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United States Patent (19) 11) 4,225,459 Faulstich Et Al

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United States Patent (19) 11) 4,225,459 Faulstich Et Al United States Patent (19) 11) 4,225,459 Faulstich et al. 45) Sep. 30, 1980 54 GLASSES HAVING A LOW NON-LINEAR 4,142,986 3/1979 Rapp .............................. 252/301.4 P REFRACTIVE INDEX FOR LASER APPLICATIONS FOREIGN PATENT DOCUMENTS 2304582 10/1976 France ................................... 106/47 Q 75) Inventors: Marga Faulstich, Mainz; Walter 781243 8/1957 United Kingdom .................. 106/47 R Jahn, Ingelheim; Georg Krolla,. 1405717 9/1975 United Kingdom .................. 106/47 Q Mainz; Norbert Neuroth, 447379 8/1975 U.S.S.R. ................................ 106/47 Q Mainz-Mombach, all of Fed. Rep. of Germany OTHER PUBLICATIONS 73) Assignee: JENAer Glaswerk Schott & Gen., Laser Program Annual Report-1975-Lawrence Liver Mainz, Fed. Rep. of Germany more Laboratory-V. of Calif-pub. Mar. 1976, pp. 197-202–Copyin Group 220. (21) Appl. No.: 897,482 Weber, M. J. et al., "Low-Index Fluoride Glasses for 22 Filed: Apr. 18, 1978 HIgh Power Neodymium Lasers', Optics Communica 30 Foreign Application Priority Data tions 18 (1) (Jul. 1976), pp. 171-172. Apr. 22, 1977 DE Fed. Rep. of Germany ....... 2717916 Primary Examiner-Helen M. McCarthy Attorney, Agent, or Firm-Haight, Rosfeld, Noble & 51) Int. Cl? .......................... CO3C 3/12; CO3C 3/16; Santa Maria C09K11/08; H01S 3/17 52 U.S. C. ........................... 252/301.4 P; 106/47 Q; 57 ABSTRACT 331/94.5 E Glass composition ranges are described which permit 58) Field of Search ........................... 106/47 Q, 47 R; the introduction of laser activators into fluorphosphate 252/301.4 P, 301.4 H, 301.4 F, 301.4 R; glass with exceptionally high fluorine content while 331/94.5 E forming glasses of high crystallization stability and per (56) References Cited mitting the realization of large melt volumes. The high U.S. PATENT DOCUMENTS fluorine content imparts to the glasses an exceptionally 3,960,578 6/1976 Krolla ................................ 106/47 Q low nonlinear refractive index n2 down to O,4 X 10-13 4,040,846 8/1977 Broemer et al. ................... 106/47 Q 6S. 4,075,120 2/1978 Myers et al. .................. 252/301.4 P 4,120,814 10/1978 Izumitani et al. ............. 252/301.4 P 6 Claims, 1 Drawing Figure O.65 0.55 0.45 89 90 9 ABBE NUMBER v U.S. Patent Sep. 30, 1980 4,225,459 O.65 O.55 g O45 O4O 84 85 86 87 88 89 90 9 92 93 ABBE NUMBER v 4,225,459 1. 2 It is also known according to U.S. Pat. Nos. {GLASSES HAVING ALOW NON-LINEAR 3,250,721, 3,846,142, and French Pat. No. 2,291,949, to REFRACTIVE INDEX FOR LASER produce laser glasses based on phosphate glasses. These APPLICATIONS glasses have large effective cross-sections of induced emission, they can also be produced with good optical BACKGROUND OF THE INVENTION homogeneity in large volume and their content of ab sorbent particles is low. However, the fluorescence life The invention relates to new glasses which are partic is restricted to approximately 300 microseconds and the ularly suitable for solid state laser amplifier applications. non-linear refractive index cannot be reduced below The most powerful coherent light impulses hitherto 0 1 x 10-13 esu. Due to their relatively high optical re known are generated by solid state lasers, in which the fraction, said phosphate glasses do not have the desired impulse of a pilot laser is amplified through a chain of low non-linear refractive index n2. amplifier stages. Such an amplifier stage primarily com It is known that glasses display a reduction of the prises a laser glass rod containing an effective amount of non-linear refractive index n2 with decreasing color activator ions, e.g. Nd, which are excited to fluores 15 dispersion and refractive power. This is the case with cence by the light of flashlamps. This energy of excita the group of fluorine phosphate glasses. High-fluoride tion is surrendered by induced emission to the laser glasses are required even for glasses with n2 <0.8. Such beam as it travels through the rod. After passing glasses are known, e.g. see German Pat. Nos. 945,408 through a large number of such amplifiers, the radiation and 1,596,877; British Pat. No. 1,405,717; and commer intensity can become so great that the resulting high 20 cially available glass type FK 51, Schott Catalog electric field intensity displaces the electrons in the shell 3060/72. Such glasses contain primarily fluorides and of the atoms of the glass so strongly that the refractive phosphoric acid and have a far stronger tendency to index is thereby increased. crystallization and segregation than conventional sili In electric fields of moderate intensity, the dielectric cate, borosilicate, silicoborate and borate glasses. As displacement is proportional to the electric field inten 25 these known glasses display no laser properties, it is sity: necessary to use for this purpose special laser activator DweeB elements from the rare earth group, e.g. Nd. wherein: OBJECTS OF THE INVENTION D= dielectric displacement E=electric field strength 30 Accordingly, it is a general object of the present e = dielectric constant. invention to provide new glass compositions which For extremely high electric field intensities, this lin exhibit both a good laser effect and simultaneously a ear relationship no longer applies and a quadratic rela low non-linear refractive index n2. tionship appears: Another object of this invention is to provide such 35 glasses which furthermore contain substantially no laser absorbent particles which would lead to destruction of the glass due to absorption when powerful laser im The root Ce2 = m2 is a measure of a so-called "non-lin pulses pass through it. ear effect.' The quantity n2 is therefore called the non An additional object of this inventions to provide linear refractive index and is expressed in electrostatic 40 such glasses which are suitable for laser amplifier appli units. Increasing the refractive index causes a focussing cations and capable of being produced in large volumes of the beam. The intensity is greatest in the interior of with extremely high optical quality. the beam cross-section and diminishes towards the mar Other objects of this invention will become more ginal zone of the beam cross-section. The non-linear fully apparent to those skilled in the art from the follow refractive index also has a corresponding distribution 45 ing description thereof. and a convex lens effect is also obtained by this means. SUMMARY OF THE INVENTION It is important that the glass which is used in the ampli fier stages should have a low non-linear refractive index Briefly, the above and other objects, features and in order that self-focussing does not become so intense advantages of the present invention are attained in one that an electric discharge is generated in the glass, 50 aspect thereof by providing glass compositions which which would destroy it. The glasses of which are made permit the introduction of laser activators into fluoro the lenses for beam spreading or beam focussing, as well phosphate glass with exceptionally high fluorine con as the plates which are present in the beam path in order tent while forming glasses of high crystallization stabil to reflect out a small part of the laser beam for measure ity and permitting the realization of large melt volumes. ments, must likewise have a low non-linear refractive 55 The high fluorine content imparts to the glasses an index, i.e. the glasses, even without incorporated activa exceptionally low non-linear refractive index n2 down tor ions, have great significance in the construction of to 0,4x10-13 esu. laser amplifier chains. In another aspect of the present invention, partial or It is known, e.g. from German Pat. Nos. 1,171,082 total replacement of P2O5 by As2O5 in specific ranges of and 1,255,215, to produce laser materials based on sili 60 the glass compositions has a further crystallization stabi cate glasses, which provide a good fluorescence life for lizing effect without appreciably influencing the n2 the Nd: ions (up to 1000 microseconds). Such silicate values. glasses can be produced in optically homogeneous form BRIEF DESCRIPTION OF THE DRAWING in large volume and the number of absorbent particles in the glass can be kept small. The disadvantage of such 65 The present invention will become more fully appar glasses is their relatively high non-linear refractive ent to those skilled in the art to which this invention index and the corresponding limited effective cross-sec pertains from the following Detailed Discussion, taken tion of induced emission. in conjunction with the annexed drawing wherein the 4,225,459 3. 4. singie FIGURE illustrates the relationship, for a given The glasses according to the invention in the optical index of refraction, between the Abbe number and the position range III: non-linear refractive index for selected glass composi ind= 1.4.6-1.475, tions according to the present invention. wd=88-83, 5 having a low non-linear refractive index DETALE) DISCUSSION n2=0.60-0.70, The inclusion of Nd2C3 or Ndf3 in known fluoro preferably comprise: phosphate glasses (such as FK 51) causes a marked P2O5: 0-15 wt.% increase in the tendency to crystallization. However, it As2O5: 0.6-12 wt.% has now been unexpectedly discovered that there are O specific glass composition ranges which permit the Alkali metal oxides: 0-5 wt.% introduction of such laser activators into the glass while MgO: 0-7 wt.% forming glasses of high crystallization stability and CaO: 8-15 wt.% whicin perinit the realization of inelts of unexpectedly SrO: 18-22 wt.% large neit voiuanes (e.g.
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