# Patent

## Title
Cr4+-doped mixed alloy laser materials and lasers and methods using the materials

## Abstract

A laser medium includes a single crystal of Cr4+:Mg2-xMxSi1-yAyO4, where, where M is a bivalent ion having an ionic radius larger than Mg2+, and A is a tetravalent ion having an ionic radius larger than Si4+. In addition, either a) 0≦x<2 and 0<y<1 or b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0. The laser medium can be used in a laser device, such as a tunable near infrared (NIR) laser.

## Background
RELATED APPLICATIONS
This patent application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/646,546, filed Jan. 25, 2005, incorporated herein by reference.


STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
This invention was made with government support under Grant No. NCC-1-03009 awarded by NASA and Grant No. W911NF0410023 from the U.S. Department of Defense. The government may have certain rights in this invention.


BACKGROUND
The development of tunable solid state lasers based on the Cr4+-ion started in 1988 with forsterite, Cr:Mg2SiO4 [V. Petricevic, S. K. Gayen and R. R. Alfano, Appl. Phys. Letters 53 (1988) 2590]. It was extended to other crystalline media, such as Cr4+-doped Y3Al5O12 [A. P. Shkadarevich, in: OSA Proceedings on Tunable Solid State Lasers, Ed. M. L. Shand and H. P. Jenssen (Optical Society of America, Washington, D. C., 1989), Vol. 5, pp. 60-65], Y2SiO5 [J. Koetke, S. Kuck, K. Petermann, G. Huber, G. Gerullo, M. Danailov, V. Magni, L. F. Qian, and O. Svelto, Opt. Commun. 101 (1993) 195], and Y3ScxAl5-xO12 [S. Kuck, K. Peterman, U. Pohlmann, U. Schonhoff, and G. Huber, Appl. Phys. B58, (1994) 153]. These materials also typically include the chromium dopant within the crystalline structure in other valence states. These other valence states can act as a trap and reduce the total concentration of Cr4+ lasing ions. Increasing Cr4+ lasing ion concentration in the laser materials can improve efficiency of laser devices.
Different approaches have been used to increase Cr4+ concentration in crystals. For example, specific crystal growth conditions have been created using different total amounts of chromium oxide in the initial charge, different oxygen content in the growth atmosphere, and/or different after-growth heat treatments. Possible mechanisms for chromium ion incorporation in a crystal structure, with appropriate charge compensation, have also been discussed (W. Chen and G. Boulon, Growth mechanism of Cr:forsterite laser crystal with high Cr concentration, Optical Materials. 24 (2003) 163-168; R. Feldman, Y. Shimony and Z. Burshtein. Dynamics of chromium ion valence transformations in Cr,Ca:YAG crystals used as laser gain and passive Q-switching media Optical Materials, Volume 24, Issues 1-2, October-November 2003, Pages 333-334; J. L. Mass, J. M. Burlitch, S. A. Markgraf, M. Higuchi, R. Dieckmann, D. B. Barber and C. R. Pollock, Oxygen activity dependence of the chromium (IV) population in chromium-doped forsterite crystals grown by the floating zone technique, Journal of Crystal Growth, Volume 165, Issue 3, 1 Aug. 1996, Pages 250-25).
BRIEF SUMMARY
One embodiment is a laser medium, comprising a single crystal of Cr4+:Mg2-xMxSi1-yAyO4, where M is a bivalent ion having an ionic radius larger than Mg2+, and A is a tetravalent ion having an ionic radius larger than Si4+. In addition, either a) 0≦x<2 and 0<y<1 or b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0.
Another embodiment is a laser, such as a tunable near infrared laser, that contains the laser medium.
Yet another embodiment is a method of making a laser medium. The method includes forming a solution comprising at least one substituent for forming the laser medium disposed in a solvent, wherein the at least one substituent is a metal oxide. At least one crystal of Cr4+:Mg2-xMxSi1-yAyO4 is formed from the solution, where M is a bivalent ion having an ionic radius larger than Mg2+, and A is a tetravalent ion having an ionic radius larger than Si4+. In addition, either a) 0≦x<2 and 0<y<1 or b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0. In one embodiment, the method includes providing a substrate; and forming a layer of Cr4+:Mg2-xMxSi1-yAyO4 on the substrate by liquid phase epitaxy.



BRIEF DESCRIPTION OF THE DRAWINGS
Non-limiting and non-exhaustive embodiments of the present invention are described with reference to the following drawings. In the drawings, like reference numerals refer to like parts throughout the various figures unless otherwise specified.
For a better understanding of the present invention, reference will be made to the following Detailed Description, which is to be read in association with the accompanying drawings, wherein:
FIG. 1 is a fluorescence spectrum of a chromium-doped Mg2GeO4 powder sample;
FIG. 2 presents fluorescence spectra for various chromium-doped Mg2(GeySi1-y)O4 powders;
FIG. 3 presents fluorescence spectra for chromium-doped Mg2GeO4 in crystals formed in a liquid phase epitaxy solution (left) and on a Mg2SiO4 substrate (right);
FIG. 4A is a schematic illustration of a first embodiment of a laser, according to the invention;
FIG. 4B is a schematic illustration of a second embodiment of a laser, according to the invention;
FIG. 5 is a schematic illustration of a third embodiment of a laser, according to the invention;
FIGS. 6A and 6B are schematic illustrations of two embodiments of laser systems, according to the invention;
FIG. 7 is a schematic illustration of another embodiment of a laser system, according to the invention; and
FIG. 8 is a schematic illustration of one embodiment of a waveguide laser/amplifier, according to the invention.



DETAILED DESCRIPTION
New laser materials, including near infrared (NIR) laser materials, can be based on alloys of forsterite (Mg2SiO4). These materials can be used as chromium doped laser materials (e.g., laser media) for lasers, such as tunable NIR lasers. Increased Cr4+ concentrations can often be achieved by certain isomorphic substitutions which provide enhanced Cr4+ incorporation conditions in the forsterite crystal structure. Examples of a suitable laser medium (material) is the Cr-doped mixed alloy single crystal composition, Mg2-xMxSi1-yAyO4, which has an olivine-type crystal structure. In this alloy, M═Ca, Sr, Ba or any other bivalent ions with a larger ionic radius than Mg2+, and A═Ge, Ti, Zr or any other tetravalent ions with a larger ionic radius than Si4+.
For these materials, either a) 0≦x<2 and 0<y<1 or b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0. In some embodiments, 0<x<2 or 0.1≦x≦1.9 or 0.1≦x≦1. In some embodiments, 0.1≦y≦0.9. In some embodiments, 0.1≦x≦1.9 and 0.1≦y≦0.9.
In some embodiments, the single crystal can have at least 0.05 wt. % Cr4+ and may have at least 0.1 wt. %, 0.5 wt. %, or 1 wt. % Cr4+ or more. In some embodiments, the single crystals have 1 to 5 wt. % Cr4+.
In the past, the laser operation of chromium-doped forsterite (Cr:Mg2SiO4) was attributed to the Cr4+ ion substituting for Si4+ in the tetrahedrally coordinated sites of the forsterite structure. Unfortunately, there is also typically Cr3+ substitution for Mg2+ in the octahedrally coordinated sites. By controlling the crystal growth process (oxidizing atmosphere, crystal growth direction, etc.) the Cr4+/Cr3+ ratio may be increased, but the total amount (e.g., concentration) of Cr4+ in forsterite typically stays at a relatively low level (typically not exceeding 0.05 wt. %). The presence of larger divalent ions, such as Ca2+, can promote the formation of an optically active Cr4+ center.
Synthesis, crystal growth and successful laser operation of another Cr4+-doped crystal, Ca2GeO4, also having the olivine structure, has been studied. (V. Petricevic, A. B. Bykov, J. M. Evans and R. R. Alfano Optics Letters 21 (1996), p. 1750). This material demonstrated that the crystalline structure, including the geometry of octahedral and tetrahedral sites, is a prominent factor for Cr4+ incorporation (e.g., substitution) in the crystal structure. The composition of the laser material defines the parameters of the crystalline structure which determines the fit of the Cr4+-ions in the tetrahedral sites. The composition can provide the conditions for improving Cr4+ concentration in a laser crystal. Growth conditions such as temperature and growth atmosphere seem to be secondary factors.
Spectroscopic studies of different alloys of Cr-doped olivines related to forsterite show changes of fluorescence properties demonstrating that the Cr4+/Cr3+ ratio depends on composition of the material. For example, a number of powder samples of Cr-doped Mg2GeO4 were synthesized by solid state reaction. Synthesis was carried out at 1400° C. for 20 hours in a muffle furnace in an air atmosphere. The initial powder mixture contained stoichiometric amounts of MgO and GeO2 doped with  ̃1 wt % Cr2O3. The cooling rate was varied from fast quenching (e.g., crucibles with the material were taken out from the hot furnace) to slow cooling from 1400° C. to room temperature over a period ranging up to 48 hours. X-ray powder diffraction analysis did not reveal any structural difference for quenched and slow cooled samples. Only the olivine structure was observed without any traces of a spinel structure.
Differential thermal analysis (DTA) experiments were also conducted to detect any polymorphic transitions. The experiments included very slow heating and cooling conditions around 800° C. No thermal anomalies have been found for the samples. As a result, no evidence of a spinel structure was revealed by this DTA study.
Fluorescence measurements, illustrated in FIG. 1, have been made for the samples. These measurements also confirmed the presence of only the olivine structure of Cr-doped Mg2GeO4. The spectrum consisted of two broad bands attributed to emission from Cr3+ ions in octahedral occupation (maximum at 925 nm) and from Cr4+ ions in tetrahedral occupation (maximum at 1170 nm). The sharp line at 1360 nm is the 2nd order emission of the pump diode laser (680 nm).
In view of the results of the X-ray diffraction, DTA, and fluorescence measurements on the powder samples, the olivine type structure of Mg2GeO4 is very stable and only this type of structure is formed during the synthesis procedure. Heating and cooling procedures do not lead to spinel transformation as demonstrated in the MgO—GeO2 diagram of the system. [C. R. Robbins and E. M. Levin, Am. J. Sci., 257, 65 (1959).]
A number of Cr-doped alloy Mg2Ge1-ySiyO4 powder samples (where y varies from 0.1 to 0.9) were generated and lattice parameters were measured using standard X-ray diffraction technique together with fluorescence measurements. It was found that the lattice parameters generally change linearly with substitution (y=0 to y=1) from pure Mg2GeO4 to pure Mg2SiO4. Fluorescence measurements revealed a very interesting feature concerning Cr3+ and Cr4+ distribution in these materials. As can be seen from FIG. 2, the emission of Cr3+ is suppressed (Cr3+/Cr4+ ratio is decreased) for the samples with a composition approaching a Si/Ge ratio equal to 1. In addition, the wavelength of maximum Cr4+ emission shifts to longer wavelength with increasing germanium content in the samples. (The sharp line at 1360 nm is the 2nd order emission of the pump diode laser (680 nm).)
Laser materials can be formed by a variety of methods including, but not limited to, liquid phase epitaxy. For oxide materials, one example of the LPE process is the following: The constituents of the solution are melted in a platinum crucible at about 50-100° C. above the saturation temperature. For example, the solution can include a solvent and stoichiometric quantities of the desired reactants, such as germanium oxide, silicon oxide, magnesium oxide, and chromium oxide (or mixed oxides such as Mg2SiO4 or Mg2GeO4) in the desired stoichiometric amounts. Before growth, the melt is stirred to provide complete dissolution of solute components. The substrate is mounted horizontally on a platinum holder and preheated in the furnace. The substrate has an alternate rotation of 50-100 rpm with a change every 5-10 s. Before dipping, in order to limit the temperature fluctuations, the substrate is to stay a few minutes above the melt. During growth, the melt temperature is kept constant. After the growth a rapid speed rotation (800 rpm) should be used in order to eliminate the solvent droplets. Then the substrate is pulled out of the furnace slowly in order to avoid thermal stresses.
Two types of solvent, based on PbO and Bi2O3, were tested. The test method was based on preparation of a number of compositions in “Solvent (PbO or Bi2O3)—Solute (Cr:Mg2GeO4)” systems with different concentrations of solute and then undergoing a heating procedure until partial melting occurred. It was found that PbO did not generally provide good crystallization parameters, but Bi2O3 proved to be very promising, because even compositions with Cr:Mg2GeO4 content less that 10 mol. % were characterized by crystallization of Cr:Mg2GeO4. The presence of Cr:Mg2GeO4 micro-crystals in solidified samples were detected by measurement of emission properties.
A starting composition for crystal growth of Cr:Mg2GeO4 was the following: MgO—0.025 mol., GeO2—0.025 mol., Bi2O3—0.25 mol., Cr2O3—0.0075 mol. Crystallization temperature for this composition was below 1050° C. It was found that Mg2SiO4 crystal placed in the melt did not exhibit any traces of dissolution. Only oriented heteroepitaxial growth of Cr:Mg2GeO4 was observed on the surface of Mg2SiO4 crystal.
Spontaneous crystallization of Cr:Mg2GeO4 was also observed in the high-temperature solution. Crystals up to 1 mm in size were formed on the surface as a crust for a period of 20 hours. Emission properties of crystals and layers grown in Bi2O3-based flux are shown in FIG. 3. Both crystals and layers exhibit Cr3+ and Cr4+ emission.
As can be seen from FIGS. 1, 2, and 3 the fluorescence spectra of powder, single crystals, and epitaxial layers of Cr-doped Mg2GeO4 are similar, and all of them contain both Cr3+ and Cr4+ emission bands. The results of fluorescence measurements of Cr-doped mixed Mg2(Ge,Si)O4 compositions indicate that compositions containing mixtures of germanium and silicon ions have spectra similar to that of Mg2GeO4 and Mg2SiO4.
FIGS. 4A and 4B illustrate two different designs for using the laser medium in a thin disk of slab laser system depending on pumping geometry. In both concepts the dielectric mirror coatings 108, 110 on the disk itself define the resonator of the oscillator. In the first configuration (FIG. 4A), the cooled face of the disc 102 is optically coated to act as a total reflector, the disk is mounted on a heat sink 104 (e.g., a copper heat sink), and pumping light 106 is directed to the front disk surface. In another configuration (FIG. 4B), the cooled face of the disk 102 is transparent to pumping radiation and highly reflecting for laser emission, the laser disk is mounted on a transparent heat sink 104 (e.g., a sapphire heat sink) and axial back pumping light 106 is directed through the transparent sapphire heat sink.
In a modified version (FIG. 5) of the first configuration, the cooled face of the disk 102 (in this embodiment, a wedge slab) is optically coated to act as a total reflector. The wedge slab can be used as an active element to increase pump efficiency. The reflective coatings 108, 110 are on different components of the laser forming a resonator cavity 112. The disk 102 also includes an antireflective coating 114 on the surface that receives the pumping light 106.
A variety of lasers, including near infrared (NIR) lasers, can be formed using these materials, including, for example, lasers containing the arrangements schematically illustrated in FIGS. 4A, 4B, and 5. One example of a laser system that can be built as an all solid state compact laser with a thin Mg2-xMxSi1-yAyO4 disk is schematically illustrated in FIG. 6A. At the heart of the laser is a Mg2-xMxSi1-yAyO4 disk 302 disposed on a transparent heat sink 304 (e.g., a sapphire heat sink.) The disk is pumped with light from diode bars 306 (or any other suitable pumping light source.) For example, a laser diode stack consisting of a number bars can be used for pumping. Pumping light is delivered to the laser head by a planar waveguide 308. The radiation emitted by each bar was first collimated individually by a cylindrical microlens 310. A planar waveguide is used to shape the emitting beams of the laser diodes. Two cylindrical lenses 312 are used to focus the collimated diode laser beam into the planar waveguide. Using imaging optics, for example, cylindrical and spherical lenses, after the waveguide, a homogeneous pumping line is obtained and coupled into the Mg2-xMxSi1-yAyO4 disk crystal through the transparent heat sink 304. The dielectric mirror coatings 314, 316 on the disk itself define the resonator of the oscillator. The cooling face of the disk attached to the heat sink is coated for high reflectivity at the laser wavelength and high transmission at the pumping wavelength, while the other side is high reflection coated for both wavelengths.
A second example is schematically illustrated in FIG. 6B, where a similar pump assembly (with laser diode bars 306, optics 310, 312, and waveguide 308) is used to pump a Mg2-xMxSi1-yAyO4 wedge 302 from its front surface. Heat management in the gain medium (wedge) is central to successful operation of this laser and is provided by a heat sink 304 (e.g., a copper heat sink.) The wedge 302 includes a high reflective coating 314 on the back side near the heat sink 304 and an antireflective coating 318 on the front side. A coupler 320 is provided with a 95% reflective coating at the laser wavelength.
In another emboidment schematically illustrated in FIG. 7, for pulsed operation, the near-IR light from the laser head (e.g., laser disk 402) can then be directed through a series of dispersive mirrors 404a, 404b to a semiconductor saturable absorber mirror 406 that induces passive mode-locking. The laser light can pass through a mirror 408 and a tuning element 410 to an output coupler 412.
An example of a waveguide laser device is schematically illustrated in FIG. 8. A pump diode laser 502 provide pumping light through a coupling optic 506 to a waveguide 504 made of the Cr4+ material described above. As an example, the waveguide has a coating 508 that is highly reflective at the laser frequency and highly transmissive at the pumping frequency and a second coating 510 that is 95% reflective at the laser frequency.
It will be recognized that these examples of lasers and waveguide laser devices can include more or fewer components or can be modified in accordance with known configurations of lasers and other devices.
The above specification, examples and data provide a description of the manufacture and use of the composition of the invention. Since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention also resides in the claims hereinafter appended. The entire disclosure of each paper, patent, patent application, and other reference cited herein is incorporated herein by reference for all purposes.

## Claims

1. A laser medium, comprising:
a single crystal of Cr4+:Mg2-xMxSi1-yAyO4, wherein
M is a bivalent ion having an ionic radius larger than Mg2+,
A is a tetravalent ion having an ionic radius larger than Si4+; and

either
a) 0≦x<2 and 0<y<1; or
b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0.

2. The laser medium of claim 1, wherein A is selected from Ge4+, Ti4+, and Zr4+.

3. The laser medium of claim 2, wherein M is selected from Ca2+, Sr2+, and Ba2+.

4. The laser medium of claim 2, wherein 0.1≦y≦0.9.

5. The laser medium of claim 1, wherein 0.1≦x≦1.9.

6. The laser medium of claim 1, wherein the laser medium is disposed on a substrate comprising Mg2SiO4.

7. The laser medium of claim 1, wherein A is Ge4+ and x is 0.

8. The laser medium of claim 1, wherein a concentration of Cr4+ is at least 1 at. %.

9. A laser comprising:
a laser medium comprising a single crystal of Cr4+:Mg2-xMxSi1-yAyO4, wherein
M is a bivalent ion having an ionic radius larger than Mg2+,
A is a tetravalent ion having an ionic radius larger than Si4+; and

either
a) 0≦x<2 and 0<y<1; or
b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0.

10. The laser of claim 9, wherein the laser is a near infrared laser.

11. The laser of claim 9, wherein the laser medium is a thin disk or thin wedge.

12. The laser of claim 9, further comprising a heat sink attached to a surface of the laser medium.

13. The laser of claim 9, further comprising a pump light source configured and arranged to provide pumping light to the laser medium.

14. The laser of claim 9, further comprising a tuning element to tune a frequency of light emitted by the laser medium.

15. The laser of claim 9, wherein the laser is continuous-wave mode-locked.

16. A method of making a laser medium, the method comprising:
forming a solution comprising at least one substituent for forming the laser medium disposed in a solvent, wherein the at least one substituent is a metal oxide; and
forming at least one crystal of Cr4+:Mg2-xMxSi1-yAyO4 from the solution, wherein M is a bivalent ion having an ionic radius larger than Mg2+, A is a tetravalent ion having an ionic radius larger than Si4+; and either a) 0≦x<2 and 0<y<1; or b) 0<x<2 and y is 0 or 1 with the proviso that if M is Ca2+ and x=1 then y is not 0.

17. The method of claim 16, wherein forming at least one crystal comprises forming a layer of Cr4+:Mg2-xMxSi1-yAyO4 on a substrate by liquid phase epitaxy.

18. The method of claim 17, wherein providing a substrate comprises providing a Mg2SiO4 substrate.

19. The method of claim 16, wherein forming at least one crystal of Cr4+:Mg2-xMxSi1-yAyO4, comprises forming at least one crystal of Cr4+:Mg2-xMxS1-yAyO4, wherein A is selected from Ge4+, Ti4+, and Zr4+.

20. The method of claim 16, wherein forming at least one crystal of Cr4+:Mg2-xMxSi1-yAyO4, comprises forming at least one crystal of Cr4+:Mg2-xMxS1-yAyO4, wherein M is selected from Ca2+, Sr2+, and Ba2+.

21. The method of claim 16, wherein forming at least one crystal of Cr4+:Mg2-xMxSi1-yAyO4, comprises forming at least one crystal of Cr4+:Mg2-xMxS1-yAyO4, wherein 0.1≦y≦0.9.

22. The method of claim 16, wherein forming at least one crystal of Cr4+:Mg2-xMxSi1-yAyO4, comprises forming at least one crystal of Cr4+:Mg2-xMxS1-yAyO4, wherein 0.1≦x≦1.9.