Optical transmission range and phase matching (PM) conditions for second harmonic generation (SHG) of Er3+:YSGG and CO2 laser in indium doped GaSe:In(0.1, 1.23, 2.32 mass%) are studied in comparison with these in pure and sulfur doped GaSe:S(0.09, 0.5, 2.2, 3 mass%) crystals. No changes in transparency curve are found in GaSe crystals up to 2.32 mass% indium content, but as small change as 0.18 degrees in PM angle for 2.79 microm Er3+:YSGG laser SHG and approximately 0.06 degrees for 9.58 microm CO2 laser emission line SHG are detected. PM properties of the crystals are evaluated as a function of temperature over the range from -165 to 230 degrees C. The value of dtheta/dT, the change in PM angle with variation of temperature, is found to be very small for GaSe:In crystals. While for SHG of Er3+:YSGG laser, dtheta/dT =22"/1 degrees C only, it is as small as -4.9"/1 degrees C for that of CO2 laser radiation. Linear variation of PM angle with temperature increasing is an indicator of absence of crystals structure transformation within temperature range from -165 to 230 degrees C. Thus, application of GaSe:In solid solutions in high average power nonlinear optical systems seems to be prospective.

In this review, we introduce the current state of the art of the growth technology of pure, lightly doped, and heavily doped (solid solution) nonlinear gallium selenide (GaSe) crystals that are able to generate broadband emission from the near infrared (IR) (0.8 mm) through the mid-and far-IR (terahertz (THz)) ranges and further into the millimeter wave (5.64 mm) range. For the first time, we show that appropriate doping is an efficient method controlling a range of the physical properties of GaSe crystals that are responsible for frequency conversion efficiency and exploitation parameters. After appropriate doping, uniform crystals grown by a modified technology with heat field rotation possess up to 3 times lower absorption coefficient in the main transparency window and THz range. Moreover, doping provides the following benefits: raises by up to 5 times the optical damage threshold; almost eliminates two-photon absorption; allows for dispersion control in the THz range independent of the mid-IR dispersion; and enables crystal processing in arbitrary directions due to the strengthened lattice. Finally, doped GaSe demonstrated better usefulness for processing compared with GaSe grown by the conventional technology and up to 15 times higher frequency conversion efficiency. INTRODUCTIONThe e-polytype of gallium selenide (hereinafter GaSe) has been known since 1934 1 and promises efficient optical frequency conversion and detection over a large range of wavelengths. The performance potential of GaSe, which belongs to the point group symmetry 6m2, can be attributed to its extreme physical properties. GaSe has a broadband transparency window over the range of 0.62-20 mm for non-polarized light continues at wavelengths o50 mm 2,3 . Other attractive physical properties of GaSe are its prodigious birefringence B 5 0.375 at l 5 10.6 mm and 0.79 at terahertz (THz) range 4 , and very high second-order nonlinear susceptibility d 22 5 54 pm V 21 at 10 mm 5 and 24.3 pm/V in the THz band 6 . Among the mid-infrared (IR) anisotropic nonlinear crystals, GaSe has the second highest optical damage threshold 7,8 and thermal conductivity in the plane of the (0001) A GaSe crystal was first used for laser frequency conversion in the mid-IR in 1972 9,10 . In subsequent years, GaSe was widely used for inlab mid-IR applications 5 . Over the past two decades, GaSe has been among the most promising nonlinear optical crystals for efficient generation of ultrabroadband radiation 0.8-5640 mm (with the

The optical properties of p-type GaSe and mixed GaSe(1-x)S(x), x=0.04, 0.023, 0.090, 0.133, 0.175, 0.216, 0.256, 0.362, 0.369, and 0.412, crystals were studied to reveal the potentials for phase matching and frequency conversion. Comparative experiment on Er3+:YSGG and CO2 laser SHG at identical experimental conditions is carried out at room temperature. Any change in polytype structure of GaSe1(1-x)S(x) was not found.

Key words synthesis of chalcogenides, Bridgman technique, nonlinear optic materials.The paper describes principal manipulations to prepare single crystals of GaSe and GaS. A new simple method of synthesis with single-zone heating furnace is proposed. Growth of crystals was performed by modified Bridgman method with the use of rotating heat field. Raman and optical depth spectra show high structural and optical quality of obtained crystals.