GB2225449A

GB2225449A - Bonding hard carbon to a base

Info

Publication number: GB2225449A
Application number: GB8927705A
Authority: GB
Inventors: Randal W Tustison; Dennis Montanari; Thomas Varitimos; Bernard Dibenedetto
Original assignee: Raytheon Co
Current assignee: Raytheon Co
Priority date: 1986-06-18
Filing date: 1989-12-07
Publication date: 1990-05-30
Anticipated expiration: 2009-12-07
Also published as: DE3720451C2; GB8713905D0; GB2192733B; FR2605417A1; JPH04362901A; FR2606164B1; DE3720451A1; FR2606165A1; JPH0682164B2; GB2225449B; GB2192733A; FR2606164A1; JPS62299901A; GB8927705D0; FR2606165B1; JPH0578001B2; FR2605417B1

Abstract

A layer of hard carbon 16 is bonded to a base 12 of a Group II-VI or Group III-V material with a first layer 14 of yttrium oxide, scandium oxide or magnesium oxide. The base 12 may consist of zinc sulphide, zinc selenide, mercury cadmium telluride, cadmium telluride, gallium arsenide or gallium phosphide. The layers may form an antireflection coating 15. <IMAGE>

Description

rl - -2225,449 IMPACT RESISTANT AND TEMPERED OPTICAL ELEMENTS

Background of the Invention

This invention relates generally to optical elements and more particularly to impact protection and strengthening of optical elements.

As is known in the art, optical imaging systems generally include externally mounted optical elements which shield the remainder df the imaging system from an external environment. For example, with infrared (IR) airborne imaging systems, an.IR transparont optical element such as a window or dome is mounted on the airborne system to isolate the remainder of the IR imaging system'from exposure to humid, corrosive and abrasive environments. Prolonged exposure to these environments generally degrade the optical and physical characteristics of the material of the optical element. Generally, the most severe environmental exposure encountered by these external elements appears to be high velocity water droplet impact which occurs when an airborne system is flown through a rain field.

This problem of water droplet impact is more generally referred to in the art as rain erosion. During flight through a rain field, water droplets impinge upon the surface of the external element producing subsurface fractures even at.subsonic velogiiEies. For very brittle materials these subsurface fractures are initiated at pre-existent microflaws lying near the surface of the optical element. Rain erosion damage to h is such optical elements occurs prior to any significant removal of material. The mere propagation of these pre-existent microflaws is sufficient to damage the optical element. in particular, these microflaws are propagated through the optical element by the 'tensile component of the urface stresswave created at the time of impact with the water droplet. Once formed, the continued propagation of the subsurface fractures through the optical element will often produce large cracks in the optical element. In the region of the crack, scattering and refraction of incident IR energy occurs producing increased internal reflections and IR energy losses. with a significant number of such cracks, the transmissivity of the optical element is severely reduced. Furthermore, as cracks propagate through theoptical element, catastrophic failure of the element may occur. When the optical element shatters or breaks, the remaining optical elements of the IR imaging system are exposed to the external environment, resulting in potential catastrophic damage to the imaging system.

Typicaily, materials which offer the best mechanical durability and optical performance for infrared imaging systems, particularly in the 8?m to 12/Am infrared band, are limited to a relatively small number. Suitable materials include zinc sulf-ide, zinc selenide, germanium, gallium arsenide, gallium phosphide, mercury cadmium telluride and cadmium telluride. Ternary sulfide materials such as calcium lanthanum sulfide are d.

1 i is also currently being developed for IR applications, particularly in the B- 12/Am band.. These ternary sulfide materials may provide some improvement in durability but even these materials are susceptible to the environmental exposures mentioned above. Generally, all of the aforementi6ned materials are relatively brittle and have a relatively low resistance to damage, particularly damage sustained during high velocity water droplet impact.

- it is also known in the art that optical energy incident upon a surface of an optical element will result in reflection of energy at such surface if the index of refraction of the material comprising the optical element is significantly different than the index of refraction of the medium from which' the energy originates. Generally, for-airborne systems, the originating medium is air having an index of refraction of about one. Accordingly, it is standard practice in the optical industry to provide coatings of material of appropriate refractive index over the incident surface of the optical element to red%;ce such reflection losses. At the deposited thicknessess, which are generally related to a fraction of an optical wavelength, these coatings are transparent in the IR band. However, heretofore such optical coati ngs have served only-to reduce reflection losses caused by a mismatch in refractive Indices and have not served to increase the impact resistance of the optical element.

1 A 1 is it is known in the art that a layer of hard carbon, that is, a carbon layer having quasi-diamond bonds and substantial optical transparency, when provided over germanium provides limited protection to germanium optical elements from impact damage caused by rain erosion. Hard carbon coatings on germanium are described in an article.entitled OLiquid Impact Erosion Hichanisms, In Transparent Materials" by J.E. Fields et al, Final Report September 30, 1982 to March 31, 1983, Contract No. AFOSR-78-3705-D, Report No. AFWAL-TR-83-4101. The hard carbon surfaces have not successfully adhered to other IR materials such as zinc sulfide and zinc selenide. Furthermore., hard carbon coatings even on germanium as- mentioned in the article are susceptible to debonding during high vdlocity waterdroplet impact. It was theorized there that the sheering force resulting from the radial outflow of water droplet impact causes debonding of the coating' from the germanium layer. This phenomena of debonding is believed to significantly increase as the thickness of the hard carbon layer is increased. Therefore, thicker hard carbon coating layers which should have resulted in further impact protection for the optical element were not successful because of the aforementioned debonding problem. A further problem with hard carbon is that the index of refraction of liaid carbon is about 2.45, substantially higher than the index refraction of many of the aforementioned optical materials such as zinc sulfide and zinc selenide. Accordingly, if an

1 optical element is coated with a hard carbon coating, reflection losses at the incident surface of the optical element will be higher than if the optical element was not coated.

A third problem in the art concerns the fracture strength of these materials. Again, most materials which are suitable for IR transparent windows particularly in the 8 I.A m to 12 1A m band have' low fracture strengths. This characteristic is particularly important in applications of these elements where the element separates a high pressure region from a low pressure region, that is, in applications where the element is under some static or dynamic mechanical load. In an article entitled "Impact Damage Threshold In Brittle Materials Impacted By Water Drops by A.G. Evans et al, Journal of Applied Physics Sl (5),, pps. 2473-2482 (May, 1980) at page 2481 it was theorized that martensite toughening (phase changes) at the surface of the brittle material may be useful in tempering such brittle materials. it was also theorized that surface compression stresses could be of benefit. However, the authors gave no specific description what they meant by - "surface compression." These brittle materials undergo surface compression when incident water drops impact the surface of the material.

1 q SunutLary of the Invention 25.

In accordance with the presen invention, an optical element which Is resistant to high velocity water droplet impact includes a base layer of a first material having a first predetermined modulus of elasticity and a coating of a second material having a second, higher modulus of elasticity. The coating layer bonds to the material of the optical element and has a high degree of resistance to debonding caused by sheer stres.ses encountered during high velocity water droplet impact.. ' Preferably, the high modulus of elasticity coating comprises a materia 1 having an index of refraction less than the index of refraction of the material comprising the optical element. Preferably still, the material is substantially transparent to infrared radiation, and.is substantiall water insoluble. With this arrangement, the coating of the second higher elastic modulus material protects the base comprised of the lower elasticity modulus material against impact damage, particularly such impact damage caused by high velocity droplet impact. Furthermore, the coat.ing materfiLl having a high resistance to debonding from sheering forces will remain intact on the optical element during high velocity water droplet impact and thereby protect the optical element from environmental exposures such as rain erosion.

In accordance with a: further aspect of the present Invention, the coating comprises a composite coating of a 1 it r- a 1 is Z5.

R mixture, preferably homogeneous mixtures of first and second materials, each having a modulus of elasticity at least twice as high as the modulus of elasticity of the material forming the base layer. The second material has a substantially higher modulus of elasticity than the first material, whereas the first material is insoluble and inert with water and the second material is reactive with water. With this arrangement, the composite coating provides a layer over the optical element having a higher modulus of elasticity than the modulus of elasticity which would be provided by just a layer of the first material. Rowever, the composite coating will also have a relatively low water solubility and reactivity with water particularly if a layer of the first material is piovided to isolate the mixture from a source of water.

In accordance-with further aspect of the present invention, the material of the base layer is selected from the group consisting of silicon, germanium, gallium arsenide, gallium phosphide, cadmium telluride, mercury cadmium telluride, zinc sulfide and zinc selenide, and more preferably, cadmium telluride, zinc sulfide, zi nc selenide or a ternary sulfide such as calcium lanthanum sulfide. The high modulus infrared transparent material comprising the first coating layer is selected from the group consisting of yttrium oxide, scandium oxide, and a homogeneous composition of yttrium oxide and magnesium oxide, a composition of scandium oxide and magnesium oxide, and a composition 1 is of scandium oxide and yttrium oxide. With such arrangements, an impact resistant anti-reflection coating for optical elements operative in the 8, 1#.m to 12 m wavelength band is provided making such elements more resistant to damage caused by rain erosion or high velocity water droplet impact.

In accordance with a still further aspect of the present inventioh, an optically transparent element, comprising a first infare transparent material having a first modulus of elasticity, is protected from high velocity water droplet impact by a composite coating comprising a first layer of a second, optically transparent material having a second, substantially higher modulus of elasticity than that of the material of the optical element, and an index of refraction less than the index of refraction of the material of the optical element. The first coating layer material is substantially. resistant to debonding from the material of the optical element In response to sheer stresses resulting from radial outflow of droplets during high velocity droplet impact. A second layer of the composite coating comprises a third material having a third relatively high modulus of elasticity, said modulus of elasticity being higher than the modulus of elasticity of the first material comprising the optical element layer and, preferrabl higher than the second material of the first coating layer. The third material comprising the second coating layer is substantially transparent to infrared radiation and has an 4 1 1 '\ 4 1 i i 1 1 1 k is 1 S index of refraction higher than the index of refraction of the second material of the first coating layer. The third material comprising the second coating layer is also substantially resistant to debonding from the second material of the first layer of the composite coating, but may have a relatively poor resistance to debonding to the first material of the optical element. "With suc an arrangement, by interposing the first layer of material having substantial resistance to radial outflow induced debonding from the material of the optical element and further having substantial resistance to radial outflow induced debonding of the third material of the secondcoating layer, a compbsite coating'is provided which is substantially resistant to radial outflow induced debonding ad further has a modulus of elasticity greater than that 6f the first material. The composite coating allows the effective physical thickness of the protective coating t6 increase, affording increased protection while still maintaining or possibly improving the optical properties of the combination of the composite coating layer and the optical element.

In accordance with a further aspect of the present invention, the first material of the optical element is selected from the group consisting of silicon, germanium, gallium arsenide, gallium phosphide, mercury cadmium telluride# cadmium telluride, zinc sulfide and zinc selenide or a ternary sulfide. Preferably, the material is selected from the group k i is consisting of cadmium telluride, zinc sulf ide and'zine selenide. The second material of the first coating layer is selected from the group consisting of yttrium oxide, scandi= oxide or mixtures of yttrium oxide or scandium oxide with magnesium oxide. The third material of the second coating layer is selected from the group consisting of cerium oxide, titanium oxide, zirconium oxide or hard carbon. With such an arrangmentj by interposing the second material comprising the first coating layer which bonds well to both the first material of the optical element and to the third material of second coating layer, in particular, the hard carbon layer, the adherence problems generally associated with hard carbon to most 8-12 ?_ m optical materials, are eliminated. Further, since materials such as hard carbon do not have the proper refractiVe index to antireflect' materials such as zinc sulfide, zinc selenide or cadmium telluride# the hard carbon layer can be used in combination with the lower index of refraction first.coating layer to provide an effectively lower index of refraction composite layer.

In accordance with a still further aspect of the present invention, an optical element is protected by a composite layer comprising a plurality of layers of a low index, high modulus of elasticity material followed by a high index, high modulus of elasticity material stacked in an iterative fashion to form a multi-layer, anti- reflective impact resistant coating. With such an arrangement, this coating could be 1 is designed to provide broadband anti-reflection characteristics or other optical functions such as filtering with the advantage that the total physical thickness of the composite multi-layer coating could be large providing increased impact resistance. Preferably, the low index, high modulus of elasticity material is selected from the group consisting of yttrium oxide, scandium oxide or mixtures of yttrium.oxide or scandium oxide with magnisiuia oxide and the high index, high modulus of elasticity material is selected from the group consisting of cerium oxide, titanium oxide, zirconium oxide or hard carbon. The material comprising the optical element is selected from the group consisting of silicon, germanium, gallium arsenide, gallium phosphide, cadmium telluride, mercury cadmium telluride, zinc sulfide and zinc selenide or a ternary'sulf ide. in accordance with a still further aspect of the present invention, an impact resistant, tempered optical element includes a base layer of an optical material having an initial fracture strength. Disposed over the base layer of optical material is a:oating comprising a compressed layer of material. The compressed layer of material has an overall thickness which is substantially smaller in comparison to the thickness of the base of the optical material. With such an arrangement, the compressed layer of material will tend to mitigate the effects of the tensile stress wave component encountered during droplet impact on surface microflaws, 1 t 1 preventing their propagation through the surface of the optical element. The compressed regions, however, will tend to close these microflaws preventing their propagation in response to the tensile stress wave component thereby reducing or compensating for the tensile stress wave component. By reducing this tensile stress component, the damage resulting from water droplet impact on' a surface of the optical element will be mitigated and hence the relatively brittle material is provided with a tempered surface which is resistant to damage caused by rain erosion This tempered surface concomitantly increases the fracture strength of the optical element.

In accordance with a further aspect of the present invention,.an optical element, tempered to resist damage encountered during high velocity impact, includes a base comprisin an optical material having disposed on a surface thereof a compressed layer of said material. The compressed layer of material comprises a plurality of furrows disposed in said layer, said furrows being sepjarated by adjacent regions of said compressed layer and having disposed under said furrows a portion of the compressed layer of material.

Preferably# the thickness of the compressed region of the optical material is 3 microns or less. The furrows are typically 10A to 10,OOOA deep and 0.01 to 0.02 mm wide. With this arrangement, a tempered optical element is provided which is highly resistant to damage encountered during high velocity k 1 1 1 1 is.

' projectile impact.

In accordance with a still further aspect of the present invention, a method of tempering an optical element comprises the steps of machining a plurality of furrows into the optical element, said furrows having a depth generally in the range of 0 0 10A to 10,OOOA providing between adjacent furrows and under said furrows a compressed region of the optical material. in ac6ordince with a still further aspect of the present invention, a method of tempering a surface of an optical material includes the step of single-point machining of the optical element to provide a compressed layer 0.5 m to 3.0 m thick into the surface of the optical element. The compressed layer includes a plurality of furrows having a depth between 10 to 10,OOOA with adjacent furrows being spaced by a p6rtion of the compressed layer of the material of the optical element. Preferably, the furrows are introduced into the optical material by rotating the optical element at a predetermin4d speed while a single-point diamond tool is brought into contact with the surface of the rotating optical element, with said tool being fed across the surface of the optical element at a predetermined rate until the aforementioned compressed layer is provided. With this arrangement, by single-point machining the surface of the optical element, a compressed layer of the material of the optical element is provided. This compressed layer will strengthen the optical t 0 1 element and aid in preventing damage to the optical element resulting from high velocity droplet impact by mitigating or reducing the near-sur face tensile forces resulting during high velocity water droplet Impact.

In accordance with'a still further aspect of the present Invention, an impact resistant, tempered optical element includes a base layer of an optical material having initial fracture strength and having a first predetermined modulus of elasticity. Disposed over the base material layer.is a compressed layer of optical material. The compressed layer of material has an overall thickness which is substantially small in comparison to the thickness of the base of the optical material generally in the range of 1-3 microns. Disposed over the compressed.layer is a coating layer 6f a: second material having a second, higher modulus of elasticity than that of the material forming the base layer of the optical element. The coating layer bonds to the compressed layer of optical material and has a high degree of resistance to debonding caused by sheer stresses encountered during high velocity water droplet impact. With this arrangement, the combination of the compressed layer and the coating layer provide an optical element having enhanced impact resistance and-strength characteristics. The outer coating layer provides a coating of a material having a second, higher modulus of elasticity thereby protecting the underlying base layer 1 -is- comprised of the lower elasticity modulus material against impact damage such as encountered by high velocity droplet impact. Moreover, the compressed layer of material will tend to mitigate the effects of this tensile stress wave component encountered during droplet impact. Therefore, the combination of the two techniques will provide an optical element having substantially improved impact resistance and fracture strength.

i 1 1 is 1 It 9 Brief Description of the Drawings

The foregoing features of this invention, as well as the invention itself, may be more fully understood from the following detailed description of the drawings, in which:

FIG. 1 is an isometric viewof an optical element, here a plate comprising a base layer and a protective layer in accordance with the present invention;.

FIG. 2 is an exploded cross-sectional view taken along line 2-2 of FIG. 1 showing the protective layer comprising a single layer coating in accordance'with one aspect of the present invention; FIG. 3 is an exploded cross-sectional view taken along line 3-3 of FIG. 1 showing the layer comprising a pair of coating layers in accordance with an additional aspect of the present invention; FIG. 4 is an exploded cross-sectional view taken along line 4-4 of FIG. 1 showing the layer comprising a plurality of pairs of alternating high index of refraction and low index of refraction coating layers in accordance with a still further aspect of the present invention; FIGS. SA-5D are a series of graphs (prior art) showing radial stress reduction as a function of normalized distance from the center of droplet impact, for coatings having different modulii of elasticity.

1 FIG. 6 is a photomicrograph of an uncoated ZnS surface exposed to a simulated rain field rate of 1 inch per hour, velocity of 450 mph, 900 Impact angle and 2 mm rain drop size;

FIG. 7 is a photomicrograph of a coated shrface in accordance with the present invention exposed to the same simulated rain field as described in FIG. 6;

FIG. 8 is a plot of 1 transmissivity vs. wavelength for a 0.20 inch thick coated ZnS plate; FIG. 9 is a cross-sectional view of a portion of a dome; FIG. 10 is a cross-sectional enlarged view of a surface portion of the dome shown In PIG. 11; FIG. 11 is a diagrammatical view in cross section of a.rain droplet. incident upon a surface of a conventional optical element having a microstructure fault;.

FIG. 12 is a diagrammatical view in cross section of a water droplet incident upon a compressed layer In accordance with a further aspect of the present invention; FIG. 13 is 4n enlarged view of the water droplet impacting the compressed layer as shown in FIG. 12; FIGS. 14A, 14B are photomicrographs of a conventionally polished dome surface and a dome surface tempered In accordance with the present invention; FIG. 15 shows plots of KNOOP hardness numbers as a function of.load for a conventional polished ZnS surface and a ZnS tempered disk surfacei q r-) 0 k -is- FIG. 16 is a plot of typical hardness difference (KNOOP) as a function of penetration depth into the compressed surface of the ZnS tempered disk; FIGS. 17A, 17B are photomicrographs, respectively, of a surface of a ZnS lens which was conventionally polished and a ZnS lens which was tempered' in accordance with the present invention each after exposure to a simulated rain field;

FIGS. 18i, 183 are photomicrographs, respectively, of a lapped ZnS lens which was conventionally polished and a lapped ZnS lens which was tempered in accordance with the present invention showing distortion caused by the compressive layer; and FIG. 19 is a cross-sectional view of a portion of an optical element such as a plate or dome having a compressed layer of optical material and a coating layer in accordance with a further aspect of the present invention.- is j 4 r_111 1 1 Description of the Preferred Mnbodiment

Referring now to FIG. 1, an optical element here a plate 10 is shown to Include a base layer 12 comprising a material having predetermined optical properties. Although the optical element is herein described in particular as being a plate, it is understood that other types of optical elements such as windows, domes, lenses, etc. having shapes other than planar may alternatively be substituted for the aforementioned plate 10. Typically base layer 12 will have a thickness of at least 0.05in. generally 0.1in. to about 0.5in. or thicker. The optical element fu'rther may.have selective optical properties. For example, the optical element may be comprised of a material which is transparent to optical energy generally in the infrared, visible, and/or ultraviolet spectrums. The material may be a dielectric - or a semiconductor material. In particular, for optical elements used in infrared imaging systems in the 11/1( M to 124m wavelength range, examples of preferred materials include silicon, germanium, gallium arsenide, gallium phosphide, mercury cadmium telluride, cadmium telluride, zinc sulfide, zinc selenide, or one of the ternary sulfides. The selected material comprising layer 12 may be fabricated by any known technique such as powder compaction and densification or chemical vapor deposition. in particular for infrared applications, the materials selected for layer 12 are generally characterized as having a relatively low modulus of elasticity typically in the range of 5XI06 psi to 1SX106 psi, a high transmittance to infrared c X 1 is energyr typically in a range of "50% to 75% over at least a portion of the infrared wavelength band of 2.0 /9 m to 30 19 m, and an index of refraction at 10 microns typically in the range of 2.2 to 4.0. The relevant mechanical and optical properties of some of these materials are shown in Table 1.

TABLE 1

Properties of Materials for. Base Layer 12 Material n @ lopm R% Thermal Expansion Elasticity Coefficient 0 7f (10-6/ C) Modulus of X(106psi) CdTe 2.6 0.01 5.9 5.0 ZnSe 2.4 0.25 7.7 9.7 ZnS 2.2 0.89 7.4 10.8 CaLa2S4 2.4 0.25 14.7 13.8 GaP 3.0 0.37 5.3 203 GaAs 3.3 1.17 5.7 15.5 Ge 4.0 4.10 6.1 15.0 R% is the reflection loss per surface resulting from a single quarter wavelength AR coating Of Y203 as will be described below, applied over the corresponding material. Disposed over base 12 is an impact resistant anti-reflection coating layer 11. Suffice it here to say that coating layer 11 may have any one of the structures now to be discussed.

Referring now to FIG. 2, coating layer 11 is shown to include a first protective layer 14 disposed over and A It i 1 1 0 is . preferably on the material comprising base 12. Protective layer 14 is comprised of a material having a modulus of elasticity substantially higher than the modulus of the material of the base 12, a high degree of infrared transparency in the deposited thickness over the selected wavelength band of the optical element, and preferably an inde;x of refraction less than the index'of refraction of the material comprising base layer 12. Furthermore, the material deposited has a high degree of adherence to the material of layer 12 and in particular Is highly resistant.to debonding caused by sheer stresses induced by radial outflow of high velocity droplet impact such as water droplet impact. Layer 14 may be deposited by any technique such as ion beam sputtering, diode sputteri.ng" or evaporation. Furthermore, layer 14..may alternatively be provided over the plate.12 by dipping plate 12 in a solution comprising an organic vehicle and the high modulus of elasticity material. The plate after being dipped in the solution of such material is removed from this solution and.placed in an oven where the orgaic ve hicle is driven off. Alternatively, thecoating may be deposited by spray drying a mixture of a vehicle and the coating material over the base layer 12 heated to a predetermined temperature. With these particular coating arrangements, a relatively Inexpensive technique is provided to form a uniform layer of coating 14 on base 12. For the aforementioned base layer materials# suitable coating materials 1 v# 1.

include yttrium oxide (Y203) p magnesium oxide (Mgo) and scandium oxide (S0203), as well as, homogeneous mixtures of these aforementioned materials. The relevant mechanical and optical properties for these materials are shown in Table 2.

TABLE 2 .iggpi"ies.Of Materials -For Layer 14 material @(i6) Y203 1.63 SC203 Mgo 1.70 1.70 missivity raigi of 0.3 - 12P 0.3 - 12g.

0.3 - 12A Expansion Coefficient 16-6/C- 7.2 8.5 12.0 (106 psi) Modulus of Elasticity 26 48 1 is E20 Solubility insol. insbl.

insol. reacts with H 0 The principal factors to be considered in selecting materials for coating layer 14 are that the selected material must have optical properties sultable.for the intended use of the optical element 10 at the thicknesses at which the material of coating layers 14 is deposited. Further, the coating layer material 14 must have a modulus of elasticity generally about at least twice the modulusof elasticity of the material of base layer 12. Further# when the intended use of" the-optical element 10 will expose the coating layer 14 to water, the material of coating. layer 14 must be insoluble and stable in water. In order to provide anti- reflection 1 1 correction, the.index of refraction of the material of coating layer 14 is preferably less than the index of refraction of the material of base 12. In general for anti-reflection correction between air having an index of about 1.00 and the material of base layer 12, the index of refraction required of the coating (n14) is approximately equal to the geometric mean of the indices of refraction of the material of base.layer 12 and the surrounding medium (nl42:--n-l2)-. As is known in general for most materials, the index of refraction varies as a function of wavelength dispersion. Accordingly, this anti-reflection correction also varies as a function of wavelength.

Preferably, layer 14 is deposited over the base layer 12 to a physical thickness corresponding to one-quarter of an optical wavelength at the particular wavelength of int6rest for the optical element. In general# the optical thickness (to) of such elements is defined as the product of the physical thickness (t) of the coating 14 and the refractive index (nc) of the material of the coating 14 (to m (t nc). The desired physical thickness for an optical thickness of A/4 is given by t - (A/4)/nc where is the wavelength of particular interest for the optical element and nc is the refractive index of the coating at the wavelength of interes.t. As will now be appreciated by those skilled in the art, the optical thickness (to) may be a higher order thickness such as 3A/4 or SA/4, and the physical thickness t is then generally given by t - MN+1)A/41/nc It is where N is an integer 0,1,2,3.... Thus, the physical thickness t of layer 14 may be increased, offering greater impact resistance protection for base 12 while still maintaining good anti-reflection and optical transmissive properties. For a material such as Y203 having an index of refraction of nc-1.63 at 10.6 microns, the optimum thickness for a single 1/4 layer at 10.6 microns would be about 1.63 microns.

Referrind now-to FIG. 3, a plate 10 is shown to include the base 12 and coating layer 11 disposed over at least a f irst. surface thereof. Coating layer 11 is here a composite, antireflective impact resistant layer 15. Layer 15 is shown to comprise the aforementioned coating layer 14 of the high elastic modulus material having an index of refraction less than the index of refraction of the material of the base 12, having good adherence qualities to the material of the base layer 12. Disposed over this first coating layer 14 is a second coating layer 16 comprising a second material having a substantially higher elastic modulus and having an index of refraction higher than those of both the. material of base 12 and first coating layer 14. Suitable materials for the aforementioned second coating layer 16 includes cerium oxide, titanium oxide, zirconium oxide and hard carbon. of these examples, hard carbon is the preferred material since it has the highest modulus of elas.ticity. However, as mentioned previously, hard carbon does not adhere well to zinc selenide a 4 f zinc sulfide etc. which are amongst the preferred materials for base layer 12, particularly at optical wavelengths in the range of 8 m to 12 m. The relevant mechanical and optical properties of these materials are shown in Table 3. TABLE 3 Of.Materials For Layer 16 material' Hard carbon Ceo T102 Z92..

Hard carbon films may be deposited by any suitable technique. For example, ion beam sputtering, as well as, chemical vapor deposition involving decomposition of hydrocarbon containing vapors may be used. Although hard carbon layers have not generally adhered well to most IR materials, as mentioned previously, it is believed that such hard carbon layers will adhere to materials suitable for use as first coating layer 14. As mentioned above, suitable materials for laye,r.14 include M90, SC203 and Y203- In general, hard carbon adheres very well to oxides of various types Including the aforementioned ones. Thus, by interposing coating layer 14 n @ (10Am) 2.2-2.4 J.11ULAUCLA vluuu.LUU Expansion Of Coefficient Elasticity 10-6-?C" -j06 si - isb 2.34 11.3 2.4 8.2 ...7.2..

B20 Solubility insol.

22 44 28 insol.

insol.

It i between the very high modulus layer 16 and base 12, the impact resistant advantages of the very high modulus layer 16 materials provide an anti-reflection, highly impact resistant composite layer 1S to protect the base 12 from high velocity water droplet impact.

Referring now to FIG. 4, an optical element here a plate is shown to include the base layer 12 and coating layer 11.

Coating laier il here is a broadband anti-reflection impact resistant coating layer 17 having a plurality of the afore mentioned composite, anti-reflective impact resistant coating layers 15, as described in conjunction with FIG. 3. With this arrangement, a very thick anti-reflective coating 11 having excellent adhesion properties to bass 12 and high impact resistance is provided. Further, by appropriate selection of thicknesses of the plurality of composite layers 15 and the individual coating layers 14 and 16 in accordance with multi layer coating optical design principals, a broadband anti reflection coating may also be provided.

Referring now to FIGS. 5A-5D,- a series of graphs from a Fields et al report entitled Liquid Impact Erosion Mechanisms

In Transparent Materials AFWAL-TR-82-4022 shows radial stress reduction as a function of the normalized 4stance from the center -of the drop impact. Each graph has plots representative of the radial stress developed on a coated surface having a modulus of elasticity higher than that of the material of the optical elements in comparison with the radial stress developed 1 01 1 25. - on an uncoated surface. AS shown in FIG. 5D# when the modulus of elasticity of the material of the coating is approximately equal to 10 times the modulus of the material of the base layer, the tensile stresses induced in the-base layer are substantially equal to zero during water droplet impact.

Referring now to FIGS. 6 and 7, photomicrographs of an uncoated surface (FIG. 8) and a coatedsurface (FIG. 9) each after exposure to a simulated rain field at the rate of I inch per hour, at a velocity of 450 miles per hour, with an incident angle of 900 and droplet diametir of 2mm. is shown. As can be observed, the amount of damage exhibited by the uncoated surfac e of zinc sulfide is substantially higher than the damage exhibited by the yttrium oxide coated zinc sulfide surface.

Referring to FIG. 8, a plot of a pircent transmissivity vs4wavelength for a 0.2 inch thick coated plate of RAYTRAN (Trademark for Raytheon Co. Lexington, Ma.) type of zinc sulfide is shown. The coating was yttrium oxide a single quarter wavelength thick at 19.0 microns. The coating was approximately 2.45 microns thick. The coating was selected to maximize the transmittance of the surface at 10 microns,.and was applied to both major-surfaces of the plate.

Referring now to FIGS. 9-12, a portion of an optical eleinent, here a dome 110, is shown to include a layer 112 comprising a material having predetermined optical properties. Although the optical element is herein described in particular as being 1 1 is a dome, it is understood that other types of optical elements such as windows, plates, lenses, etc. may alternatively be substituted for the aforementioned dome 110. Typically, base layer 112 will have a thickness as base layer 12. The optical element further may have selected optical properties. For example, the optical element may be comprised of a material which is transparent to optical energy-generally in the infrared, v1siSle, or ultraviolet spectrums. The material of the optical element may be a dielectric or a semiconductor material. In particular, for optical elements used for infrared imaging systems, examples of preferred materials include silicon, germanium, gallium arsenide, gallium phosphide, mercury cadmium telluride, cadmium telluride, zinc sulfide, zinc selenide or one of the ternary sulfides of the general form MN2S4 where M is a monovalent ion, N is a ion selected from the lanthanide series and S is the sulfide ion S-2. The selected material comprising layer 112 may be fabricated by any known technique such as powder compaction and ensification or chemical vapor deposition. In general,' materials which are selected for layer 112 are characterized as having a relatively high transmittance to a particular energy, for example, infrared energy typically in excess of 501 at least over a portion of the infrared band, are generally very brittle and fairly stiff materials having a modulus of elasticity in the range of 5 to 1SX106psi, but are generally fairly weak materials having a fracture strength of it 1 1 1 f 1 is i 1 -29typically Sp560 to 15,000 psi.

The dome 110 further includes a plastically deformed compressive layer 114 (FIG. 10) provided over surface 112a of the optical element 110. Preferably, the compressive layer 114 is a portion of the material of layer 112. As shown more par ticularly in FIG. 12, the compressive layer 114 includes a plurality of furrows or grooves 113 w#h adjacent ones of said grooves or- fu:erows 113 being spaced by compressed regions 113a of the material of layer 112 and having disposed under said furrows a compressed layer 113b. The degree to which the layer 114 is compressed is a function of the magnitude of the compressive forces which are provided during treatment of the dome 110 as will be described.

Referring now to FIGS. 11 and 12, the mechanism by which the compressive layer 114 strengthens and protects the dome 110 from damage encountered during high velocity water impact or mechanical loading will now be described.

As shown in FIG. 11, a conventionally polished surface 112a has a water droplet 115 having a resultant velocity VO normal to a surface 112a impinging upon surface 112a of layer 112. Present in surface.112a of layer 112 is a pre-existent microflaw 116 created during fabrication of the polished surface or otherwise associated with the morphology of base 112. During impact of water droplet 115 with conventional surface 112a, a tensile component of the resulting surface stress wave 14 is -represented by arrows 118 is produced. In response to this tensile force 118 in the region of the microflaw 116, the microflaw propagates as crack 1161. If the tensile force is sufficiently high, the crack 1161 can. propagate completely through the base 112 of optical element 10. With a sufficient number of "these cracks,. the optical transparency of the element can be severely reduced due to intern41 reflections and refractior; inthe region of the crack. More importantly, the optical. element with sufficient cracks is susceptible to shattering or breaking thus exposing the remainder of the optical system (not shown' to catastrophic damage.

As shown In FIGS. 12 and 13 in accordance with the present _invention, as compressed layer 114 Is provided over the dome 110, the pre-existing microflaws' 116 provided in the base 112 are healed by c6mpression of the material in region 114. During fabrication of the compressed layer 114, opposing compressive forces 114 are provided which cause the microflaws to shrink in size resulting in smaller Microflaws 117. Furthermore# the material surrounding the microflaw 117 is still under compregalon as represented by arrows 120 pushing in on the material. around - the- microf law 117, During water droplet impact, as mentioned above, a tensile stress component 118 1 is provided' at the site of the microflaw 117. Accordingly, since the microflaw 117 is smaller, 'the velocity at which the water droplet may impact the surface layer without causing damage has 1 1 is 2 10 t _ increased since the velocity threshold is increased by reducing the size of the microflaw. Furthermore the material remains in compression after the furrows 113 are provided and the reduced tensile force component 1181 created at microflaw 117 will not propagate through the compressive layer 113 and into the base layer 112 unless the tensile force component 1181 can overcome the compressive foice-representing the degree to which the layer 114 Is nder compression. Accordingly, the compressive layer 114 provides two mechanisms to increase the velocity threshold at which impact damage will occur: it generally reduces the extent of the microflaws present in the material the-reby creating,for a given water droplet impact velocity a smaller resulting tensile component; and provides a compressimb' force to dampen or reduce the propagation of the tensile force produced through the compressed layer 13.

The pre ferred method for providing the compressive layer 114 is to machine a surface-portion of the optical element with a single diamond point. Generally, the surface may be machined in tw6 steps. The first step, a rough cut,' has machining parameters selected to remove substantial amounts of material 119 as shown in FIG. 10, this may be on the order of 1 to 5 mils or more of material. The second cut, a "finishing cut," may be of one or several passes or cuts where a small amount of material, typically 0.1 to 0.5 mils is removed to provide a substantially flat, yet furrowed surface.

1 i is 1_..

Typical surface characteristics for the tempered compressive layer 114 shown in FIG. 10 are as follows:

The furrows 113 typically may have a width wf typically of 0.01 to 0.02 mm. The' sidewall portions 113a generally have a height hf of 10 A to 10, 000 A.

Typical machining parameters that are useful to machine a compress.ive layer 114 in I inch zinc sulfide discs are as follows:

Useful Single-Pt Machining Parameters for Creating Compressive Surface Layers Rough Cut:

Depth of Cut - 0.003 inch Rotation Speed - 750 rpm Feed Rate - 0.5 inches/min. Tool Radius - 0.12S inches Finish Cut Depth of Cut - 0.0002 inches Rotation Speed = 550 rpm Feed Rate - 0.250 inches/min. Tool Radius - 0.125 inches Sixty samples of zinc sulfide discs were fabricated in accordance with the present techniques. Mechanical parameters measured on these discs were knoop microhardness (Kg/mm2) and fracture strength. Fracture strength was generally at least 19,SOO psi which is greater than the fracture strength (15,SOO) of conventional polished samples. Accordingly, this technique provides about a 25% increase in fracture strength.

t 0 1 1 X 4; 2 1 1 As shown in PIGS. 14A, 14B the conventionally polished surface is substantially smooth, uniform and featureless, whereas# the surface prepared in accordance with the present invention has substantially regularly spaced apart furrows or grooves.

As shown in FIGS. 15 and 16, typical microhardness plots of knoop hardness numbers vs. load for conventionally polished zinc sulfide discs and zinc sulfide discs having the compressed layer 114 are shown. The knoop hardness for Aiscs having the compressed layer 114 are generally between 50 and 100 numbers higher than the knoop hardness numbers for conventionally polished discs for loads of 30 grams or less. Furthermore, as shown in FIG. 16, the hardness difference expressed as difference in knoop hardness numbers as a function of ' penetration depth into the compressed layer 114 indicates that a significant increase in hardness is provided. for penetration depths of 2 microns or less. By extrapolation of this data, it is interred that the hardness effect is confined within a 3 micron surface portion of the machined samples.

A comparison of FIGS. 17A and 17B, conventionally polished vs. diamond point machined zinc sulfide plates following 5 minutes of exposure at 4SO miles per hour to a 1 inch per hou simulated rain fieldr 2 mm drop diameter, shows that the conventionally polished sample sustained significantly more damage consisting primarily of subsurface fractures; whereas the damage sustained by the plate having the compressed layer provided by single diamond point machining a zinc sulfide sample (FIG. 17B) is substantially reduced.

Comparison of PIGS. 18A and 18B indicates that layer 13 is a compressed layer of optical material. Two zinc sulfide lens blanks from the same lot of zinc sulfide ma:terial were polished. One lens had its surface polished optically flat using conventional polishing techniques, the other lens had its surface machined flat in accordance with the present invention. Following fabrication, each sample was mounted face down on a lapping pad and thinned down from approximately 0.2 ihches to 0.01 inches in hickness and to a quarter wavelength flatness in the visible spectrum across the lapped surface. When these samples were released from the lapping pads, some distortion in each sample took place. This distortion Is shown in the interference topographs of FIGS. 18A and 18B. As shown in FIG. 18A, the distortion in the conventionally polished sample was minimal resulting in a-final irregular surface. However, as shown in FIG. 18B, for the sample having the compressed layer 114 in accordance with the present Invention, the distortion was so severe that it could not be measutred on the' interferometer. Furthermore, once the specimen inFIG. 18B was released from the lapping pad, the sample distorted into a highly concave surface. This distortion is related to the inherent stresses contained in the 1 t...

r.

1 A layers of the lapped sample. Accordingly, it is clear that substantially no compressive stress is provided in the conven tionally polished blank (FIG. 18A); whereas, the sample represented in FIG. 18B was provided with a highly compressed layer 114. The radius of the concave surface was optically measured and this radius was used to estimate the amount of compressive stress present at the surface of the machined sample (FIG. i8B). Compressive stress (S) as related to the radius (R) of the curvature of the surface was as follows:

S E'd2 6 (I-V)ZRwhere E is Young Modulus given as 10.8 X 106 psi; d is the sample thickness estimated to be 0.009 inches; R is the radius of curvature measured as 129.2 X 10-2m; t is the thickness of the compressed layer, estimated as I X 10-6m and V is the Possion's ratio estimated as 0. 28. Solution for S provides S - 7100 kg/cm2 or 1 X 105 psi. Accordingly, the strengthening and hardened effects demonstrated in the previous data are clearly the result of the formation of a surface compressive surface layer on the zinc sulfide blanks during the operations described above. Therefore, by proper choice of machining parameters such as the tool speed, tool type, depth of cut, the feed.rate, tool angle, etc. the magnitude of the compressive layer provided on the zinc sulfide surface may be selected and, hence, the degree of strengthening/hardening of the zinc 1 1 f.

sulfide may also be controlled.

Referring now to FIG. 19, a portion of an optical element, here a plate 130 is shown to include the layer 12 comprising a material having predetermined optical properties as described above. Disposed over layer 12 is a compressed layer of material 114 as described in conjunction with FIGS. 9-18. Disposed over compressed layer 114 is.a coating layer 11 comprising on of ihe aforementioned single layer or multilayer coatings described in conjunction with FIGS. 1-8. With this particular arrangement, it is believed that the c enhanced hardening and rain erosion resistant properties of both techniques described previously will aid in providing an optical element having substantially improved rain erosion resistance andfracture strength.

Having described preferred embodiments of this invention, it will now be apparent to one of skill in the art that other embodiments incorporating its concept may be used. It is felt, therefore, that this invention should not be limited to -the disclosed embodiments, but rather should be limited only by the spirit and scope of the appended claims.

1 p A15,11 1 1

Claims

Claim

1. A method of bonding a layer of hard carbon to a base rising a material selected from the group consisting of a Group II-V or Group III-V material comprising the step of: providing a first layer rising a material selected from the group consisting of yttrium oxide, scandium oxide and magnesium oxide between the base and the hard carbon layer.

2. The method of claim 1 wherein the Group II-VI material is selected from the group consisting of zinc sulfide, zinc selenide, mercury cadmium telluride, cadmium telluride and the Group III-V material is selected from the group consisting of gallium arsenide and gallium phosphide.

3. The method as recited in claim 2 wherein the base of the first layer and hard carbon layer provide an optically transparent element.

4. The method as recited in claim 3 wherein the first layer has a physical thickness (t) related to = (2N+1) /4/nc where is a wavelength - of interest, nc is the refractive index of the material of the first layer at and N is an integer 0,1,2,3....

Published 1990atThe Patent Office. State House. 66'71 High Holborn. London WClR4TP.Further copies maybe obtained from The Patent OMce Sales Branch, St Mary Cray, Orpington. Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent, Con V87