Chalcogenide compositions for optical fibers and other systems

Abstract

The present disclosure relates to compositions that can be used for optical fibers and other systems that transmit light in the near-, mid- and/or far-ranges of the infrared spectrum, such as for example in the wavelength range of 1.5 μm to 14 μm. The optical fibers may comprise a light-transmitting chalcogenide core composition and a cladding composition. In some embodiments, the light-transmitting chalcogenide core composition has a refractive index n(core) and a coefficient of thermal expansion CTE(core), and the cladding composition has a refractive index n(cladding) and a coefficient of thermal expansion CTE(cladding), wherein n(cladding) is less than n(core) and in some embodiments wherein CTE(cladding) is less than CTE(core). In some embodiments, the chalcogenide glass core composition comprises a) sulfur and/or selenium, b) germanium, and c) gallium, indium, tin and/or one or more metal halides.

Claims

1. A glass fiber for transmitting infrared radiation, the glass fiber comprising: a chalcogenide glass core, the core having a core composition with a refractive index n(core) and a coefficient of thermal expansion CTE(core); and a cladding, the cladding having a cladding composition with a refractive index n(cladding) and a coefficient of thermal expansion CTE(cladding), wherein n(cladding) is less than n(core), and wherein the core composition consists essentially of: a) 65-75 mol % of sulfur; b) 15-30 mol % of germanium; and c) 1-10 mol % gallium.

2. The glass fiber of claim 1, wherein the cladding composition comprises a) sulfur and/or selenium, b) germanium, and c) gallium, indium, tin and/or one or more metal halides.

3. The glass fiber of claim 1, wherein the cladding composition consists essentially of a) 50-90 mol % of sulfur, b) 5-35 mol % of germanium, and c) 1-40 mol % of gallium.

4. The glass fiber of claim 1, wherein the cladding composition consists essentially of a) 65-75 mol % of sulfur, b) 15-30 mol % of germanium, and c) 1-10 mol % of gallium.

5. The glass fiber of claim 1, wherein the cladding composition consists essentially of a) 50-60 mol % of sulfur, b) 10-20 mol % of germanium, c) 10-20 mol % of indium, and d) 10-20 mol % of a metal halide.

6. The glass fiber of claim 1, wherein the cladding composition consists essentially of a) 35-80 mol % of selenium, b) 5-35 mol % of germanium, c) 5-20 mol % of indium, d) 1-10 mol % of tin, and e) 10-20 mol % of one or more metal halides.

7. The glass fiber of claim 1, wherein the cladding composition consists essentially of a) 45-55 mol % of selenium, b) 5-15 mol % of germanium, c) 10-20 mol % of indium, d) 1-10 mol % of tin, and e) 10-20 mol % of one or more metal halides.

8. The glass fiber of claim 1, wherein the cladding composition consists essentially of a) 65-75 mol % of selenium, b) 20-30 mol % of germanium, and c) 1-10 mol % of indium.

9. The glass fiber of claim 1, wherein the cladding composition has a higher content of sulfur than the core composition.

10. The glass fiber of claim 1, wherein the cladding composition has a lower content of sulfur than the core composition.

11. The glass fiber of claim 1, wherein the core composition and the cladding composition have the same composition except for the amount of sulfur.

12. The glass fiber of claim 1, wherein the cladding composition is a polymer.

13. The glass fiber of claim 12, wherein the polymer comprises at least one compound selected from the group consisting of: a UV curable acrylate, a silicone, and a polyimide.

14. The glass fiber of claim 1, wherein the CTE(cladding) is less than the CTE(core).

15. The glass fiber of claim 1, wherein the diameter of the chalcogenide glass core is from 10 μm to 300 μm.

16. The glass fiber of claim 1, wherein the outer diameter of the fiber is from 10.5 μm to 350 μm.

17. The glass fiber of claim 1, wherein the glass fiber is a step index fiber.

Description

DETAILED DESCRIPTION OF THE DISCLOSURE

(1) The present disclosure relates to compositions that can be used for optical fibers and other systems that transmit light in the near-, mid- and/or far-ranges of the infrared spectrum, such as for example in the wavelength ranges of 1.5 μm to 14 μm, 2.5 μm to 6 μm and 8 μm to 11 μm.

(2) The optical fibers may comprise a chalcogenide glass core having a light-transmitting chalcogenide core composition and a cladding having a cladding composition. In some embodiments, the light-transmitting chalcogenide core composition has a refractive index n(core) and a coefficient of thermal expansion CTE(core), and the cladding composition has a refractive index n(cladding) and a coefficient of thermal expansion CTE(cladding), wherein n(cladding) is less than n(core). In some embodiments, CTE(cladding) is less than CTE(core), which is particularly useful when the cladding is a chalcogenide glass composition of the current disclosure. The lower CTE(cladding) compresses the chalcogenide core to prevent the core from being damaged. When the cladding is a polymer of the current disclosure, the CTE(cladding) can, but is not required to be, less than the CTE(core).

(3) In some embodiments, the chalcogenide glass core composition comprises a) sulfur and/or selenium, b) germanium, and c) gallium, indium, tin and/or one or more metal halides.

(4) The glass compositions described herein can be used as the core, the cladding or both. The glass fibers can be manufactured according to techniques known in the art, such as for non-limiting example the techniques described in US 2005/0274149 and US 2005/0066689.

(5) The refractive indices of the core and the cladding can be modified in any manner known to those skilled in the art. In some embodiments, one possible way to modify the refractive index in the core or the cladding is to increase or decrease the content of the components. For non-limiting example, an increase in the sulfur and/or selenium content typically reduces the refractive index and reduces the coefficient of thermal expansion.

(6) A reduction in the refractive index is usually necessary for effective light transmission but a reduction in the coefficient of thermal expansion usually increases the compressive stress of the fiber and the bending stability. The fiber may be compressively stressed by wrapping the glass preform in a polymer with a similar glass transition temperature, for example polyether sulfone, which will protect the preform and the fiber from damage, will create a compressive stress in the glass due to the high coefficient of thermal expansion, and will prevent evaporation of the glass during drawing.

(7) The fibers of the current disclosure should be able to withstand mechanical loads. If the fibers are excessively mechanically sensitive, it is easy for the fibers to break. One criterion for assessing the strength of a fiber is the so-called loop test. In this test, a tightened loop is formed from the fiber. The smaller the diameter of the loop at which the fiber breaks, the more the fiber is resistant to breakage.

(8) Strong fibers can be produced by pretensioning the fibers which causes the coefficient of thermal expansion (CTE) of the chalcogenide glass core composition to be greater than the coefficient of thermal expansion of the cladding composition. Since the cladding composition may have a higher glass transition temperature relative to the core composition, the cladding composition may cool more quickly during drawing than the core composition. This produces a stress in the fiber that mechanically stabilizes the fiber. Such a prestressed fiber is generally substantially more fracture resistant than a non-prestressed fiber. Of course, other methods for introducing a stress are also possible. For example, the fiber can be chemically prestressed during the production process or thereafter by introducing ions into the cladding using known processes.

(9) In some embodiments of the disclosure, the diameter of the chalcogenide glass core is 10 μm to 300 μm and the outer diameter of the fiber is 10.5 μm to 350 μm. However, other diameters and thicknesses are within the scope of the current disclosure since the suitable values are dictated in most cases by the application. For example, a large core diameter increases the transmission and a thin cladding thickness in some applications is beneficial, while in other applications a small core diameter and a very thick cladding are useful.

(10) The fibers of the current disclosure may be used in fiber bundles alone or with other types of light-guiding fibers.

(11) The principles of suitable fiber drawing processes are described for example in DE 10344205 and DE 10344207, the entire contents of each of which are hereby incorporated by reference and are useful to produce the fibers of the current disclosure. Other fiber drawing techniques are suitable as known to those skilled in the art of fiber manufacture.

(12) The compositions of the chalcogenide glass core composition and the cladding composition may be similar. In some embodiments, the compositions are identical except for the amounts of sulfur and/or selenium. Increasing the sulfur and/or selenium content reduces the refractive index and increases the coefficient of thermal expansion.

(13) The disclosure includes chalcogenide glass core compositions comprising a) sulfur and/or selenium, b) germanium, and c) gallium, indium, tin and/or one or more metal halides. The disclosure also includes cladding compositions comprising a) sulfur and/or selenium, b) germanium, and c) gallium, indium, tin and/or one or more metal halides. The metal halides may include without limitation cesium bromide and indium(III) bromide.

(14) Suitable chalcogenide glass core compositions and suitable cladding compositions include those of Formula A and Formula B:

(15) TABLE-US-00001 Formula A Component Mole % S 50.00-90.00    Ga 0-25.00 As 0-40.0  Ge 0-35.00 R.sup.1 (added in the form of R.sup.1Hal) 0-7.25  R.sup.2 (added in the form of R.sup.2Hal) 0-13.5  M.sup.1 (added in the form of M.sup.1Hal.sub.2) 0-5    M.sup.2 (added in the form of M.sup.2Hal.sub.2) 0-7.25  Ln (added in the form of LnHal.sub.3) 0-4    Sum of Ga, As, and Ge 10.00-42.00    Sum of R.sup.1, R.sup.2, M.sup.1, M.sup.2, and Ln 0-16.00 Sum of Hal  0-16.00. Or Formula B Component Mole % Se 30.00-75.00    Ga 5.00-30.00   Ge 0-25.00 R.sup.1 (added in the form of R.sup.1Hal.sup.1) 0-25.00 R.sup.2 (added in the form of R.sup.2Hal.sup.1) 0-25.00 M.sup.1 (added in the form of M.sup.1Hal.sup.1.sub.2) 0-12.50 M.sup.2 (added in the form of M.sup.2Hal.sup.1.sub.2) 0-20.00 Ln (added in the form of LnHal.sup.1.sub.3) 0-8.00  Sum of Se, Ga, and Ge 50.00-93.33    Sum of R.sup.1, R.sup.2, M.sup.1, M.sup.2, and Ln 1.67-25.00   Sum of Hal.sup.1 0-25.00

(16) wherein

(17) Hal=fluoride, chloride, bromide, and/or iodide,

(18) Hal.sup.1=chloride and/or bromide,

(19) R.sup.1=Li, Na, K, Rb, and/or Cs,

(20) R.sup.2=Ag and/or Cu,

(21) M.sup.1=Mg, Ca, Sr, and/or Ba,

(22) M.sup.2=Zn, Cd, Hg, and/or Pb,

(23) Ln=La, Ce, Pr, Nd, Pm, Sm, Eu, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc; and;

(24) wherein in Formula A and Formula B, some or all of the gallium can be replaced by indium, wherein in Formula A some or all of the arsenic can be replaced by antimony.

(25) Irrespective of Formula A and Formula B, the chalcogenide glass core composition and the cladding composition may each consist essentially of a) 50-90 mol % of sulfur, b) 5-35 mol % of germanium, and c) 1-40 mol % of gallium, indium and/or a metal halide. The chalcogenide glass core composition and the cladding composition may each consist essentially of a) 65-75 mol % of sulfur, b) 15-30 mol % of germanium, and c) 1-10 mol % of gallium. The chalcogenide glass core composition and the cladding composition may each consist essentially of a) 50-60 mol % of sulfur, b) 10-20 mol % of germanium, c) 10-20 mol % of indium, and d) 10-20 mol % of a metal halide.

(26) The chalcogenide glass core composition and the cladding composition may each consist essentially of a) 35-80 mol % of selenium, b) 5-35 mol % of germanium, c) 5-20 mol % of indium, d) 1-10 mol % of tin, and e) 10-20 mol % of one or more metal halides. The chalcogenide glass core composition and the cladding composition may each consist essentially of a) 45-55 mol % of selenium, b) 5-15 mol % of germanium, c) 10-20 mol % of indium, d) 1-10 mol % of tin, and e) 10-20 mol % of one or more metal halides. The chalcogenide glass core composition and the cladding composition each consists essentially of a) 65-75 mol % of selenium, b) 20-30 mol % of germanium, and c) 1-10 mol % of indium.

(27) All of the numerical ranges disclosed herein include all subranges therebetween. For example, the range 50-90 mol % includes 51-90, 50-89, 60-80, and all other numerical possibilities.

(28) The compositions of the chalcogenide glass core composition and the cladding composition may be similar or different. In some embodiments, the compositions are identical except for the amounts of sulfur and/or selenium. The refractive indices for the core and the cladding, as well as the coefficients of thermal expansion for the core and the cladding, can be adjusted by adjusting the content of the sulfur and/or selenium in the chalcogenide glass core composition or the cladding compositions. In some embodiments, the cladding composition has a higher content of sulfur and/or selenium than chalcogenide glass core composition. In other embodiments, the cladding composition has a lower content of sulfur and/or selenium than chalcogenide glass core composition. The variation in the content of sulfur and/or selenium depends on many factors, such as 1) the desired NA, where the amount of sulfur and/or selenium to increase or decrease is guided by the impact on refractive index, 2) the impact of the sulfur and/or selenium content on the CTE of the core and cladding compositions, and 3) the overall optical and mechanical design of the system.

(29) The cladding composition is a polymer in some embodiments, such as for non-limiting example a UV curable acrylate such as PMMA, a silicone, a polyimide, or a mixture thereof. Other known polymers and mixtures thereof can be used as the cladding. The polymer cladding can be used to form a fiber with the chalcogenide glass core compositions described herein.

(30) The chalcogenide glass core and the cladding in some embodiments transmit at least 75% of incident light at wavelengths from 500 nm to 11,000 nm, at least 70% of incident light at wavelengths from 650 nm to 12,000 nm, and at least 70% of incident light at wavelengths from 500 nm 14,000 nm. The chalcogenide glass core and the cladding in some embodiments exhibit an extinction coefficient of <0.1 cm.sup.−1 at wavelengths from 500 nm to 11,000 nm, from 650 nm to 12,000 nm or from 500 nm 14,000 nm.

(31) The water and oxygen contaminant levels should be controlled to achieve a low attenuation in a manner known to those skilled in the art. Similarly, it is known that the purity of the raw materials affects crystallization and attenuation. Still further, it is known that the do/dT should be low to minimize the runaway effect.

(32) For both the sulfur based compositions and the selenium based compositions, the properties of most interest, in addition to good chemical and mechanical durability and desired light transmission, are index dispersion, coefficient of thermal expansion, and thermal dependency of refractive index.

(33) The index dispersion is preferably as low as possible. The amount of index dispersion is measured as the Abbe number in the visible, V.sub.d, which is calculated as V.sub.d=(n.sub.d−1)/(n.sub.F−n.sub.C) where n.sub.d, n.sub.F and n.sub.C are the refractive indices of the material at the d line, F line, and C line (F line: 486.13 nm, d line: 587.56 nm, C line: 656.27 nm). Abbe number in the mid-IR range (3-5 μm) is generally calculated using the index at 3,000, 4,000, and 5,000 nm while the Abbe number in the long-wave range (8-12 μm) may be calculated using the index at 8,000, 10,000 and 12,000 nm.

(34) In general, the higher the Abbe No. the lower the index dispersion. The glass compositions according to the disclosure in some embodiments exhibit an Abbe No. in the visible range of at least 15, for example, 20-30, especially greater than 25. In the mid-infrared range, the glasses in some embodiments exhibit an Abbe No. of at least 100, for example, 100-300, especially at least 180, particularly greater than 200. In the far-infrared range, the glasses in some embodiments exhibit an Abbe No. of at least 60, for example, 60-185, especially at least 100, particularly greater than 120.

(35) Similarly, the coefficient of thermal expansion, a, in some embodiments is preferred to be as low as possible for the glass compositions according to the disclosure. Thus, the glasses according to the disclosure in some embodiments have a coefficient of thermal expansion that is less than 50×10.sup.−6/K or example, 15×10.sup.−6/K-25×10.sup.−6/K. In some embodiments, the core composition has a refractive index of 2.7782 at 10 μm and a CTE of 20.8×10.sup.−6/K at 10.6 μm and the cladding composition has a refractive index of 2.775 at 10 μm and a CTE of 19.5×10.sup.−6/K at 10.6 μm

(36) The thermal dependency of the refractive index, measured as dn/dT (the temperature coefficient of the refractive index), is low in some embodiments. Thus, the glasses according to the disclosure in some embodiments have a dn/dT value of less than 30×10.sup.−6/K, for example, 5×10.sup.−6/K-30×10.sup.−6/K.

(37) The selection of halide compounds can affect the critical cooling rate of the glass composition. For example, the halides M.sup.2Hal.sub.2 (M.sup.2=Zn, Cd, or Pb) and R.sup.2Hal (R.sup.2=Ag or Cu) produce glass at lower cooling rates while glass made with the halides R.sup.1Hal (R.sup.1=Li, Na, K, Rb, or Cs) and M.sup.1Hal.sub.2 (M.sup.1=Mg, Ca, Sr, or Ba) tend to require more rapid cooling. At a given cooling rate, a higher total halogen content may be achieved using M.sup.2Hal.sub.2 and R.sup.2Hal halides, as compared to R.sup.1Hal and M.sup.1Hal.sub.2.

(38) The addition of chlorine modifies the visible transmission and thereby the short wavelength dispersion which are linked though the Kramers-Kronig relation. The addition of Br has a somewhat larger effect than Cl on increasing thermal expansion and thereby reducing dn/dT which is linked through the Lorenz-Lorentz relation. Br has an impact on increasing IR transmission but a lower impact on increasing visible/NIR transmission relative to Cl. The identity of the alkali elements also impacts thermal expansion. Larger alkali ions (such as Cs) will generally tend to increase thermal expansion compared to smaller ions (such as Li). On the other hand, the identity of the alkali element will have very little effect on the transmission or dispersion.

(39) The glasses of the present disclosure may be used for non-limiting example to produce optical fibers. The fibers may be used for non-limiting example in medical applications for laser and endoscoping surgery and dermatology, in industrial applications for laser-based processing of materials, in automotive applications for optical data delivery, in medical and industrial applications for laser-based imaging systems, and in military and civilian applications for night vision systems.

(40) For medical applications in particular, the fibers of the disclosure can transmit IR radiation at, for example, 2.94 μm by using an Er:YAG laser, at 5.5 μm by using a CO laser, or at 9 to 11 μm by using a CO.sub.2 laser (main radiation at 10.6 μm).

(41) For industrial applications, the fibers of the disclosure can transmit IR radiation at, for example, 2 to 11 μm for pyrometers and other devices, where the lenses and the fibers can be made from the chalcogenide glass according the disclosure.

(42) For thermal visioning, the fibers of the disclosure can detect objects (e.g. missile defense) and can be used in small systems.

EXAMPLES

(43) Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present disclosure to its fullest extent. The following embodiments are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

(44) Tables 1A, 1B, 1C, 1D, 1E, and 1F list examples of the glass composition according to the disclosure. Tables 1A-1D list examples of the sulfur based glass compositions and Tables 1E-1F list examples of the selenium based glass compositions.

(45) TABLE-US-00002 TABLE 1A Examples of Sulfur Based Glass Compositions (mol %) according to the Disclosure Component Examples Content (mol %) 1 2 3 4 5 6 7 S 60 60 60 65 58 65 70 Ge 5 10 10 20 25 23 Ga As 40 35 30 25 12 10 7 Total 100 100 100 100 100 100 100

(46) TABLE-US-00003 TABLE 1B Further Examples of Sulfur Based Glass Compositions (mol %) according to the Disclosure Examples Component Content (mol %) 8 9 10 11 S 70 70 75 70 Ge 25 20 20 23 Ga 5 10 5 7 As Total 100 100 100 100

(47) TABLE-US-00004 TABLE 1C Examples of Selenium Based Glass Compositions (mol %) according to the Disclosure Component Content Examples (mol %) 12 13 14 15 16 17 18 19 Se 37 37 52.5 54.2 55.6 52.5 54.2 55.6 Ga 21 21 9.5 8.3 7.4 9.5 8.3 7.4 Ge 19 20.9 22.2 19 20.9 22.2 Br 21 9.5 8.3 7.4 Cl 21 9.5 8.3 7.4 Cs, Na, K, Ag 21 21 9.5 8.3 7.4 9.5 8.3 7.4 (Cs) (Cs) (Na) (Na) (Na) (Na) (Na) (Na) Total 100 100 100 100 100 100 100 100

(48) TABLE-US-00005 TABLE 1D Examples of Selenium Based Glass Compositions (mol %) according to the Disclosure Component Content Examples (mol %) 20 21 22 23 24 25 26 27 Se 37 37 52.5 54.2 55.6 52.5 54.2 55.6 Ga 21 21 9.5 8.3 7.4 9.5 8.3 7.4 Ge 19 20.9 22.2 19 20.9 22.2 Br 21 9.5 8.3 7.4 Cl 21 9.5 8.3 7.4 Cs, Na, K, Ag 21 21 9.5 8.3 7.4 9.5 8.3 7.4 (Ag) (Ag) (K) (K) (K) (K) (K) (K) Total 100 100 100 100 100 100 100 100

(49) TABLE-US-00006 TABLE 1E Further Examples of Selenium Based Glass Compositions (mol %) according to the Disclosure Examples Component Content (mol %) 28 29 30 31 32 33 Se 55 65.5 57.7 55 65.5 57.7 Ga 10 8.7 7.7 10 8.7 7.7 Ge 20 21.8 23 20 21.8 Br 10 8.7 7.7 Cl 10 8.7 7.7 Zn 5 4.3 3.9 5 4.3 3.9 Total 100 100 100 100 100 100

(50) TABLE-US-00007 TABLE 1F Further Examples of Selenium Based Glass Compositions (mol %) according to the Disclosure Examples Component Content (mol %) 34 35 36 37 38 39 Se 55 65.5 57.7 55 65.5 57.7 Ga 10 8.7 7.7 10 8.7 7.7 Ge 20 21.8 23 20 21.8 Br 10 8.7 7.7 Cl 10 8.7 7.7 Pb 5 4.3 3.9 5 4.3 3.9 Total 100 100 100 100 100 100

(51) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this disclosure for those used in the preceding examples. Fibers can be drawn from these compositions using any fiber drawing techniques known to those skilled in the art of fiber manufacture. Furthermore, the content of the sulfur and selenium can be adjusted to modify the refractive indices and the coefficients of thermal expansion to produce the fibers of the current disclosure.

(52) From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this disclosure and, without departing from the spirit and scope thereof, can make various changes and modifications of the disclosure to adapt it to various usages and conditions.