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Diamond and Related Materials 10 Ž2001.

1846 ᎐ 1849

Diamond-like carbon films in multilayered interference coatings for IR optical elements
O.M. Kutsay a,U , A.G. Gontar a , N.V. Novikov a , S.N. Dub a , V.N. Tkacha , B.A. Gorshtein b, O.V. Mozkovab

Institute for Superhard Materials of the National Academy of Sciences of Ukraine, 2, A¨ toza¨ ods’ka Str., Kyi¨ , 04074, Ukraine b ‘ Arsenal’ Central Design Bureau, 8, Mosko¨ s’ka Str., Kyi¨ , 03601, Ukraine

Abstract In the majority of modern IR interference multilayer coatings ŽMLC., conventional film-forming materials ŽFFM. of fluoride and chalcogenide types are used. Such coatings are characterized by relatively low mechanical strength and stability against enhanced humidity and, therefore, require surface protection. Our present results support the view that mechanical strength of these MLCs can be improved by applying a diamond-like carbon ŽDLC. film as an external layer. Nanoindentation measurements show that the addition of a DLC film to ZnSerBaF2rY2 O 3 IR antireflection MLC increases the combined hardness of the coatings from 0.5 to 3.6 GPa. The formation of an indent on the upper and subsequent layers of MLC has been studied by SEM and X-ray spectrum microanalysis. The resistance of DLC films applied onto MLC against light irradiation, organic solvents as well as against environmental factors was also studied. Atomic force microscopy ŽAFM. was used to study variations of the surface morphology of the initial MLC components before and after DLC film deposition. ᮊ 2001 Elsevier Science B.V. All rights reserved.
Keywords: Diamond-like carbon; Applications; Mechanical properties; Wear

1. Introduction The majority of modern interference coatings for optical elements applied in infrared ŽIR. spectral region use fluorides ŽPbF2 , ThF4 , BaF2 ., chalcogenides ŽSb 2 S 3 , ZnSe, PbS. and oxides ŽTiO 2 , ZrO 2 , Y2 O 3 .. Unfortunately, chalcogenides and, especially fluorides, are characterized by insufficient mechanical strength and stability under climatic conditions. Multilayer coatings ŽMLC. made of such film forming materials ŽFFM. require upper protective layers with improved operating characteristics Žhigh mechanical stability and adhesion.. Oxide films used for these purposes have very

Corresponding author. E-mail address: ŽO.M. Kutsay..

large absorption coefficient in the low-frequency IR region Ž8 ᎐ 20 ␮ m.. Therefore, oxide layers no more than 30 ᎐ 50 nm in thickness are used. Besides, the oxides have a rather high refractive index, while the upper layers of anti-reflection MLC should have the lowest refractive index. Thus, the search for new possibilities to eliminate the above disadvantages of conventional interference MLC is urgent to improve their operating characteristics. Applying films of new FFM and optimization of the deposition parameters could solve this problem. Diamond-like carbon ŽDLC. films offer promise as protective layers w1 ᎐ 3x. The use of a DLC film as a component of interference MLC is attractive due to the possibility of varying the film refraction index over a wide range by changing the deposition parameters w2x.

0925-9635r01r$ - see front matter ᮊ 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 5 - 9 6 3 5 Ž 0 1 . 0 0 4 5 7 - 5

Consequently. To measure the mechanical properties of multilayer coating. A DLC film deposited onto a MLC has significantly improved mechanical properties of the sample surface ŽFig.3 mN Žat an indent depth of approx. Thus. The films fail even at a load of 0. Fig. the nanohardness was approximately 0.. the thickness of the protective Y2 O 3 layer was approximately 50 nm. the oxide film does not affect indenter penetration. was assessed by comparing the optical transmission of the MLC q DLC sample before and after the tests. DLC films from 50 to 100 nm in thickness have been deposited at low substrate temperatures Ž300 ᎐ 330 K. isopropyl spirit boiling for 30 min. using a Berkovich indenter w4 ᎐ 6x. Nanohardness tests performed at a minimal load of 0. . all optical elements retained their transparency values.0 ␮ m were recorded by a Carl Zeiss Specord M80 ŽGermany. The elastic recovery of oxide films is much greater. To measure nanohardness as a function of depth using the loading segment data. The nanohardness at this depth has increased to 3. organic solvents Žacetone. After DLC film deposition. Almost all of the indenter displacement during the test is due to elastic deformation of the sample surface. Bias voltage was y300 V and methane concentration varied in the range of 30 ᎐ 70 vol. Also. covered with a cambric cloth. Load ᎐ displacement curve for MLC. Experimental 3.% w3x. 3. 1. Results and discussion Optical transmission spectra were measured for initial MLC samples and after deposition of DLC films ŽMLC q DLC. For the initial MLC sample. Measurements at a peak load of 120 mN allow us to study the mechanical behavior of MLC to a depth of approximately 2000 nm. The stability of MLC covered with a DLC film ŽMLC q DLC. the protective properties of the Y2 O 3 films appear to be poor. was used to study variations of surface morphology in the MLC. mechanical properties of Y2 O 3 and underlying BaF2 films have been analyzed. penetration to a depth of 50 nm requires 10 times higher loading. carbon tetrachloride. The thickness of the quarter-wave layers of ZnSe and BaF2 was approximately 2 ␮ m. The low nanohardness Ž0. The Electron-beam deposited polycrystalline ZnSer BaF2rY2 O 3 films were used as the MLC standard for comparison. USA.5 ᎐ 20.55 GPa. The load ᎐ displacement curve of the MLC down to a depth of 50 nm is given in Fig. Once failed. were used as substrates. A Digital Instrument ŽUSA. respectively. The wear resistance tests were carried out according to the industrial requirements for optical coatings. atomic force microscope ŽAFM. toluene. we applied the technique proposed in w8x.e.0 mm. only at peak loads.005 mN. the essential increase of the indent depth elastic recovery has been observed during unloading. Kutsay et al. a relative humidity of 98% at 35 and 100ЊC. and ultraviolet irradiation Ža UV light flux of 60 Wrm2 power. 50 nm. spectrophotometer. 2. In this case. The hard and brittle oxide film deposited onto soft BaF2 .6 GPa. in the methane ᎐ hydrogen atmosphere. The high elastic recovery during nanohardness tests is typical for carbon and hydrocarbon diamond-like films and is one of the main reasons for their high wear resistance w9x.O. The unloading curve demonstrates slight elastic recovery of the indent depth that is typical for such a soft material as BaF2 . has been destroyed by the indenter at a depth of 10 nm. The dependence of nanohardness on indenter displacement is shown in Fig. Nanohardness at the peak loads for MLC will average the values for layers having different properties. 3000 revolutions of a rubber tip Žradius of a spherical surface of 3. at a depth of 50 nm and the unloading curve shape point to this fact. in the indent ŽMeier hardness.. The IR transmission spectra in the wavelength range of 2. In this case. The Oliver and Pharr technique is the most widespread for the analysis of the load-displacement curve w7x. irradiation time s 240 h. It allows one to find the average contact pressure ŽACP. 1. r Diamond and Related Materials 10 (2001) 1846 ᎐ 1849 1847 2. depth-sensing nanoindentation tests were used.5 GPa in the displacement range from 500 to 1000 nm. action time was 40 and 1 h. onto them. Silicon and germanium wafers Žwhich are optically transparent in the IR region. Loading on the tip was 200 g. give information on mechanical properties of the upper layer. Tests were performed on a Nano Indenter II device ŽMTS. by plasma-enhanced chemical vapor deposition ŽPECVD. under the action of climatic factors Ženhanced humidity. i. the indenter sharply descends to a depth of 30 nm and then penetrates into soft fluoride.M.

DLC decreases the indent depth. At a greater depth. 4 Žbottom of the image. The traces of failure of the surface of MLC without a DLC film could be seen in Fig. The surface of a sample with MLC q DLC Žthe top of the image. The ZnK ␣-radiation from the bottom layer of ZnSe has not been detected. and MLC Žbottom. observed surface nanohardness increase is due to the influence of the Y2 O 3 film at a depth . The YL ␣-radiation intensity profile for the 50-nm deep indent is evidence that the protective DLC coating prevents the MLC from being damaged. r Diamond and Related Materials 10 (2001) 1846 ᎐ 1849 Fig. the nanohardness at a depth ) 1000 nm begins to increase.. the nanohardness of the DLC-coated sample differs only slightly from that of the uncoated sample. It is confirmed by the fact that at maximal loading Ž150 mN. to the contact zone. . 4. and MLC Žbottom. Kutsay et al. which is harder than the BaF2 layer. 5. The DLC film deposition increases abruptly the hardness at a depth of .. The failure of the MLC q DLC has been observed only after adding diamond micron powder Žgrain size s 2 ᎐ 3 ␮ m. 4.500 nm.. 2.500 nm. The regularities of MLC q DLC failure at nanoindentation are confirmed by SEM and X-ray spectrum microanalysis of an indent profile. To characterize the failed layer of the indent.1848 O.M. in the contact zonex: MLC q DLC Žtop. exhibits no mechanical damages even after increasing the total number of wearing tip revolutions up to 15 000. Optical images of MLC and MLC q DLC surfaces after wear test: MLC q DLC Žtop. The use of DLC film as a protective layer increases the stability of the optical and mechanical properties of the MLC system under the influence of external factors. Fig. displacement of the indenter.. This fact confirms that the indenter destroys only the upper layers. Even after processing by the micron powder. Hardness of MLC and MLC q DLC vs. Fig. The influence of the DLC film is observed to the 1500-nm depth. The results of preliminary testing of these properties of the DLC-coated surface of the monocrystalline Fig. the characteristic X-ray radiation of Zn. As a result. At displacement greater than 1000 nm. Y and Ba was used. 5. the indenter begins to penetrate into the ZnSe layer. 3.. Load ᎐ displacement curves for MLC and MLC q DLC. the MLC q DLC showed less mechanical damage than the MLC ŽFig. Optical images of MLC and MLC q DLC surfaces after wear test wdiamond micron powder Žgrain size s 2 ᎐ 3 ␮ m. The results of the wear resistance tests are shown in Fig...

Chugunova. y s 0. Phil. D.A. to increase optical transparency. W.F. Res. Novikov.W.V. This is indicative of the ability of DLC films to reduce the roughness of a polycrystalline surface. Mater. Kutsay et al. whilst retaining their optical characteristics. w9x N. w6x E. New York.J. A.C. it was necessary to prove not only the mechanical stability of the MLC q DLC system but also the fact that it retains its optical properties. Rowcliffe. Soderlund. Hutchings. 792. such as porosity and low stability to the environmental influence. w10x N. Res.6 Gpa. Diam.B. Novikov. 407. and with a DLC film Žb. 574. Photo-Opt. Nix. Novikov. Lytvyn for AFM images of sample surfaces. ŽAllerton Press Inc. 48 Ž1983.M. Voronkin. J. Gridneva. Gontar. Mag. 1356.I. w8x N.D. the MLC rootmean-square ŽRMS. J.M. Thus. J. W.0 nmrdiv. 6. Multilayer coatings are necessary for parts made of materials with high refraction indices ŽSi. Milman. Dub et al. 7 Ž1992. Oliver. Acknowledgements This work was supported by the Science and Technology Center in Ukraine ŽSTCU project no. Yu. The authors thank P.5 to 3. Instrum.C.. For this purpose. 4. Gontar.2 ␮ mrdiv. G. Relat. Khandozhko. AFM images of MLC surfaces: initial Ža. we have examined the MLC q DLC samples exposed to enhanced humidity. w7x W. I. Ž1996. Mater. S. S. 6 Ž1997.0 = 5. A. Forum 52r53 Ž1989. w4x J.V. 2. J.V. and z s 100. 32. Hard Mater. Savvides.V. Considerable improvement of MLC mechanical properties Žincreased combined nanohardness of the coatings from 0.C. 15. were obtained from statistical analysis of the frontal image for a scanning area of 5. roughness was reduced from 30 to 20 nm. Angus. References w1x J. 149.I. Mater.1 standard. Pharr. Kutsay. w2x N.G. could be achieved by DLC film deposition. Surface morphologies of the MLC before and after DLC film deposition are shown in Fig. Proc.V. 1 Ž1986. Vapor Deposition 4 Ž1. Mater. Diam. R.I. 601. Khandozhko et al. Eng. The quantitative parameters of the roughness Žaccording to the ASME B46. No changes have been observed in optical transmission after expo- . Relat. Superhard Mater. Sci. Doerner. 18 Ž3. Hoffman.N. S. 6. Dub. 593. Hayman. M. organic solvents and ultraviolet irradiation. w3x A. S. The MLC are characterized by a polycrystalline structure and have some disadvantages. 1564. Chem. S. Ge and Si are reported in w10x. J. r Diamond and Related Materials 10 (2001) 1846 ᎐ 1849 1849 sure of the MLC q DLC system to these environmental factors. Ge and GaAs. 969 Ž1989. R.. Soc.C. Fig. Scale: x . Ž1995. A. C. A. Mater. 5 Ž1994. w5x M.N.0 ␮ m.G.A. Doroshenko..V. Conclusions The possibility of improving the mechanical properties of MLC by DLC deposition has been studied.O. 9 Ž2000. Pethica. After DLC deposition.M. Oliver.