptical silver cylinder of 73.2 and 66.7 mm for

eeeee casco (relative intensity)

1.0

0. 5

1.02

1.04

1.06

1.08

1.10

+.12

Ii

Fig. 2. Fluorescence spectra of Nd-doped glasses.

Alk Optical Density

1.0

0.9

0.8
Nd-doped

0.7

phosphate glass Nd-doped

0.6
silicate glass Emission of a tungsten - iodine

0.5

lamp

0.4

0.3

0.2

0.1

./

........ ....... 0.0 0.5

I

0.6

0.7

0.8

0.9

Fig. 3. Absorption spectra of Nd-doped glasses.

(b) (a) Fig. 4. "Emission modes," (a) for a phosphate glass, (b) for a commercial silicate glass.

DEUTCHBEIN AND PAUTRAT: OW LASER USING VITREOUS SUBSTANCES

A t( 1,:7:t!,`.* I.I:..tr)
1 .0

51

20 ms
Fig. 5. Variations of emission of glass rod versus time.
Optical Density

1.12

Fig. 6. Fluoresence spectra of Nd-doped glasses.

---

0.9

Nd-doped fluoride glass

0.7

0.6

Nd-doped silicate glass of a lamp

0.5

Emission

tungsten. iodine 0.4

0.3

0.2

0.1

00

0.5

0.6

0.7

0.8

0.9

Fig. 7. Absorption spectra of Nd-doped glasses.

major and minor axes. The rod is pumped by a krypton arc lamp supplied with alternative current (50 Hz). The lamp and the rod are cooled by tap water. With only one alternation- of electric current (50 Hz) supplied to the arc lamp, the threshold was 720 watts and with the two alternations 1100 watts, as compared with 500 watts for a Ca W0 4Nd rod of the same dimensions. (Fig. 5) shows the variation of the emission of the rod versus time. Rods can operate with 1-kW pumping power without deterioration. FLUORIDE GLASSES It was found that the fluoride glasses have even more promising properties. Their width of fluorescence band is smaller (Fig. 6), and their optical pumping efficiency is still better, as seen on Fig. 7. The near infrared absorption bands are the most intense, and correspond to the region of maximum emission of tungsten-iodine lamps. On the contrary, their preparation is much more difficult and a special technology for the elaboration of laser ingots

and for manufacturing of rods is in progress. One liter melts have not yet been prepared, and the rods made at this time of melts of a cubic inch volume only, are of very poor optical quality. In spite of this, their laser thresholds (6 to 7 joules) are equivalent to those of the best commercial silicate glasses for pulsed operation. When homogeneous rods will be available, real CW operation at room temperature should be possible. REFERENCES 11 1 For a review article on glass lasers see E. Snitzer,
Appl. Optics,

vol. 5, no. 10, pp. 1487-1499, 1966. 121 C. G. Young, Appl. Phys. Lett., vol. 2, pp. 151-152, April 15, 1963. 161 C. G. Young, Appl. Optics, vol. 5., pp. 993-997, June 1966. 14/ R. Tomaschek and 0. Deutschbem, Glastech. Ber., vol. 16, p. 155, 1938. 16/ 0. Deutschbein, C. C. Pautrat, and I. MISvirchevsky, Rev. Phys. Appl., vol. 2, pp. 29-37, 1967. 16/ J. R. van Wazer Phosphorus and Its Compounds, vol. 1, Chemistry. New York: Interscience, ' 1958. 171 Grimm and Hoopert, U. S. Patent 1964-239, 1934. [ 8 ] Schott, French Patent 1302-063. 161 0. K. Deutschbein, G. Grimouille, C. Pautrat, and G. Petit Le Du, Rev. Phys. Appl., vol. 1, pp. 128-132, June 1966.