Treatment and/or stabilizing gases in an optical gyro based on an inorganic waveguide
10095057 ยท 2018-10-09
Assignee
Inventors
- Nancy E. Iwamoto (Ramona, CA)
- Steven J. Sanders (Scottsdale, AZ, US)
- Timothy J. Callaghan (Roseville, MN, US)
- Stephen Yates (South Barrington, IL, US)
- Austin Taranta (Scottsdale, AZ, US)
- Jason C. Grooms (Saint Petersburg, FL, US)
- Kara L. Warrensford (Tampa, FL, US)
Cpc classification
G01C19/64
PHYSICS
B05C3/02
PERFORMING OPERATIONS; TRANSPORTING
International classification
G02F1/03
PHYSICS
G01C19/64
PHYSICS
B05C3/02
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A system is provided, the system including at least one integrated optical circuit (IOC) formed from at least one material, and a support-structure configured to support the at least one IOC to couple light between other components. A performance of the at least one IOC is improved by treatment with at least one selected gas.
Claims
1. A system comprising: at least one integrated optical circuit (IOC) formed from a lithium-niobate-based material, wherein a bandgap of the at least one IOC is increased by exposure to at least one selected fill gas as compared to an IOC operated in a vacuum; and a support-structure configured to support the at least one IOC to couple light between other components; and a sealed enclosure enclosing the at least one IOC and the at least one selected fill gas; wherein the at least one selected fill gas includes one of: nitrogen oxide (NO); nitrogen dioxide (NO.sub.2); sulfur dioxide (SO.sub.2); nitrous oxide (N.sub.2O); ammonia (NH.sub.3); or trimethylphosphine (PMe.sub.3).
2. The system of claim 1, wherein the at least one selected fill gas further includes at least one dilution gas.
3. The system of claim 2, wherein the at least one selected fill gas includes N.sub.2O.
4. The system of claim 2, wherein the at least one dilution gas includes at least one of: N.sub.2, a noble gas, CO.sub.2, or a saturated hydrocarbon.
5. The system of claim 1, wherein the system is a gyroscope system, wherein the at least one IOC formed from the lithium-niobate-based material is a phase modulator.
6. The system of claim 5, wherein the support structure is one of: at least a portion of the enclosure in which the phase modulator is enclosed; or positioned within the enclosure in which the phase modulator is enclosed, and wherein at least one of the at least one selected fill gas is enclosed in the enclosure with the phase modulator.
7. The system of claim 6, wherein the at least one selected fill gas includes at least a first selected fill gas and a second selected fill gas.
8. The system of claim 7, wherein the first selected fill gas is added to the enclosure prior to adding the second selected fill gas to the enclosure.
9. The system of claim 7, wherein the first selected fill gas is N.sub.2O and the second selected fill gas is N.sub.2.
10. The system of claim 5, wherein the lithium-niobate-based material is pre-treated with a gas prior to enclosing the phase modulator in the enclosure with the at least one selected fill gas.
11. The system of claim 5, wherein the gyroscope system further comprises: a light source; a coupler; an input fiber coupled to the light source, the coupler, and the phase modulator; an output fiber coupled to the coupler; a sensing coil coupled to the phase modulator; and a rate detector coupled to the output fiber.
12. The system of claim 11, wherein the at least one selected fill gas includes N.sub.2O.
13. The system of claim 1, wherein the at least one selected fill gas includes N.sub.2O.
14. A gyroscope system comprising: at least one phase modulator formed from a lithium-niobate-based material, wherein a bandgap of the at least one phase modulator is increased by exposure to at least one selected gas as compared to a phase modulator operated in a vacuum; and a sealed enclosure in which the at least one phase modulator is enclosed, wherein at least one of the at least one selected gas is enclosed in the enclosure with the at least one phase modulator, wherein the at least one selected gas enclosed in the enclosure with the at least one phase modulator includes one of: nitrogen oxide (NO); nitrogen dioxide (NO.sub.2); sulfur dioxide (SO.sub.2); nitrous oxide (N.sub.2O); ammonia (NH.sub.3); or trimethylphosphine (PMe.sub.3).
15. The gyroscope system of claim 14, wherein the at least one selected gas includes N.sub.2O.
16. The gyroscope system of claim 14, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, wherein the lithium-niobate-based material is pre-treated with at least the first selected gas, by one of: exposing the lithium-niobate-based material to the first selected gas prior to enclosing the phase modulator in the sealed enclosure with the second selected gas; and exposing the lithium-niobate-based material to the first selected gas after enclosing the phase modulator in the enclosure in order to equilibrate the lithium-niobate-based material to the first selected gas prior to adding the second selected gas to the enclosure.
17. The system of claim 14, wherein the at least one selected gas includes at least a first selected gas and a second selected gas.
18. The system of claim 14, wherein the gyroscope system further comprises: a light source; a coupler; an input fiber coupled to the light source, the coupler, and the phase modulator; an output fiber coupled to the coupler; a sensing coil coupled to the phase modulator; and a rate detector coupled to the output fiber.
19. The system of claim 18, wherein the at least one selected gas includes N.sub.2O.
20. The system of claim 14, wherein the at least one selected gas further includes a dilution gas.
Description
DRAWINGS
(1) Understanding that the drawings depict only exemplary embodiments and are not therefore to be considered limiting in scope, the exemplary embodiments will be described with additional specificity and detail through the use of the accompanying drawings, in which:
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(42) In accordance with common practice, the various described features are not drawn to scale but are drawn to emphasize specific features relevant to the exemplary embodiments.
DETAILED DESCRIPTION
(43) In the following detailed description, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific illustrative embodiments. However, it is to be understood that other embodiments may be utilized and that logical, mechanical, and electrical changes may be made. Furthermore, the method presented in the drawing figures and the specification is not to be construed as limiting the order in which the individual steps may be performed. The following detailed description is, therefore, not to be taken in a limiting sense.
(44) High-performance fiber-optic gyroscopes may include lithium niobate modulators. Such lithium niobate modulators include an optical waveguide (e.g., an integrated optical chip (IOC)) formed in the lithium niobate material. Lithium niobate (also referred to herein as LN) is a dielectric material that is highly electrically insulating at room temperature. Good gyroscopic performance relies on the insulating property and the stability of the insulating property of LN over time and over temperature changes. The terms gyroscope and gyro are used interchangeably herein. As defined herein, gyro performance includes angle noise and scale factor nonlinearity. A high performance gyro has an angle noise of less than 10 arcesc over some bandwidth of interest and a scale factor nonlinearity of less than 100 ppm over some rotation dynamic range.
(45) The modeling and testing techniques described herein are used to select gases to overcome the disadvantages of the currently available LN-based phase modulators. The LN-based phase modulators include modulators formed from proton exchanged (HN) lithium niobate materials in an IOC. As defined herein proton exchanged lithium niobate materials are lithium-niobate-based materials. The technology described herein selects one or more gas that is optimally suited to remove, prevent, or minimize surface defect states of lithium-niobate-based material based on modeling and testing a plurality of test gases. The IOCs described herein are formed from a niobium oxide-based electro-optic inorganic material. The term inorganic material as used herein refers to niobium oxide-based electro-optic inorganic material or lithium-niobate-based material.
(46) The gases that provide a relatively high band gap (with reference to a vacuum) are used to pretreat the material, enclose the gas in a sealed enclosure with the material, or both. For example, a selected gas can be used as a pre-treatment gas and/or fill gas for a LN-based phase modulator in a gyroscope.
(47) Over time and temperature changes, an integrated optical chip that includes a lithium niobate waveguide that is not treated according to the technology described herein can become slightly more conductive, allowing electrical leakage. This electrical leakage degrades gyro performance. Specifically, this electrical leakage can cause increases in both angle noise and in the scale factor nonlinearity. As is known to one skilled in the art, electrical leakage in any crystalline inorganic materials (e.g., LN) is related to the width of the electronic band gap for any surface defect states. More specifically, as is known to one skilled in the art, the electrical leakage in the LN (or HN) is related to the width of the electronic band gap for any surface defect states.
(48) As described above, exposure to oxygen serves to stabilize these defects that allow electrical leakage and prevent changes in LN performance. This is due to the O.sub.2 filling valence bonding sites on the niobium. There are different types of bonds that can form with ligands. One type is due to a neutral coordination from a ligand (usually found in zero charged metal centers), in which case there is electron donation from O.sub.2 p orbitals usually to empty d orbitals on the metal. The type is due to covalent bond formation, in which case electrons from Nb and O.sub.2 are shared and the O.sub.2, as well as the Nb, contributes electrons into the bond. The stronger sigma bonds have some s hybridization pulling the ligand closer than for a neutral ligand. For covalently bonded ligands, the bond becomes even stronger if there is pi bond back-donation from the metal center from d on the metal to p on the ligand. In other words there is more sharing, but also a loss of electrons from the metal center to the oxygen. In the partial density of states, without O.sub.2, there are s, p, and d bands above the valence band, which disappear when O.sub.2 is added. These bands shift below the Fermi into the bonding levels.
(49) As known to one skilled in the art, the conductivity of a solid is low when the energy gap between the valence band and the conduction band of the material is large compared to thermal energy at the temperatures of operation. Hence, a large energy gap, or bandgap, ensures lower conductivity, and a small bandgap is indicative of higher conductivity.
(50) Numerical modeling and simulations may be used to determine the effect on bandgap of exposing the lithium niobate surface to oxygen. Calculations show that the conduction bandgap is relatively large in the presence of oxygen and that, conversely, the bandgap is a relatively low value when the surface is deprived of oxygen.
(51) When a properly selected gas contacts a material, the chemistry causes a reduction in surface defect states. As defined herein, treating at least one surface of an inorganic material comprises: (1) passive pre-treatment with no extra forcing conditions, (2) active pre-treatment under temperature, pressure, radiation, etc.; (3) fill with no pre-treatment; (4) fill with activating temperature, pressure, radiation conditions; (5) passive pre-treatment plus passive fill; (6) passive pre-treatment with fill under activating conditions; (7) activated pre-treatment plus passive fill; and (8) active pre-treatment plus active fill. The gas encasing the inorganic material is referred to herein as a fill gas (or backfill gas). In this case, the inorganic material is positioned in a housing or sealed enclosure and the housing is filled with the gas to encase the inorganic material in the gas. In this manner, the encased gas contacts (treats) the inorganic material. The housing or sealed enclosure is appropriately designed to permit use of the inorganic material in a test unit or a system.
(52) As is understandable to one skilled in the art, temporary exposure of the IOC to a treatment gas prior to operation of the IOC-based device in a system is distinguished from an exposure of the IOC to a fill gas during operation of the IOC-based device in a system.
(53) The backfill gases and/or treatment gases that ensure the highest LN band gaps represent optimum candidates for stabilizing the LN in an IOC. The lithium niobate IOC is packaged with stabilizing gases (selected based on modeling) to: 1) stabilize the lithium niobate performance; and 2) minimally or negligibly interact with other internal components/materials of the fiber optical gyroscope.
(54) A method is provided for determining the optimal fill gas or gases for lithium niobate stabilization, based on: 1) numerically modeling the lithium niobate surface; 2) observing the interaction of the modeled lithium niobate surface with various fill gases, including the coordination of niobium to the fill-gas atoms; and 3) estimating the electronic band gaps of any observed surface states. The models consist of a periodic unit LN cell containing an infinite layer of the niobate, with vacuum space above and below the infinite layer. The test gas is energy-optimized to one surface of the infinite layer, and a calculation of the band structure is done. All calculations employ commercially available quantum mechanics software employing density functional theory (such as CASTEP from Accelrys, Inc.).
(55) In some embodiments, the lithium in lithium niobate of the IOC is partially exchanged for hydrogen. This produces a mixture of hydrogen niobate referred to herein as FIN within LN. LN can be the base inorganic material used in the IOC. The partially proton exchanged lithium niobate is the active form used in the integrated optical chip waveguide and is commonly referred to as annealed proton exchanged lithium niobate (or APE lithium niobate). The cases in the modeling described below, which correspond most closely to APE lithium niobate, are fully hydrogen exchanged lithium niobate. The fully hydrogen exchanged lithium niobate is referred to herein as hydrogen niobate (or FIN). In this latter case, a periodic unit cell of hydrogen niobate is used in the modeling. Both LN and FIN have the same performance concerns when used to form an IOC in a gyroscope.
(56) The band gap of either LN or FIN is determined by calculating the specific electronic bands and the density of states, and using band energies above and below the minimum in the density of states nearest the Fermi level to establish a relative band gap. This method accounts for energies near the Fermi level which may be populated due to surface states, in a consistent manner for comparisons.
(57) A remediation gas is also referred to herein as a coordinating gas. An uncoordinated site is also referred to herein as an unbonded site or defect. A coordinating species is a species that is stable by itself, but prefers to be associated with another species. A coordinating species is also referred to herein as a ligand. Given enough thermal treatment, a coordinating species can be disassociated from a surface to which is it bonded. A reactive species is a species that is less stable by itself, but is more stable when bonded to another species or breaks bonds in order to from species that are most stable when bonded to another species. More energy is required to remove a reactive species when bonded to another species. A reactive gas will possibly react to other gases generated by the components associated with the integrated optical chip. A reactive species also includes an oxidizing species in which the oxidizing species either causes the reactant surface to increase its oxidation state or reduces the electron density of the reactant surface.
(58) The modeling described here has been done for a plurality of test gases on LN and FIN. For bulk FIN, which has no gas exposure, the lowest band gap is 2.887 eV. When FIN is in a vacuum, the lowest band gap is 0.242 eV. Thus, the vacuum strongly influences the FIN material by producing a drop in the bandgap. Table 1 shows the model-estimated results for electronic band gaps of observed surface states for the respective plurality of test gases applied to FIN material (all proton exchanged). The first column and fourth columns indicate the test gas. The second column shows the lowest band gap in electron volts (eV) for the test gas in the first column. The fifth column shows the lowest band gap in electron volts (eV) for the test gas in the fourth column. In the tables shown herein, the number of molecules is indicated to illustrate the relative ratio when two or more types of molecules are combined.
(59) TABLE-US-00001 TABLE 1 Lowest Lowest HN (all proton band gap HN (all proton band gap exchanged) (eV) exchanged ( eV) 4O 2.802 4Ar 0.293 4O + 4CO.sub.2 2.659 4Ne 0.292 2O + 4CO.sub.2 2.168 4CH.sub.3 0.291 2O 2.054 4CH.sub.4 0.291 4O.sub.2 + 4Ne 1.916 4He 0.29 4NO 1.686 4Kr 0.288 4NO.sub.2 1.662 2Ne 0.286 (4Xe + 4O.sub.2 optimized) then 1.559 2He 0.286 CO.sub.2 added to model 4O.sub.2opt + 4Ne 1.533 2x butane 0.286 4Xe + 4O.sub.2 1.474 2x butene 0.286 4Xe + 4CO.sub.2 + O.sub.2 1.438 6Xe 0.285 (4Xe + 4CO.sub.2 optimized) 1.289 6He 0.284 then O.sub.2 added to model 4NO + 4CO.sub.2 1.232 4Rn 0.284 4O.sub.3 1.076 6Ne 0.284 4SO.sub.2 0.972 4MeOH 0.283 4O.sub.2 + 4N.sub.2 0.891 4x butene 0.283 4O.sub.3 + 4CO.sub.2 0.793 4H.sub.2 0.282 6N.sub.2O 0.724 1O 0.279 4NH.sub.2CO.sub.2H 0.692 4N.sub.2O + 2CO 0.276 4N.sub.2O 0.607 2CO.sub.2 0.274 4NH.sub.3 0.591 4CO.sub.2 + 4Ne 0.248 4N.sub.2O + 4NH.sub.3 0.56 4CO.sub.2 + 4He 0.246 6NH.sub.3 0.552 4x ipa 0.241 4CO.sub.2 + 4NH.sub.3 0.519 4N.sub.2O + 4CO 0.229 6CO (3 coord) 0.495 4x isobutene 0.228 4PMe.sub.3 0.494 4NH.sub.3 0.225 4CO (4 coord) 0.442 4CF.sub.4 0.19 4N.sub.2O + 4CO.sub.2 0.435 hexamethyl disilane 0.197 4O.sub.2 + 4He 0.396 2Si(Me)(OMe)2OH 0.197 6O.sub.2 + 1CO.sub.2 0.383 6NH.sub.3 0.196 4O.sub.2 0.349 2x isobutene 0.189 6O.sub.2 0.346 4OPMe.sub.3 0.177 4O.sub.2 + 1CO.sub.2 0.345 2O.sub.2 0.168 2x 1butene 0.341 4HCN 0.165 4x butane 0.336 6CO.sub.2 0.165 2N.sub.2O 0.321 1O.sub.2 0.165 4Xe 0.32 CF.sub.3CH.sub.2CFH.sub.2 0.161 2N.sub.2O + 2CO.sub.2 0.317 hexamethyl 0.151 trisiloxane 4O.sub.2 optimized then 4He 0.309 2O.sub.2 + 1CO.sub.2 0.151 added to model 4CO (1 coord) 0.305 4CHF.sub.3 0.149 6O.sub.2 + 1CO.sub.2 0.302 1 (Me.sub.2OHSi)2O 0.138 4Xe + 4CO.sub.2 0.3 2Si(Me.sub.3)OH 0.101 6N.sub.2 0.299 1CO.sub.2 0.073 4N.sub.2 0.293 1CO.sub.2 0.065
(60) For bulk LN the lowest band gap is 3.305 eV and the Fermi level is 4.176 eV. When LN is in a vacuum, the lowest band gap is 0.025 eV. The vacuum strongly influences the LN material by producing a drop in the bandgap. Table 2 shows the model-estimated results for electronic band gaps of observed surface states for the respective plurality of test gases applied to LN material. The first column indicates the test gas. The second column shows the lowest band gap in electron volts (eV).
(61) TABLE-US-00002 TABLE 2 LN (all proton exchanged Lowest band gap (eV) 4O.sub.2 2.254 4CO.sub.2 0.018 4O.sub.3 2.703 4N.sub.2O 0.807
(62) Some gases interact with the surface of LN or FIN to create relatively high LN or FIN band gaps or to increase the band gaps over the gas-free case by: 1) forming a capping bond (typically O) on the niobium; 2) increasing the formal coordination around the niobium; and/or 3) providing an electron-donating species to niobium. As an example, O.sub.2, which has been mentioned as a typical fill-gas, raises the vacuum bandgap from 0.242 eV to 0.349 eV for FIN and from 0.025 eV to 2.254 eV for LN. In one implementation of this embodiment, N.sub.2O and O.sub.3 gases form a formal NbX capping bond (X is an O or N atom) that results in high band gaps. In another implementation of this embodiment, non-reactive gases such as NH.sub.3 and PMe.sub.3 gases form coordination with Nb and thereby change the mechanism from classic oxidation.
(63) In some embodiments, the test gas is an electron-rich noble gas. For example, Xe gas keeps the band gap above the vacuum level. When combined with O.sub.2, Xe is observed to enhance the NbO bond and thereby raise the band gap. As shown in Table 1 above, 4Xe+4O.sub.2 on HN has a band gap of approximately 1.474 eV and 4Xe+4CO.sub.2+0.sub.2 on FIN has a band gap of approximately 1.438 eV. Thus, Xe is combined with O.sub.2 for maximal effect. Xe appears to force better coordination of the O.sub.2 as the NbO (from O.sub.2) bond distances are shortened. Instead of a terminal NbOO coordination there is a 3 membered ring center for the NbO.sub.2. A treatment of O.sub.2 followed by Xe enhances the Nb-bond and thereby raises the band gap. The same effect found for Xe was also found for Ne, but not for He. As shown in Table 1 above, 4O.sub.2opt+4Ne on FIN has a band gap of approximately 1.533 eV. As shown in Table 1 above, 4O.sub.2+4He on FIN has a band gap of approximately 0.396 eV. The O.sub.2 gas, which forms coordination to niobium, increases the band gap over that of the gas-free vacuum on HN (i.e., 0.242 eV), especially when the O.sub.2Nb bond becomes shorter indicating a stronger bond.
(64) Non-reactive gases, such as CO.sub.2 and fluorocarbons, lower the band gap because they do not help to satisfy the coordinate state of niobium.
(65) As indicated in Tables 1 and 2, the gases N.sub.2O, O.sub.3, NH.sub.3 and PMe.sub.3 increase the band gap as they can help satisfy the coordination state of niobium. The gases NH.sub.3 and PMe.sub.3 are useful coordinating gases that do not further react. The gases O.sub.3 and N.sub.2O are useful reactive gases. O.sub.3 may provide a capping oxygen atom to the niobate surface, liberating O.sub.2 which may coordinate to the niobium. However, N.sub.2O functions both as a reactive and coordinating gas, depending upon the conditions.
(66) Other treatment gases that exhibit large band gaps above that of N.sub.2O include NO, NO.sub.2 and SO.sub.2, which are highly coordinating gases and reactive. The latter gases may have other reactions (such as acid formation with water). In one implementation of this embodiment, coordinating gases, such as but not limited to N.sub.2O, NO, NO.sub.2, SO.sub.2, NH.sub.3 and PMe.sub.3, are used as the gyro or modulator-encasing atmosphere.
(67) Although NH.sub.3 is a classic Lewis base, and may corrode metal parts, other nitrogen-based or Group V-based molecules with lower basicity are likely to be useful without corrosion, such as triazines, phosphazines, and phosphines. For example, PMe.sub.3 on an HN surface was found to have a calculated bandgap of 0.494 eV, which is better than O.sub.2. However, PMe.sub.3 should not be used with oxygen due to PMe.sub.3's high tendency to oxidize and form an oxide, which lowers the HN band gap to 0.177 eV (lower than the O.sub.2). PMe.sub.3 is related to a general group of alkyl phosphine compounds sometimes used in corrosion inhibitors and most commonly used in more stable phosphonate forms. Thus, a more stable phosphine, with less reactivity than PMe.sub.3 or side reactions than NH.sub.3, is useful in increasing the band gap.
(68) The results shown in Tables 1 and 2 were obtained by modeling. Some exemplary modeling cases are now described with reference to
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(73) The band gap shown for
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(80) As shown in
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(82) The test system 200 includes the test component 100 formed from a test material (e.g., LN or FIN) and a structure 250 to support the test component 100. As shown in
(83) The selected-test gas 221 is selected by: numerically modeling at least one surface of the test material; simulating a plurality of exposures of the at least one surface of the modeled test material to a respective plurality of test gases (e.g., test gases 41, 46, 42, 47, 44, and 48 shown in respective
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(85) As shown in
(86) The selected-test gas 223 is selected in the same manner that selected-test gas 221 was selected as described above with reference to
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(88) Table 3 shows a listing of the preferred gas combinations and conditions. Column 1 of Table 3 lists the preferred gases and the column 2 of Table 3 shows the lowest bandgap for the associated gas in column 1.
(89) TABLE-US-00003 TABLE 3 Gas/condition Gap eV no gas 0.242 4O.sub.2 0.349 2N.sub.2O 0.321 4N.sub.2O 0.607 6N.sub.2O 0.724 2N.sub.2O optimized, then 4N.sub.2 added 1.780 4N.sub.2O optimized, then 4N.sub.2 added 0.334 2N.sub.2O + 4N.sub.2 optimized at same time 0.094 4N.sub.2O + 4N.sub.2 optimized at same time 0.296 4N.sub.2O + 4Xe optimized at same time 0.313 4N.sub.2O + 4CO.sub.2 optimized at same time 0.435 4N.sub.2O + 4O.sub.2 optimized at same time 0.314 4N.sub.2O optimized, then 4O.sub.2 added 0.327 2N.sub.2Ooptimized then 4Xe 0.833 2N.sub.2Ooptimized then 4Ne 1.576
(90) Other gases have a relatively high bandgap, with reference to the bandgap in a vacuum. Table 4 shows a listing of the beneficial gas combinations. Column 1 of Table 4 lists the preferred gases and the column 2 of Table 4 shows the lowest bandgap for the associated gas in column 1.
(91) TABLE-US-00004 TABLE 4 Gases/Gas Mixtures Lowest bandgap (eV) 4O 2.802 2O 2.066 4NO 1.686 4NO.sub.2 1.662 4NO + 4CO.sub.2 1.232 4O.sub.3 1.080 4SO.sub.2 0.972 4O.sub.3 + 4CO.sub.2 0.793 4NH.sub.2CO2H 0.692 4NH.sub.3 0.591 6NH3 0.552 4CO.sub.2 + 4NH.sub.3 0.519 6CO 0.495 4PMe.sub.3 0.494 4CO 0.442 4O.sub.2 0.349
(92) The modeling and testing described above indicates that a dilution gas can be combined with the preferred gases, which have a relatively high bandgap with reference to the bandgap in a vacuum, to enhance the stabilization of the inorganic material. Table 5 shows a listing of the beneficial gas combinations. Column 1 of Table 5 lists the preferred gases and the column 2 of Table 4 shows the lowest bandgap for the associated gas in column 1.
(93) TABLE-US-00005 TABLE 5 Dilution gases Lowest bandgap eV 4Rn 0.284 4Xe 0.320 4Kr 0.288 4Ar 0.293 4Ne 0.292 4He 0.290 4N2 0.293 6N2 0.299 4x butane 0.336 4CO2 0.294
(94) In one implementation of this embodiment, the gases are simultaneously introduced into an enclosure as a combined mixture. In another implementation of this embodiment, a first gas (for example, N.sub.2O) is added first to the enclosure and then a second gas is added to the same enclosure. In yet another implementation of this embodiment, the first selected gas is N.sub.2O is added to the enclosure before the second selected gas, N.sub.2. In yet another implementation of this embodiment, the first selected gas is N.sub.2O is added to the enclosure at the same time the second selected gas CO.sub.2 is added. In this latter case, when N.sub.2O and CO.sub.2 are added at the same time, the bandgap is high.
(95) Non-reactive gases may be used as a second gas. Examples of nonreactive gases are N.sub.2, CO.sub.2, a noble gas, CO. Other non-reactive gases would include NH.sub.3, PH.sub.3, PMe.sub.3, O.sub.2, saturated hydrocarbons. The gases that are truly non-reactive gases are the noble gases and saturated hydrocarbons. The coordinating gases that coordinate on Nb but do not break bonds are N.sub.2, CO.sub.2, CO, NH.sub.3, PH.sub.3, PMe.sub.3 and O.sub.2. The gas N.sub.2O is either a reactive or a coordinating gas, depending upon the conditions.
(96) In one implementation of this embodiment, first selected gas used to pretreat the lithium-niobate-based material is a reactive oxide such as O.sub.3, O, NO, NO.sub.2, N.sub.2O, SO.sub.2, SO and second selected gas, in which the lithium-niobate-based material is enclosed, is a nonreactive gas. For example, the first selected gas used to pretreat the lithium-niobate-based material can be selected from the following listing of reactive oxides: O.sub.3, O, NO, NO.sub.2, N.sub.2O, SO.sub.2, SO and second selected gas in which the lithium-niobate-based material is enclosed is a mixture of N.sub.2O and a noble gas.
(97) In one implementation of this embodiment, a first selected gas used to pretreat the lithium-niobate-based material is a reactive oxide such as O.sub.3, O, NO, NO.sub.2, N.sub.2O, SO.sub.2, SO, and the second selected gas, in which the lithium-niobate-based material is enclosed, is a mixture of N.sub.2O and a non reactive gas.
(98) The process of obtaining the highest coordination saturation may be achieved by alternate gases or treatments. For instance N.sub.2O may be used to either oxidize the surface or coordinate a neutral (N.sub.2O) ligand to fulfill niobium coordination saturation.
(99) N.sub.2O is known to form a reactive oxidant O species at elevated temperatures, so increasing the reactivity of N.sub.2O may be accomplished by various methods such as an increase in temperature. Temperatures in the 200-300 C. range may be needed without other activation methods. However other activation methods can be used to reduce the oxidation temperatures to as low as 100-200 C., by adding O.sub.2 or air into the gas mixture and/or using an alkali activator impregnated at the surface which may be applied by a solution coat, dip or wash procedure of an alkali metal salt. Alkali activators also help to maintain reactivity of the surface toward N.sub.2O in the presence of water. In this context, an alternate processes use a combination of moisture-free IOC surface, and/or a pretreatment with an alkali metal salt, and the N.sub.2O used in an O.sub.2 or an O.sub.2 mixture (air, N.sub.2 or CO.sub.2 as examples of other gases in the mixture) at elevated temperatures at 100 C. or above.
(100) As shown in
(101) The selected treatment for the IOC to be used in the gyroscope should be made in consideration of the fabrication processes used to form the IOC, since any wet or dry etching processes potentially provide a pretreatment to the IOC.
(102) In one implementation of the embodiments shown in
(103)
(104) The IOC 110 is enclosed in a selected-gas-filled sealed enclosure 222. The selected-gas-filled sealed enclosure 222 is filled with the selected gas 221. The IOC 110 is supported on the structure 252 in the sealed enclosure 222. In one implementation of this embodiment, the sealed enclosure 222 supports the IOC 110. The structure 252 supports the IOC 110 to couple light between the laser 701 and the circulator 704. In another implementation of this embodiment, the structure 252 to support the test component 100 is at least a portion of the sealed enclosure 222. In yet another implementation of this embodiment, the structure 252 to support the test component 100 is positioned within the sealed enclosure 222.
(105) As described above, the at least one selected gas 221 is selected based on: numerically modeling a surface of the material; simulating a plurality of exposures of the surface of the modeled material to a respective plurality of test gases; simulating a plurality of interactions of the surface of the material exposed to the respective plurality of test gases; and estimating a plurality of electronic band gaps of observed surface states for the respective plurality of test gases.
(106) In one implementation of this embodiment, the IOC 110 the IFOG system 10 is undergoing gyro tests to determine if the performance of the IFOG system 10 is improved by the exposure of the IOC 110 to the selected gas. In another implementation of this embodiment, the IOC 110 is functional in IFOG system 10 which is operational to measure an orientation of a vehicle in which the IFOG system 10 is housed. In yet another implementation of this embodiment, the IOC 110 is in another type of gyroscope system. For example, if the optical system is a resonant fiber optic gyroscope, the IOC 110 can be replace with a CCW modulator and a CW modulator as is understandable to one skilled in the art.
(107)
(108) As described above, the at least one selected gas 223 is selected as described above with reference to
(109)
(110) In one implementation of this embodiment, the IFOG system 12 is undergoing gyro system performance testing. In another implementation of this embodiment, the IFOG system 12 is operational in a moving vehicle. In yet another implementation of this embodiment, the first selected gas 223 and the second selected gas 221 are the same gas.
(111)
(112) The IFOG system 13 is designed with appropriate stabilizing fill gases (e.g., 221) and/or treatment gases (e.g., 223) to stabilize the performance of the lithium niobate and to minimize reaction with the other components/materials in the IFOG system 13 (e.g., the light source 701, the input fiber 702, the output fiber 706, the coupler 704, and the rate detector 708) that are encased in the enclosure 222 with the stabilizing fill gases (e.g., 221). The fill-gases are chosen as an alternative to molecular-oxygen-(O.sub.2)-containing fill gases. Based on the modeling described herein, the selected fill-gases, which were modeled and then tested in a test system, have a better ability than O.sub.2 to increase the band gap of the lithium niobate.
(113) In one implementation of this embodiment, the IFOG system 13 is undergoing gyro system performance testing. In another implementation of this embodiment, the IFOG system 13 is operational in a moving vehicle. In yet another implementation of this embodiment, the first selected gas 223 and the second selected gas 221 are the same gas. In yet another implementation of this embodiment, the IOC 110 is not treated with a selected gas 223 but is positioned in the sealed enclosure 222 filled with a selected gas 221.
(114) In one implementation of this embodiment, the LN material is pre-treated with (exposed to) O.sub.3, N.sub.2O, NO, NO.sub.2 and SO.sub.2 before assembly of the LN material phase modulator (or LN phase modulator). This can be done in place of a fill gas that encloses the LN or FIN phase modulator, to get around any negative effects of the fill gases themselves on the LN or HN phase modulator. The pre-treatment of the LN material for use in a phase modulator is considered within the assembly, if the gases are then flushed. Once the surface of the LN material is oxidized, the niobate should be more stable. At that point, the fill-gas is inert. A fully oxidized surface is less sensitive to CO.sub.2 or products of organic decomposition.
(115) In one implementation of this embodiment, LN material chips are designed to have a high band gap and are also designed with the complete system in mind so that the selected gases do not react to any outgassing by neighboring components. The system designer uses the modeling techniques described herein to balance the tradeoff between the reactive nature of a reactive species, which typically has a relatively high band gap, and the coordinating species, which typically has a slightly lower band gap, but both of which have higher band gaps than the untreated chip. A lone pair is an electron pair that will attach to an electron deficient center; lone pair is required with both reactive and coordinating species to satisfy the coordinate deficient state of niobium.
(116) The gases described herein can be used as one of: 1) a coordinating gas (remediation gas) that includes a coordinating species; 2) a reactive gas that includes a reactive species; or 3) both a coordinating gas and a reactive gas. In one implementation of this embodiment, the same gas is used as both a coordinating gas and a reactive gas.
(117) The gases disclosed herein are selected to bond to the uncoordinated sites on a surface of the lithium niobate (or hydrogen niobate) test component or the optical component in a system (e.g., a phase modulator) in order to provide relatively high band gaps. Analysis shows that LN (lithium niobate) has a much higher band gap recovery with O.sub.2 than FIN (proton exchanged lithium niobate), suggesting that lithium, or possibly another cation, helps stabilize the larger band gap at the gas surface.
(118) The gases are tested on test components and, when a suitable gas is selected, the selected gas is used on optical components (e.g., optical modulators) in a gyroscopic system in one of three ways described above with reference to
(119) In one implementation of this embodiment, the phase modulators 110 in the IFOG systems 10, 12, and 13 described with reference to
(120) In yet another implementation of this embodiment, the phase modulators 110 in the IFOG systems 10, 12, and 13 described with reference to
(121) In yet another implementation of this embodiment, at least one IOC is at least one of: treated by at least one of the at least one selected gas prior to an operation of the system; and enclosed in a sealed enclosure filled with at least one of the at least one selected gas during the operation of the system.
(122)
(123)
(124) At block 1902, a surface (e.g., surface 40 in
(125) At block 1904, a plurality of exposures of the surface of the modeled material to a respective plurality of test gases are simulated. The simulation is done for each of the test gases in a plurality of test gases. The test gases include at least two of the gases listed in Tables 1 and 2 above.
(126) At block 1906, a plurality of interactions of the surface of the material exposed to the respective plurality of test gases are simulated.
(127) Blocks 1908 to 1914 are used together to estimate the plurality of electronic band gaps of the observed surface states for a test gas in the plurality of test gases. At block 1908, the test gas is energy-optimized to one surface of the material. At block 1910, specific electronic bands for the test gas energy-optimized to the one surface of the material are calculated. At block 1912, the density of states for the test gas energy-optimized to the one surface of the material is calculated.
(128) At block 1914, a band structure based on the calculated electronic bands and the density of states for the test gas energy-optimized to the one surface of the material is determined. The band energies above and below the minimum in the density of states nearest the Fermi level are used to estimate the electronic band gap for the test gas. In one implementation of this embodiment, method 1900 is performed by implementing quantum-mechanics software employing density functional theory.
(129) As described above, the gases that are determined (by modeling) to increase the band gap are selected for testing on test components.
(130) At block 2002, at least one of the test gases in the plurality of test gases is selected for testing on a test component formed from the material (e.g., LN or FIN). The selecting is based on the estimated respective plurality of electronic band gaps for the respective plurality of test gases on the material in accordance with method 1900. In one implementation of this embodiment, the selecting is also based on minimizing reaction of the at least one test gas in the plurality of test gases with at least one of: other components (e.g., the light source 710 and detector 708) in an IFOG system 13 as described above with reference to
(131) At block 2004, it is determined if the test component is to be treated (e.g., exposed to the selected test gas, other than a fill gas, prior to testing). When the test system, includes a test component that is treated with a test gas, the flow proceeds to from block 2004 to 2206. At block 2006, at least a portion of the test component is treated with the selected at least one test gas of the plurality of test gases. The selected at least one test gas of the plurality of test gases is also referred to herein as a selected at least one of the plurality of test gases and as a selected test gas. In one implementation of block 2006, the selected at least one of the plurality of test gases is a first-selected-test gas. At block 2008, it is determined in if the treated test component is to be enclosed in a sealed enclosure with a test gas. If it is determined at block 2008, that the treated test component is not to be enclosed in a sealed enclosure with a test gas, the flow of method 2000 proceeds to block 2010. At block 2010, the test component is tested. In one implementation of this embodiment of block 2010 of method 2000, the test component 101 is tested in the test system 201 of
(132) If it is determined at block 2008, that the treated test component is to be enclosed in a sealed enclosure with a test gas, the flow of method 2000 proceeds to block 2012. At block 2012, the treated test component is enclosed in a sealed enclosure filled with the selected at least one test gas of the plurality of test gases. In one implementation of block 2012, the selected at least one of the plurality of test gases is a second selected one of the at least one of the plurality of test gases, which is also referred to herein as a second-selected-test gas. In this case, the test component is treated with a first-selected-test gas and enclosed in a second-selected-test gas.
(133) At block 2014, the test component is tested. In one implementation of this embodiment of block 2014 of method 2000, the test component 101 is enclosed in sealed enclosure 221 and is tested in the test system 202 of
(134) When the test system, does not include a test component that is treated with a test gas (other than a fill gas) prior to testing, the flow proceeds to from block 2004 to 2216. At block 2016, the test component is enclosed in a sealed enclosure filled with the selected at least one of the plurality of test gases. At block 2018, the test component is tested in the fill gas. In one implementation of this embodiment of block 2018 of method 2000, the test component 100 is enclosed in sealed enclosure 221 and is tested in the test system 200 of
(135) In one implementation of this embodiment, a complete testing is done for a plurality of test gases and a matrix of first and second test gases for a plurality of test component formed from a plurality of inorganic materials. In this complete testing every type of test component is tested in each of the methods of blocks 2010, 2014 and 2018 in order to determine which test gas or combination of test gases in which type of testing system (e.g., test system 200, 201, or 202) provides the best performance. In one implementation of this embodiment, a system (e.g., a gyroscopic system 10, 11, or 12) uses an optical component that is formed and prepared in the manner of the test component and test system that provide the best performance.
(136) It will be understood that various modifications to the described embodiments may be made without departing from the spirit and scope of the invention. In the following pages the chemical notations are not in subscript form but are in a form which is understandable to one skilled in the art.
Example Embodiments
(137) Example 1 includes a system comprising: at least one integrated optical circuit (IOC) formed from at least one material, wherein a performance of the at least one IOC is improved by exposure to at least one selected gas; and a support-structure configured to support the at least one IOC to couple light between other components.
(138) Example 2 includes the system of Example 1, wherein the at least one selected gas includes a reactive gas.
(139) Example 3 includes the system of any of Examples 1-2, wherein the at least one selected gas includes at least one reactive gas and at least one nonreactive gas.
(140) Example 4 includes the system of any of Examples 1-3, wherein the system is a gyroscope system, wherein the at least one IOC formed from at least one material is a phase modulator formed from a lithium-niobate-based material.
(141) Example 5 includes the system of Example 4, further comprising: an enclosure, wherein the support structure is one of: at least a portion of the enclosure in which the phase modulator is enclosed; or positioned within the enclosure in which the phase modulator is enclosed, and wherein at least one of the at least one selected gas is enclosed in the enclosure with the phase modulator.
(142) Example 6 includes the system of Example 5, wherein the at least one selected gas includes at least a first selected gas and a second selected gas.
(143) Example 7 includes the system of Example 6, wherein the first selected gas is added to the enclosure prior to adding the second selected gas to the enclosure.
(144) Example 8 includes the system of any of Examples 6-7, wherein the lithium-niobate-based material is pre-treated with the first selected gas prior to enclosing the phase modulator in the enclosure with the second selected gas.
(145) Example 9 includes the system of Example 8, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, wherein the first selected gas includes a reactive oxidizing gas and the second selected gas includes N2O.
(146) Example 10 includes the system of any of Examples 4-9, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, and wherein the first selected gas is N2O and the second selected gas is N2.
(147) Example 11 includes the system of any of Examples 4-10, wherein the at least one selected gas includes at least a first selected gas and a second selected gas wherein the first selected gas includes a reactive oxidizing gas and the second selected gas includes a nonreactive gas.
(148) Example 12 includes the system of any of Examples 4-11, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, and wherein the IOC is treated with the at least one of the selected gases prior to operation of the IOC.
(149) Example 13 includes the system of any of Examples 1-12, wherein the at least one selected gas includes at least one first selected gas and at least one second selected gas, and wherein the at least one IOC is: treated by the at least one first selected gas prior to an operation of the system; and enclosed in a sealed enclosure filled with the at least one second selected gas during the operation of the IOC.
(150) Example 14 includes the system of any of Examples 1-13, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, and wherein the first selected gas includes a reactive oxidizing gas and the second selected gas is mixture of N2O and a non reactive gas.
(151) Example 15 includes a gyroscope system comprising: at least one phase modulator formed from a lithium-niobate-based material, wherein a performance of the at least one phase modulator is improved by exposure to at least one selected gas; and a sealed enclosure in which the at least one phase modulator is enclosed, wherein at least one of the at least one selected gas is enclosed in the enclosure with the at least one phase modulator.
(152) Example 16 includes the gyroscope system of Example 15, wherein the at least one of the at least one selected gas includes N2O.
(153) Example 17 includes the gyroscope system of any of Examples 15-16, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, wherein the first selected gas includes a reactive oxidizing gas and the second selected gas includes N2O.
(154) Example 18 includes the gyroscope system of any of Examples 15-17, wherein the at least one selected gas includes at least a first selected gas and a second selected gas, wherein the lithium-niobate-based material is pre-treated with at least the first selected gas, by one of: exposing the lithium-niobate-based material to the first selected gas prior to enclosing the phase modulator in the sealed enclosure with the second selected gas; and exposing the lithium-niobate-based material to the first selected gas after enclosing the phase modulator in the enclosure in order to equilibrate the lithium-niobate-based material to the first selected gas prior to adding the second selected gas to the enclosure.
(155) Example 19 includes the gyroscope system of Example 18, wherein the first selected gas used to pretreat the lithium-niobate-based material is a reactive oxiding gas and wherein the second selected gas is N2O.
(156) Example 20 includes a method to determine a gas to stabilize surface states of a material, the method comprising: numerically modeling a surface of the material; simulating a plurality of exposures of the surface of the modeled material to a respective plurality of test gases; simulating a plurality of interactions of the surface of the material exposed to the respective plurality of test gases; and estimating a plurality of electronic band gaps of observed surface states for the respective plurality of test gases, wherein numerically modeling the surface of the material comprises: modeling the surface of the material by forming a periodic unit cell of the material including an infinite layer of the material with a vacuum above and below the infinite layer, and wherein estimating the plurality of electronic band gaps of the observed surface states, comprises, for a test gas in the plurality of test gases: energy-optimizing the test gas to one surface of the material; calculating specific electronic bands for the test gas energy-optimized to the one surface of the material; calculating density of states for the test gas energy-optimized to the one surface of the material; and determining a band structure based on the calculated electronic bands and the density of states for the test gas energy-optimized to the one surface of the material, wherein band energies above and below the minimum in the density of states nearest the Fermi level are used to estimate electronic band gap for the test gas.
(157) Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement, which is calculated to achieve the same purpose, may be substituted for the specific embodiments shown. Therefore, it is manifestly intended that this invention be limited only by the claims and the equivalents thereof.