US20040089220A1

US20040089220A1 - Materials for use in optical and optoelectronic applications

Info

Publication number: US20040089220A1
Application number: US10/669,145
Authority: US
Inventors: Milan Kokta; Dennis Peressini; Jeffrey Cooke; Kevin Goodnight
Original assignee: Saint Gobain Ceramics and Plastics Inc
Current assignee: Saint Gobain Ceramics and Plastics Inc
Priority date: 2001-05-22
Filing date: 2003-09-23
Publication date: 2004-05-13
Also published as: GB0326373D0; WO2002095887A3; WO2002095887A2; FR2826519B1; US6839362B2; GB2403339A; US20030007520A1; FR2826519A1; GB2403339B

Abstract

A single crystal ceramic material for optical and optoelectronic applications is d, including a single crystal spinel having a general formula aAD·bE₂D₃, wherein A is selected from the group consisting of Mg, Ca, Zn, Mn, Ba, Sr, Cd, Fe, and combinations thereof, E is selected from the group consisting Al, In, Cr, Sc, Lu, Fe, and combinations thereof, and D is selected from the group consisting O, S, Se, and combinations thereof. A ratio b:a>1:1 such that the spinel is rich in E₂D₃, and the single crystal spinel is formed by a melt process

Description

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation-in-part of application Ser. No. 09/863,013, filed May 22, 2001, published as US 2003/0007520 on Jan. 9, 2003, priority to which is claimed.[0001]

BACKGROUND

1. Field of the Invention

The present invention is generally directed to materials for use in optical and optoelectronic applications, and particularly materials and processes for forming same having crystallographic structures related to the spinet crystal structure.

2. Description of the Related Art

Single crystal materials, such as those having or related to the spinet crystal structure have been used in various optical and optoelectronic applications. For example, single crystal spinet boules have been formed and processed into wafers for fabrication of optoelectronic devices such as LEDs and lasers. In this context, wafers are sliced from a single crystal boule, then subjected to wafer processing to form a plurality of devices in the form of individual die, which are then severed from the wafer. In other applications, spinel-based materials are formed into Q-switches for lasing operations.

Q-switching is a method for obtaining single laser pulses of very high power by protracting the period of population inversion of electrons in excited states just prior to emission. Extending the period of population inversions typically can be achieved acousto- or electro-optically by use of shutters, mechanically (with an orthogonal mirror or rotating mirror), or by use of saturable absorbers (in the form of dyes or doped crystals).

The term “Q-switching” is a reference to the fact that a “Q-factor” or “Quality factor,” which can be defined as v/Δv _c, where v is cavity resonance frequency, and Δv_cis cavity linewidth, shifts from a very low value to a very high value during laser pulse emission. More specifically, population inversion of electrons is extended by blocking emission from the laser cavity. At the time a laser pulse is to be emitted, the blockage is removed, thereby causing the threshold gain of electrons to be deliberately and suddenly reduced. Population inversion is much higher than the threshold gain value, and actual gain greatly exceeds cavity losses. As a result, the excited states are quickly depopulated, causing energy to be discharged in a single laser pulse. The sudden discharge causes actual gain to be reduced to a point below the threshold value, thereby terminating the pulse.

Saturable absorber Q-switches operate passively, whereby absorptivity of the laser wavelength decreases with increasing irradiance until “bleaching” occurs. Population inversion increases until the Q-switch is bleached, at which time the threshold value is reduced, resulting in a laser pulse. Passive Q-switches typically are easy to implement relative to other mechanisms. Historically, examples of saturable absorber Q-switches are dyes, such as bis 4-dimethyl arninodithiobenzyl-nickel (BDN) dissolved in 1,2 dichloroethane for Nd:YAG lasers, and gases, such as SF ₆for CO₂lasers.

More recently, solid state Q-switches have been employed that include crystals doped with tetrahedrally coordinated Co ²⁺ ions as a tunable laser source in wavelengths that range from about 1.5 to about 2.3 μm. Among the crystals that have been doped with Co²⁺ ions for 1.34 μm Nd³⁺:YAlO₃and 1.54 μm-Er³⁺:glass lasers are Y₃Al₅O₁₂, Y₃Sc₂Ga₃O₁₂, LaMgAl₁₁O₁₉, MgAl₂O₄(MALO) and ZnSe. MgAl₂O₄crystals, having the spinel crystal structure, include tetrahedral and octahedral positions. Co²⁺ dopant ions displace Mg²⁺ ions from tetrahedral positions of the crystal. The amount of Co²⁺ ion dopant in MgAl₂O₄crystals typically ranges from about 0.0003 atomic weight percent to about 0.05 atomic weight percent. However, the frequency of the peak emission of doped solid state passive Q-switches typically is not affected by the amount of dopant. Further, the efficiency of a Q-switch (and, thus, the power of the laser pulse) is significantly diminished if it does not have an absorption band that matches the lasing transition. For example, spinel having the empirical formula of MgAl₂O₄and doped with Co²⁺ typically has an absorption band (⁴T₁spectrum) of about 1536 nanometers (nm), whereas the lasing transition of Er:Yb:glass lasers is about 1540 nm. Generally, the efficiency of cobalt-doped spinel Q-switches in Er:Yb:glass and other lasers is limited by the difference in specific absorption bands from the lasing transition wavelengths of such lasers.

Therefore, a need exists to significantly diminish or eliminate the above-mentioned problems of cobalt-doped saturable absorber Q-switches.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, a single crystal ceramic material for optical and optoelectronic applications is provided. The material comprises a single crystal spinel having a general formula aAD·bE ₂D₃, wherein A is selected from the group consisting of Mg, Ca, Zn, Mn, Ba, Sr, Cd, Fe, and combinations thereof, E is selected from the group consisting Al, In, Cr, Sc, Lu, Fe, and combinations thereof, and D is selected from the group consisting O, S, Se, and combinations thereof, wherein a ratio b:a>1:1 such that the spinel is rich in E₂D₃, and the single crystal spinel is formed by a melt process.

According to another aspect of the present invention, a method of forming a monocrystalline spinel material includes: forming a melt, and growing a spinel single crystal from the melt. The single crystal spinel has a general formula aAD·bE ₂D₃, wherein A is selected from the group consisting of Mg, Ca, Zn, Mn, Ba, Sr, Cd, Fe, and combinations thereof, E is selected from the group consisting Al, In, Cr, Sc, Lu, Fe, and combinations thereof, and D is selected from the group consisting O, S, Se, and combinations thereof, wherein a ratio b:a>1:1 such that the spinel single crystal is rich in E₂D₃.

Other embodiments are directed to a cobalt-doped saturable absorber Q-switch, to a laser system that employs a cobalt-doped saturable absorber Q-switch, and to a method of forming a cobalt-doped saturable absorber Q-switch.

In one embodiment, the saturable absorber Q-switch includes a monocrystalline lattice having the formula Mg _1-xCo_xAl_yO_zwhere x is greater than 0 and less than 1, y is greater than 2 and less than about 8, and z is between about 4 and about 13. The lattice has tetrahedral and octahedral positions, and most of the cobalt and magnesium occupies tetrahedral positions. In a preferred embodiment, essentially all of the cobalt and magnesium occupies tetrahedral positions of the monocrystalline lattice.

In a laser system of the invention, a laser resonator cavity has a resonant axis and a lasing element within the resonator cavity. Suitable means optically pump the lasing element. A saturable absorber Q-switch lies along the resonant axis of the laser resonator cavity. The Q-switch includes a monocrystalline lattice having a formula Mg _1-xCo_xAl_yO_zwhere x is greater than 0 and less than about 1, y is greater than 2 and less than about 8, and z is between about 4 and about 13. The monocrystalline lattice has tetrahedral and octahedral positions, and most of the magnesium and cobalt occupy tetrahedral positions. In a preferred embodiment, essentially all of the magnesium and cobalt occupy tetrahedral position of the monocrystalline lattice. In one embodiment, the lasing element is an Er:Yb:glass laser (or any laser source of 1.5-1.6μ frequency). In another embodiment, the laser element is a Nd³⁺:YAlO₃lasing element.

A method of forming a monocrystalline lattice of a saturable absorber Q-switch of the invention includes forming a melt of magnesium, cobalt, aluminum and oxygen, wherein the molar ratio of magnesium:cobalt:aluminum is (1-x):x:y, where x is greater than 0 and less than about 1, and y is greater than 2 and less than 8. A spinel seed crystal is immersed in the melt and rotated at a rate in a range of between about 4 and about 12 revolutions per minute, while withdrawing the seed crystal from the melt at a rate in a range of between about 0.04″/hr and about 0.1″/hr to thereby form the monocrystalline lattice. In one embodiment, the melt is formed by combining MgO, Co ₃O₄and Al₂O₃powders, and then heating the combined powders to a temperature sufficient to form the melt.

Embodiments of the present invention have several advantages. For example, the saturable absorber Q-switch of the invention includes a ratio of aluminum to magnesium that is greater than that of stoichiometric spinel (MgAl ₂O₄) having an equal amount of cobalt dopant. Despite the relatively high ratio of aluminum to magnesium, most or essentially all magnesium and cobalt dopant occupy only tetrahedral positions of the crystal. Modification of the relative amount of aluminum to magnesium in the saturable absorber Q-switches of the invention enables adjustment of the ⁴T₁spectrum of cobalt dopant to more closely match a peak of 1544 nanometers, which is the lasing wavelength of erbium:ytterbium:glass (Er:Yb:glass) lasers. In another embodiment, modification of the relative amount of aluminum to magnesium also enables emission of a band at about 1340 nanometers, which is about the lasing wavelength of Nd³⁺:YAlO₃lasers. Both emission bands can significantly increase the efficiency of saturable absorber Q-switches employed with such lasers. Also, the saturable absorber Q-switches of the invention generally are relatively stable at reduced temperatures, such as at about 8 Kelvin (K).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of one embodiment of the laser system of the invention, employing a cobalt-doped Q-switch of the invention. [0018]
FIG. 2 shows light absorption in a 1:3 spinel as a function of wavelength at 8 Kelvin (K). [0019]
FIG. 3 shows light absorption in a 1:3 spinel as a function of wavelength at 300 Kelvin (K). [0020]
FIG. 4 shows fluorescence intensity of a 1:3 spinel as a function of wavelength at 8 Kelvin (K). [0021]
FIG. 5 shows fluorescence intensity of a 1:3 spinel as a function of wavelength at 300 Kelvin (K). [0022]
FIG. 6 is an overlay of FIGS. 4 and 5, as a comparison.[0023]

DETAILED DESCRIPTION OF THE INVENTION

The features and other details of the invention will now be more particularly described with reference to the accompanying figures and pointed out in the claims. It will be understood that the particular embodiments of the invention are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. This application is related to and incorporates by reference the subject matter of copending application Ser. No. ______, filed Sep. 22, 2003, to Kokta et al., bearing attorney docket number 1035-BI4282. This application is related to and incorporates by reference the subject matter for copending application Ser. No. ______, filed Sep. 22, 2003, to Kokta et al., bearing attorney docket number 1035-BI4307. This application is also related to and incorporates by reference the subject matter for copending application Ser. No. ______, filed Sep. 22, 2003, to Stone-Sundberg et al., bearing attorney docket number 1035-BI4281. [0024]
In one embodiment, a single crystal ceramic material for optical and optoelectronic applications is provided. The material comprises a single crystal spinel having a general formula aAD·bE[0025] ₂D₃, wherein A is selected from the group consisting of Mg, Ca, Zn, Mn, Ba, Sr, Cd, Fe, and combinations thereof, E is selected from the group consisting Al, In, Cr, Sc, Lu, Fe, and combinations thereof, and D is selected from the group consisting O, S, Se, and combinations thereof, wherein a ratio b:a>1:1 such that the spinel is rich in E₂D₃. In certain embodiments, the spinel is rich in E₂D₃such that the ratio b:a is not less than about 1.2:1, 1.5:1, or even 2.0:1. Particular working embodiments have a b:a ratio of about 2:1 and 3:1. Typically, b:a does not exceed about 4:1. Due in part to use of E₂D₃-rich compositions, the material has lower mechanical stress and/or strain as compared to stoichiometric spinels having a b:a ratio of 1:1.
In a particular embodiment, A is Mg, D is O, and E is Al, such that the single crystal spinel has the formula aMgO.bAl[0026] ₂O₃. The material may consist essentially of a single phase of spinel, with substantially no secondary crystalline phases.
Generally, the single crystal spinel is formed by a melt process, by growing a boule from a melt provided in a crucible. Here, a seed crystal, such as stoichiometric MgO.Al[0027] ₂O₃spinel is contacted to the melt provided in the crucible, the melt and the seed crystal are rotated with respect to each other, such as at a rate between 2 and 12 rpms, and the seed crystal (with growing single crystal boule) are drawn from the melt.
In another embodiment, the material further includes Co, providing a saturable absorber Q-switch. The Q-switch has a monocrystalline lattice, wherein the monocrystalline lattice has a formula of Mg[0028] _1-xCo_xAl_yO_z, and wherein x is greater than 0 and less than about 1, y is greater than 2 and less than about 8, and z is between about 4 and about 13. The monocrystalline lattice of the saturable absorber Q-switch employed in the laser system of the invention has tetrahedral and octahedral positions, and most of the magnesium and cobalt occupy tetrahedral positions. Preferably, essentially all of the cobalt and magnesium occupy tetrahedral positions.
An example of a laser system of the invention is shown in FIG. 1. As shown therein, [0029] laser system 10 includes resonator cavity 12. Resonator cavity 12 is defined by flat mirror 14 and outcoupler mirror 16. Flat mirror 14 and outcoupler mirror 16 are oriented along a resonant axis 18, whereby a light beam within resonator cavity 12 can operate in a cavity mode. Lasing element 20 is located along resonant axis 18 within resonator cavity 12. Typically, lasing element 20 is a cylindrical rod oriented parallel to resonant axis 18. Examples of suitable lasing elements include Er:Yb:glass (erbium:ytterbium:glass), Er:glass (erbium doped into a phosphate glass host) and Nd³⁺:YAlO₃(erbium doped into a yttrium-aluminum oxide host).
A suitable means for optically pumping the lasing element, [0030] optical pump 22, is proximate to lasing element. Focusing lens 24 is located between lasing element 20 and outcoupler mirror 16.
Q-[0031] switch 26 is located between focusing lens 24 and outcoupler mirror 16. Saturable absorber Q-switches of the invention include a monocrystalline lattice of a cobalt-doped spinel-like material wherein the molar ratio of aluminum to the sum of magnesium and cobalt components of the monocrystalline lattice exceeds 2:1. More specifically, the saturable absorber Q-switch of the invention includes a monocrystalline lattice having the formula Mg_1-xCo_xAl_yO_zwhere x is less than 1 (in some embodiments greater than 0), y is greater than 2 and less than 8, and z is between about 4 and 13. A “1:1 spinel” refers to an embodiment wherein y is about 2. A “1:2 spinel” refers to an embodiment where y is about 4. A “1:3 spinel” refers to an embodiment where y is about 6. Most of the magnesium and cobalt of the saturable absorber Q-switch occupy tetrahedral positions of the monocrystalline lattice. In a preferred embodiment, essentially all of the cobalt and magnesium occupy tetrahedral positions.
In one embodiment of the invention, the monocrystalline lattice has a value of z of about 4. In another embodiment, y is about 4 and z is about 7. In still another embodiment, y is about 6 and z is about 10. Generally, the saturable absorber Q-switch has a [0032] ⁴T₁spectrum between about 1537 nm and about 1544 nm. In one preferred embodiment, wherein the lasing element of the laser system of the invention is an Er:Yb: glass lasing element, the value of y is sufficient to cause the monocrystalline lattice of the saturable absorber Q-switch to have a ⁴T₁spectrum of cobalt ion (Co²⁺) to emit light at a wavelength of at least about 1.54 μm (1540 nm). In an especially preferred embodiment, the saturable absorber Q-switch has an absorption band of about 1544 nm.
In another preferred embodiment, such as wherein the lasing element is a Nd[0033] ³⁺:YAlO₃lasing element, the value of y is sufficient to cause the monocrystalline lattice to have an absorption band of between about 1337 nm and about 1365 nm, such as an absorption band of 1337 nm, 1360 nm, 1365 nm or, most preferably, about 1340 nm.
In one embodiment, the excited state absorption for the cobalt ion in the saturable absorber Q-switch of the invention is about the same as that of a saturable Q-switch absorber wherein a molar ratio of aluminum to the combined magnesium and cobalt amount is about 2. Generally, the unit cell dimension of the monocrystalline lattice will be less than about 8.085 Å. In a preferred embodiment, the unit cell dimension is between about 7.970 Å and about 8.083 Å. In still another embodiment, the saturable absorber Q-switch of the invention has a decay time (τ[0034] ₃₁) greater than about 30×10⁻⁶seconds.
Typically, the amount of cobalt ion in the saturable absorber Q-switch of the invention is greater than about 0.02 atomic percent. Preferably, the amount of cobalt ion present is in an amount in a range of between about 0.02 and about 0.043 atomic percent of the monocrystalline lattice. [0035]
The saturable absorber Q-switches of the invention can be formed by use of a spinel seed (MgAl[0036] ₂O₄) having a major axis oriented along the <111> axis. Preferably, the spinel seed is cylindrical. The crystal is grown, for example, in an inductively-heated ten kHz radiofrequency (RF) generator. Control of crystal growth can be maintained by use of suitable computer software, such as Automatic Diameter Control (ADC) software, commercially available from, for example, FEC Crystal Growing Systems, which can control the shape of the growing crystal, temperature increase, cooling rates, and other pertinent parameters. Crystal growth is commenced by heating a growth chamber of a suitable crucible, such as an iridium crucible, containing thoroughly mixed powders of magnesium oxide (MgO), cobalt oxide (Co₃O₄) and aluminum oxide (Al₂O₃). The growth chamber is heated to a suitable temperature, such as a temperature in a range of between about 1900° C. and about 2150° C. Preferably, the growth chamber is heated to a temperature of about 2150° C. to form a melt.
The spinel seed is immersed into the molten mixture and rotated while being withdrawn from the growth medium at a controlled rate. In one embodiment, the withdrawal rate is in a range of between about 0.25 and about 1.0 millimeters per hour at a rotation speed in a range of between about 4 and about 12 revolutions per minute (RPM). Preferably, the withdrawal rate is about 1 millimeter per hour and the rotation of the seed is about 8 RPMs. Crystal growth continues for a suitable period of time to form a monocrystalline lattice of suitable dimension. In one embodiment, crystal growth is continued for a period of about 150 hours. Thereafter, the crystal is cooled to about 25° C. over a period of time in a range of between about 72 and about 100 hours. Preferably, the crystal is cooled from the melt temperature, of about 2150° C. to about 25° C. over a period of time of about 100 hours. Thereafter, the crystal can be machined by known methods to form the saturable absorber Q-switch of the invention. [0037]
The invention is illustrated by the following examples, which are not intended to be limiting in any way. [0038]

EXEMPLIFICATION

EXAMPLE 1

General Method for Spinel Growth

The various cobalt doped spinel compositions were grown on 1:1 (MgAl[0039] ₂O₄) spinel seed oriented along the <111> axis. Desired compositions were melted in iridium crucibles of sizes appropriate for growth of 30 mm diameter, and 50 mm diameter crystals. The sizes of the melts for larger crystals were circa 3000 gms. The iridium crucibles were inductively heated by 10 kHz RF (radio-frequency) generators. The diameter control was based on controlling the growing crystals weight via controlling the generator output in accordance to the signal from a load cell. On an average, the melting point of the spinel was about 100 degrees higher than the melting point of sapphire. Prior to and during the growth, the melts were maintained under an ambient atmosphere strictly inert. The volatility of the Co oxide dopant was very low. The Co oxide apparently reacted with the spinel components on the heat up, and did not evaporate from the melt. The crystals of 1:1 and 1:2 compositions appeared to grow relatively easily, with linear growth rates exceeding 1-2 mm/hr. The charge preparation in a case of the 1:3 compound included a very thorough mixing of the constituent oxides. In addition, the results were sensitive to establishing a good equilibrium condition during seeding of the crystal, and also to the crystal growth rate.

EXAMPLE 1A

1:3 Spinel Growth

Composition [0040]
206.05 gms of MgO [0041]
0.41 gms of Co[0042] ₃O₄
1043.54 gms of Al[0043] ₂O₃
The composition was mixed and loaded into 3″ diameter 4½″ tall iridium crucible of 440 ml volume. The crucible was placed into growth system comprising RF (radio frequency), generator (power) supply, a growth chamber containing the RF coupling coil, zirconium oxide insulation material in an ambient gas enclosure—“Bell Jar,” and an electronic control system. Control was accomplished by controlling the RF generator output in response to the mass of the growing crystal. “ADC” (Automatic Diameter Control) software, supplied by F. Bruni, controlled the shape of growing crystal, temperature increase, and cool down rates, and all other pertinent parameters. The crucible with the oxide mixture was heated to 2150° C. to form a melt. <111> spinel “seed” (small rod-shaped crystal) was immersed (dipped) into the molten mixture. Applying a withdrawal rate of 1 mm/hr along with rotation of the seed at 8 rpm, the crystal growth was started. Growth continued for 150 hours followed by a 100 hour cool down period. [0044]
Result: A blue crystal, “Spinel” crystal structure, ¼″ diameter, 7″ long A[0045] ₀=8.012A⁰Optical measurement: O.D. (Optical Density): 0.7 cm⁻¹

EXAMPLE 1B

1:2 Spinel Growth

Composition [0046]
141.56 gms of MgO [0047]
0.87 gms of Co[0048] ₃O₄
1107 gms of Al[0049] ₂O₃
The composition was loaded into same crucible as described in Example #1, and placed in an identical growth system. Heat-up time was 6 hours to 2150° C. Rotation rate applied was 8 rpm, pull rate 1 mm/hr under strictly inert atmosphere. Growth time of 150 hours was followed by a 100 hour cool-down period. Grown crystal was harvested at room temperature. [0050]
Result: A blue crystal [0051]
Structure: “Spinel”[0052]
[0053] _A0=7.97 A⁰
Optical Density: 2.4 cm[0054] ⁻¹

EXAMPLE 1C

1:1 Spinel Growth

Composition [0055]
353.68 gms of MgO [0056]
0.70 gms of CO[0057] ₂O₃
895.62 gms of Al[0058] ₂O₃
Raw materials were mixed and loaded into an iridium crucible. The crucible was placed in the previously described system. Temperature was increased over a period of 6 hours to 2150° C. to complete melting. <111> spinel seed was immersed (dipped) into the melt. A withdrawal rate of 1 mm/hr, crystal growth was started. Growth continued for 150 hours followed by a 100 hour cool down period. [0059]
Result: A single crystal spinel ¼″ diameter, 7″ long [0060]
Structure: “Spinel”[0061]
Optical Density: 0.63 cm[0062] ⁻¹

EXAMPLE 2

Experimental Details

Crystals of MgAl[0063] ₂O₄, MgAl₄O₇, and MgAl₆O₁₀doped with varying amounts of cobalt from 0.02 to 0.04 percent atomic cobalt were grown by the method described in Example 1. We labeled the different spinels according to 1:1 (MgO.Al₂O₃), 1:2 (MgO.2Al₂O₃), and 1:3 (MgO.3Al₂O₃). The structural analysis for each crystal gave unit cell dimensions of 8.083 Å for 1:1, 8.012 Å for 1:2, and 7.970 Å for 1:3. Each spinel belonged to the space group O_h ⁷-Fd3m with the Mg²⁺ ions having tetrahedral coordination with full T_dsymmetry and the Al³⁺ ions having octahedral coordination (P. R. Staszak, et al., J. Phys C: Solid State Phys., 17:4751 (1984) and H. St. C. O'Neill and A. Navrotsky, Am. Mineralogist, 68:181 (1983), the teachings of which are incorporated herein by reference in their entirety). The lattice constant for 1:1 reported in the literature was 8.085 Å (R. D. Gillen and R. E. Salomon, J. Phys. Chem., 74:4252 (1970), the teachings of which are incorporated herein by reference in their entirety). Previous studies, including thermodynamic phase diagram analyses of MgO.nAl₂O₃and optical studies of Co²⁺, showed a strong preference for Co²⁺ in tetrahedral sites when the crystal had both tetrahedral and octahedral cation sites (A. Navrotsky and O. J. Kleppa, J. Inorg. Nucl. Chem., 29:2701 (1967); A. Navrotsky and O. J. Kleppa, J. Inorg. Nucl. Chem., 30:479 (1968); A. Navrotsky, et al., J. Am. Ceramic Soc., 69:418 (1986); A. Navrotsky, Am. Mineralogist, 79:589 (1994); and N. V. Kuleshov, et al., J. Luminescence, 55:265 (1993), the teachings of which are incorporated herein by reference in their entirety). Our results, described infra, indicated that the tetrahedral site were preferred sites of occupation by Co²⁺.
Polished samples used in spectroscopic measurements ranged from [0064] circular disks 4 cm in diameter and 0.5 cm thick, to rectangular pieces for low-temperature studies that measured 10 mm by 5 mm by 2.15 mm thick. Crystals having the optimum optical density at 1.54 μm were examined for use as saturable absorbers. Room temperature absorption spectra were obtained between 3000 nm and 300 nm with a Perkin-Elmer Lambda-nine spectrophotometer. Calibration of the instrument over the wavelength of interest indicated that spectral lines and bands were measured to an accuracy of 0.22 nm. The low temperature (8K) absorption spectrum was obtained with an upgraded Cary Model 14R spectrophotometer controlled by a desktop computer. The spectral bandwidth was set at 0.5 nm and the instrument was internally calibrated to an accuracy of 0.3 nm. Spectra were analyzed and plotted by using the computer software program Sigma Plot. Fluorescence spectra at room temperature and at 8K were also obtained by using the instrument together with appropriate mirrors and filters and a Spex Model 340 E monochromator. For fluorescence studies, excitation at 514.5 nm was provided by an argon ion laser.
For low-temperature studies, the sample was mounted at the cold finger of a CTI Model-22 closed-cycle helium cryogenic refrigerator capable of operation between 8K and room temperature. The sample temperature was monitored with a silicon-diode sensor attached to the base of the sample holder and maintained by using a Lake Shore control unit. [0065]
The fluorescence lifetime of the strongest emission band centered between 650 nm and 700 nm was measured by exciting each sample with the second harmonic (532 nm) of a Quanta-Ray pulsed Nd:YAG laser Model GCR-12S. The pulse width was about 6 ns and the beam divergence was less than 0.5 μrad. The output energy was 15 mJ at 10 Hz. The signal was detected by a photomultiplier tube attached to the exit slit of the monochromator and sent to a 150 MHZ Tektronix oscilloscope Model 2445A having a resolution of 10 ns. [0066]
Observed Spectra [0067]
The room temperature absorption spectrum of Co[0068] ²⁺ in the three spinel crystals is given in Table 1. The concentration of Co²⁺ in each sample was 0.033% (atomic weight percent, or “at.”) Co for 1:1, 0.02% at. Co for 1:2, and 0.0429% at. Co for 1:3. The general features in all three spectra were similar and consisted of two relatively strong bands centered near 600 nm and 1350 nm and weaker bands appearing between 550 nm and 470 nm, and between 2500 nm and 1900 mn (N. V. Kuleshov, et al., J. Luminescence, 55:265 (1993), the teachings of which are incorporated herein by reference in their entirety). However, comparable peaks and bands showed a noticeable shift to longer wavelengths from the 1:1 crystals to the 1:3 crystals. Of particular interest was the shift of the ⁴T₁spectrum of Co²⁺ in the 1:3 sample to wavelengths even more favorable for Q-switching at 1.54 μm than the saturable absorber Co²⁺:MgAl₂O₄(the 1:1 host crystal) (J. B. Gruber, et al., Proc. of SPIE, 3928:142 (2000), the teachings of which are incorporated herein by reference in their entirety). The peak at 1544 nm was observed where stimulated emission occurred in the Er:Yb:glass laser. Its estimated absorption cross section at this wavelength was higher than the value employed for Co²⁺:MgAl₂O₄(4×10⁻¹⁹cm²) and was considerably larger than the stimulated emission cross section of Qx/Er at 1535 nm (0.6×10⁻²⁰cm²) (V. P. Mikhailov, et al., OSA TOPS, 21(ASSL):145 (1999); M. B. Carmargo, et al., Opt. Letts, 20:339 (1995); J. B. Gruber, et al., Proc. of SPIE, 3928:142 (2000); and R. Wu, et al., OSA TOPS, 22(ASSL):421 (2000), the teachings of which are incorporated herein by reference in their entirety). Excited state absorption (ESA) for Co²⁺ near 1540 nm in 1:1 samples has been reported by several groups (V. P. Mikhailov, et al., OSA TOPS, 21(ASSL):145 (1999); M. B. Carmargo, et al., Opt. Letts, 20:339 (1995); and M. Birnbaum, et al. OSA TOPS, 19(ASSL):148 (1997)) including our group (J. B. Gruber, et al., Proc. of SPIE, 3928:142 (2000)) that has done extensive modeling studies on saturable absorbers. The ESA cross section for Co²⁺ in the 1:3 compound, was similar to the value reported by Co²⁺ in the 1:1 compound (M. B. Carmargo, et al, Opt. Letts, 20:339 (1995)).
The similarity in the room temperature spectra of the three samples led us to examine the details of the absorption spectrum for Co[0069] ²⁺:MgAl₄O₁₀at 8K. Table II presents the absorption spectrum between 2590 nm and 476.5 nm. FIGS. 2 and 3 show light absorption of the 1:3 spinel as a function of wavelength at 8 Kelvin and 300 Kelvin, respectively. The pattern of light absorption between 1200 mm and 1600 mm indicates possible use of this material for passive Q-switches for “eye-safe” (1.546μ (micron)) lasers, but also for lasers operating in a range of between about 1.3 and about 1.35μ, which is useful in medicine as well as in optical communications business. The comparison at the two temperatures indicates that the material also is useful at room temperature. The observed spectra were similar to the spectra reported earlier for Co²⁺ ions in tetrahedral sites in MgAl₂O₄(N. V. Kuleshov, et al., J. Luminescence, 55:265 (1993), the teachings of which are incorporated herein by reference in their entirety). There were some differences in the magnitude of the crystal-field splitting of Co₂₊ in tetrahedral sites which can be seen by comparing the energy levels in Table II., col. 5, with the energy levels of Co²⁺ in ZnAl₂O₄, for which the data of Ferguson, et al. (J. Ferguson, et al., J. Chem. Phys., 51:2904 (1969)) allowed us to do extensive modeling (J. B. Gruber, et al., Proc. of SPIE, 3928:142 (2000). Table II, Col. 2, shows the Tanabe-Sugano labels where (^2s+1L) represents the principal state (either quartet or doublet); the wavelength, absorption coefficient and the energy of the transition are given in Cols. 3-5. The energy-level calculations and modeling are described below.
The fluorescence spectra at 8K and at 300K were characterized by a strong emission band between 600 nm and 700 nm. As can be seen in FIGS. 4, 5 and [0070] 6, fluorescence emissions as a function of wavelength of 1:3 spinels are comparable at 8 Kelvin and 300 Kelvin. These materials are useful as active materials for broadly tunable lasers. Also, two very weak, broad bands centered around 920 nm and 1300 nm which typically were observed only in more concentrated samples (N. V. Kuleshov, et al., J. Luminescence, 55:265 (1993)). The assignment of the transitions could be made with help from the analysis of the levels given in Table II. The strong red emission band centered at 660 nm was due to vibronic and electronic transitions from the ²E, ⁴T excited states to the ground state, ⁴A₂, the weak broad band observed at 920 nm represented similar transition types from ²E, ⁴T₁to the ⁴T₂state, and the weak band around 1300 nm represented vibronic and electronic transitions from ²E, ⁴T₁to the ⁴T₁manifold observed in absorption between 1540 nm to 1230 nm. A weak band observed at 725 nm at 8K may have represented ²A₁□⁴T₂transitions (see FIG. 5).
The room temperature fluorescence of the Co[0071] ²⁺(²E⁴T₁I) state was a single exponential, and the lifetime was measured to be about 30 μs. The emission intensity did not appear to change appreciably with decrease in temperature to 8K, and so we did not expect the low temperature lifetime to vary significantly from the room temperature value. Using crystals of the 1:1 sample containing between ten and twenty times more Co²⁺ than we report, in Table II, for Co²⁺:MgAl₄O₁₀. Kuleshov, et al. (. V. Kuleshov, et al., J. Luminescence, 55:265 (1993)), found that the luminescence lifetime for all three bands was the same. The emission decay was strongly nonexponential and dependent on the temperature and Co²⁺ ion concentration. However, their results were expected given the extent to which the 3d⁷orbitals interacted with the lattice of the host crystal at such Co²⁺ ion concentrations.
Energy Levels of Co[0072] ²⁺
The absorption spectra of Co[0073] ²⁺ (3d⁷) in tetrahedral cation sites of the spinels consist of vibronically-coupled electronic transitions (including zero-phonon transitions) from the ground state ⁴A₂(⁴F) to excited quartet states such as ⁴T₂(⁴F) and ⁴T₁(⁴P), and excited doublet states, including ²E(²G), ²T₁(²G), ²A₁(²G), ²T₁(²P), and ₂T₂(²H). The electronic (Stark) levels for the 3d⁷configuration are determined using a Hamiltonian that consists of atomic and crystal-field terms (C. A. Morrison, “Crystal Fields for Transition-Metal Ions in Laser Host Materials,” (Springer, N.Y.) (1992), the teachings of which are incorporated herein by reference in their entirety). The atomic or “free-ion” part is given as, $\begin{matrix} {\hat{H}}_{Fl}^{(} = \sum_{k = 2, 4} F^{(K)} \sum_{i > j}^{n} C_{kq}^{n} (\hat{i}) C_{kq} (\hat{j}) + α \hat{L} (\hat{L} + 1) + γ G ({\hat{R}}_{5}) + ζ_{d} \sum_{j} {\overline{l}}_{\overline{l}} \cdot {\overline{s}}_{l}, & (1) \end{matrix}$
where F[0074] ^(k)are the Slater coulombic repulsion parameters between equivalent d electrons, α and γ are interconfiguration parameters and ζ_dis the spin-orbit coupling parameter for the 3d electrons (C. A. Morrison, “Angular Momentum Theory Applied to Interactions in Solids,” (Springer, N.Y.) (1988), the teachings of which are incorporated herein by reference in their entirety). The crystal-field terms for Co²⁺ in tetrahedral sites are given $\begin{matrix} {\hat{H}}_{CF} = B_{20} \sum_{i} C_{20} (\hat{i}) + B_{40} \sum_{i} C_{20} (\hat{i}) + B_{44} \sum_{i} [C_{44} (\hat{i}) + C_{4 - 4} (\hat{i})], & (2) \end{matrix}$
as, [0075]
where the B[0076] _nmrepresent crystal-field parameters that are related to the lattice-sum parameters, A_nm, through the three-parameter theory with B_nm=ρ_nA_nm(C. A. Morrison, et al., Chem. Phys., 154:437 (1991), the teachings of which are incorporated herein by reference in their entirety). The initial set of atomic and crystal-field parameters are listed in Table III and are obtained from several sources (C. A. Morrison, “Crystal Fields for Transition-Metal Ions in Laser Host Materials,” (Springer, N.Y.) (1992). We treat F^(k)and the three B_nmparameters as adjustable, beginning with a set of F⁽²⁾and F⁽⁴⁾proposed originally by Morrison (C. A. Morrison, “Crystal Fields for Transition-Metal Ions in Laser Host Materials,” (Springer, N.Y.) (1992)) and an initial set of B_nmbased on lattice-sum modeling using ion separations based on our x-ray crystallography studies of the spinel series.

Matrix elements for the Hamiltonian were computed using coefficients of fractional parentage for the 3d ⁷electronic configuration. The complete Hamiltonian was diagonalized in the basis states S,L, and the calculated levels for Co²⁺ in MgAl₆O₁₀are given as an example in Table II, Col. 6. The splitting of the ground-state, ⁴A₂(⁴F) was not fully resolved in the temperature-dependent spectra. The predicted splitting given in table II is 5 cm⁻¹. The observed splitting in Co²⁺:ZnAl₂O₄, wherein Co²⁺ occupies the Zn²⁺ tetrahedral site, was 12 cm⁻¹(J. Ferguson, et al., J. Chem. Phys., 51:2904 (1969), the teachings of which are incorporated herein by reference in their entirety). Only one of the observed levels was used to establish the energy of the ⁴T₂(⁴F) state since the spectra of this manifold were very weak in the 0.0429% at Co spectrum reported in Table II. Longer pathlengths and greater concentrations of Co²⁺ provided spectra that support the predicted levels 3 through 8 for this manifold splitting. Levels 15 through 25 showed a strong mixing of ²G states into the ⁴p states (Col. 7, Table II). Many of the zero-phonon transitions allowed in T_dsymmetry were obscured by the vibronic bands making it difficult to attempt an overall fitting of the observed-to-calculated energy levels. However, the continuity in general band shape and structure throughout the series was predicted very well, with the final set of spectroscopic parameters given in Table III.

TABLE I


Room temperature absorption bands of Co²⁺in MgO.nAl₂O₃

MgAl₂O₄

MgAl₄O₇

MgAl₆O₁₀

STATE^α	Λ (nm)^b	α^c(cm⁻¹)	E (cm⁻¹)^d	Λ (nm)^b	α^c(cm⁻¹)	E (cm⁻¹)^d	Λ (nm)^b	α^c(cm⁻¹)	E (cm⁻¹)^d

⁴T₂	2519	0.03	3970	2556		0.04	3912	2580		0.05	3870
	2448	0.03	4085	2476		0.04	4039	2500		0.04	4000
(⁴F)				2365	(sh)	0.05	4228	2390	(sh)	0.05	4184
	2252	0.05	4441	2279		0.07	4388	2300		0.09	4347
	2163	0.03	4623	2190	(sh)	0.05	4566	2220	(sh)	0.06	4505
⁴T₁	1536	5.21	6510	1537		5.78	6506	1544		5.91	6476
(⁴F)	1417	4.82	7057	1450		5.12	6897	1460	(sh)	5.32	6849
	1350	5.03	7407	1360		5.32	7353	1365		5.50	7326
	1229	4.36	8137	1234		4.72	8104	1238		4.50	8077
²E (²G)	671	1.36	14900	672		1.28	14880	675		1.31	14815
⁴T₁	625	16.3	16000	626		14.3	15974	628		15.6	15923
(⁴P)	598	15.9	16722	599		14.7	16694	598		15.2	16700
	580	17.1	17241	581		16.0	17211	583		17.2	17150
²A₁	545	2.8	18343	545		2.8	18348	546		2.6	18315
(²G)
²T₁	475	0.8	21053	476		0.7	21008	476.5		0.8	20986
(²P)

TABLE II


Absorption spectra of Co²⁺in MgAl₄O₁₀at 8 K^a

MgAl₄O₁₀

E (cm⁻¹)

Level	State	Λ (nm)_abc	α (cm⁻¹)	E (cm⁻¹)	Calc.^b	Mixture SL States^c

1	⁴A₂				0	−7	1.00 ⁴F
2	(⁴F)					−2	1.00 ⁴F
3	⁴T₂	2590		vwk	3861	3728	0.98 ⁴F + 0.01 ⁴P + 0.01 ¹G
4	(⁴F)	2500	(b)	vwk	4000	4019	0.99 ⁴F + 0.01 ²G
5		2400	(b)	vwk	4166	4146	0.99 ⁴F + 0.01 ⁴P
6						4411	0.99 ⁴F + 0.01 ⁴P
7		2231.5^d		1.11	4481	4544	0.99 ⁴F + 0.01 ⁴P
8		2110		vwk	4739	4713	0.99 + ⁴F + 0.01 ⁴P
9	⁴T₁	1539^d		5.33	6498	6479	0.91 ⁴F + 0.09 ⁴P
10	(⁴F)	1460	(sh)	4.82	6849	6854	0.86 ⁴F + 0.13 ⁴P + 0.01 ²G
11		1337^d		5.24	7479	7507	0.99 ⁴F + 0.01 ⁴P
12						7925	0.95 ⁴F + 0.01 ⁴P + 0.01 ²D (2)
13		1241^d		4.17	8058	8065	0.91 ⁴F + 0.08 ⁴P + 0.01 ²D (2)
14		1230	(sh)	3.82	8130	8119	0.97 ⁴F + 0.02 ⁴P + 0.01 ²D (2)
15	⁴E	673^d		1.12	14860	14877	0.39 ²G + 0.20 ⁴P + 0.15 ²P
16	(²G)	670	(sh)	1.00	14925	14913	0.56 ²G + 0.17 ⁴P + 0.15 ⁴F

17	⁴T₁	Band	3.0	15267	15246	0.65 ⁴P + 0.18 ²G + 0.11 ⁴F
18	(⁴P)	Band		Unresolved	15356	0.45 ²G + 0.18 ²P + 0.15 ⁴P
				band
19		Band			15357	0.66 ²G + 0.13 ²D (2) + 0.09 ²H
20		Band			15690	0.49 ²G + 0.20 ²P + 0.16 ²H
21					15718	0.48 ⁴P + 0.24 ²G + 0.14 ²P

22		621^d		15.07	16103	16167	0.90 ⁴P + 0.06 ²G + 0.02 ⁴F
23		605^d		16.1	16529	16451	0.67 ⁴P + 0.22 ²G + 0.04 ²H
24		598		17.40	16722	16696	0.82 ⁴P + 0.11 ²G + 0.02 ²H
25		583	(b)	18.1	17150	16852	0.70 ⁴P + 0.23 ²G + 0.04 ²H
26	²A₁	552	(sh)	11.0	18116	18080	0.65 ²G + 0.21 ⁴P + 0.07 ²D (1)
27	(²G)	546^d		9.3	18315	18286	0.85 ²G + 0.09 ²D (2) + 0.03 ²D (1)
28						18389	0.87 ²G + 0.05 ²D (2) + 0.07 ²H

29		Band			18746	0.63 ²G + 0.24 ²D (2) + 0.08 ²D (1)
30					19831	0.42 ²G + 0.37 ²P + 0.12 ²H

31		500^d		0.7	20000	19870	0.43 ²G + 0.40 ²P + 0.09 ²H
32	²T₁	490	(sh)	0.50	20408	20494	0.62 ²2P + 0.23 ²G + 0.08 ²H
33	(²P)			0.60	20986	20862	0.34 ²H + 0.25 ²G + 0.23 ²D (2)
34	²T₂					21476	0.45 ²H + 0.24 ²D (2) + 0.18 ²G
35	(²H)					21906	0.41 ²D (2) + 0.36 ²H + 0.10 ²D (1)

TABLE III


Spectroscopic parameters for Co²⁺in T_dsites^a

MgAl₂O₄

MgAl₄O₇

MgAl₆O₁₀

	Initial	Final	Initial	Final	Initial	Final
	Value	Value	Value	Value	Value	Value
Parameter	(cm⁻¹)^b	(cm⁻¹)	(cm⁻¹)^c	(cm⁻¹)	(cm⁻¹)^d	(cm⁻¹)

F⁽²⁾	59367	59746	60520	61050	61045	61542
F⁽⁴⁾	42210	41946	41843	41325	41705	40168
B₂₀	2720	2566	2641	2814	3119	3949
B₄₀	−8640	−8693	−8714	−8920	−9267	−9081
B₄₄	5163	5120	5092	5040	5171	5242
ζ_d	420	420	537	537	515	515
α	86	86	108	108	108	108

Modeling of Crystals as Saturable Absorbers [0080]
Co[0081] ₂₊has been modeled as a saturable absorber for passively Q-switching the eyesafe (1.54 μm) Er:Yb:glass laser (J. B. Gruber, et al., Proc. of SPIE, 3928:142 (2000)). The model makes use of the rate equations based on quasi-three level gain medium and a four-level absorber that includes excited-state absorption (ESA). The model was expanded to include energy transfer between Yb and Er and excited state absorption in the gain medium. The spectroscopic parameters for the various gain media are available in the open literature (J. B. Gruber, et al., Proc. of SPIE, 3928:142 (2000), the teachings of which are incorporated herein by reference in their entirety)). For the saturable absorber Co²⁺:MgAl₆O₁₀, which we modeled recently, we used concentrations equivalent to that reported in the present study; an index of refraction we determined near 1.54 μm (1.742); an experimental σ(gs)=5.2×10⁻¹⁹cm²; an experimental σ(gs)=1.87×10⁻¹⁹cm², and a delay time (τ₃₁) of 30×10⁻⁶s.
The 1:3 material is a better performer as a saturable absorber than 1:1 and 1:2 spinels given comparable Co[0082] ₂₊ ion concentrations and a laser cavity design that is the same for all three spinel samples.
In summary, all members of the series may prove to be efficient high performance absorbers for Q-switching at the 1:54 μm wavelength. [0083]
Equivalents [0084]
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. [0085]

Claims

What is claimed is:

1. A single crystal ceramic material for optical and optoelectronic applications, comprising a single crystal spinel having a general formula aAD·bE₂D₃, wherein A is selected from the group consisting of Mg, Ca, Zn, Mn, Ba, Sr, Cd, Fe, and combinations thereof, E is selected from the group consisting Al, In, Cr, Sc, Lu, Fe, and combinations thereof, and D is selected from the group consisting O, S, Se, and combinations thereof, wherein a ratio b:a>1:1 such that the spinel is rich in E₂D₃, and the single crystal spinel is formed by a melt process.

2. The material of claim 1, wherein A is Mg, D is O, and E is Al, such that the single crystal spinel has the formula aMgO.bAl₂O₃.

3. The material of claim 1, wherein the single crystal spinel is grown from a melt provided in a crucible.

4. The material of claim 1, wherein the material has a lower mechanical stress and strain compared to stoichiometric spinel.

5. The material of claim 1, wherein the material consists essentially of a single phase of said spinel, with substantially no secondary crystalline phases.

6. The material of claim 1, wherein b:a is not less than about 1.2:1.

7. The material of claim 1, wherein b:a is not less than about 1.5:1.

8. The material of claim 1, wherein b:a is not less than about 2.0:1.

9. The material of claim 1, further comprising Co, wherein the ceramic material forms a saturable absorber Q-switch.

10. The material of claim 9, wherein the saturable absorber Q-switch has a formula Mg_1-xCo_xAl_yO_zwhere x is greater than 0 and less than about 1, y is greater than 2 and less than about 8, and z is between about 4 and about 13, said single crystal having tetrahedral and octahedral positions, and wherein most of the magnesium and cobalt occupy tetrahedral positions.

11. A method of forming a monocrystalline spinel material, comprising:

forming a melt; and

growing a spinel single crystal from the melt, the single crystal spinel having a general formula aAD·bE₂D₃, wherein A is selected from the group consisting of Mg, Ca, Zn, Mn, Ba, Sr, Cd, Fe, and combinations thereof, E is selected from the group consisting Al, In, Cr, Sc, Lu, Fe, and combinations thereof, and D is selected from the group consisting O, S, Se, and combinations thereof, wherein a ratio b:a>1:1 such that the spinel single crystal is rich in E₂D₃.

12. The material of claim 11, wherein A is Mg, D is O, and E is Al, such that the single crystal spinel has the formula aMgO.bAl₂O₃.

13. The material of claim 11, wherein b:a is not less than about 1.5:1.

14. The method of claim 11, wherein the melt is provided in a crucible.

15. The method of claim 11, wherein the single crystal is grown by contacting a seed crystal with the melt.

16. The method of claim 15, wherein the seed crystal and the melt are rotated with respect to each other during growing.

17. The method of claim 16, wherein rotation is carried out at a rate within a range of about 2 to about 12 rpms.

18. The method of claim 15, wherein the seed crystal is withdrawn from the melt within a range of about 0.04 inches/hour to about 0.1 inches/hour.

19. The method of claim 11, wherein A is Mg, D is O, and E is Al, the spinel single crystal further includes Co, and the spinel single crystal forms a saturable absorber Q-switch.

20. The method of claim 19, wherein a molar ratio of Mg:Co:Al of the spinel is (1-x):x:y, where x is greater than 0 and less than about 1, and y is greater than 2 and less than about 8.

21. The method of claim 11, wherein the melt is heated to a temperature greater than about 2150° C.