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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

O.M. Kutsay et al. r Diamond and Related Materials 10 (2001) 1846 ᎐ 1849


2. Experimental

3. Results and discussion Optical transmission spectra were measured for initial MLC samples and after deposition of DLC films ŽMLC q DLC. onto them. After DLC film deposition, all optical elements retained their transparency values. The load ᎐ displacement curve of the MLC down to a depth of 50 nm is given in Fig. 1. In this case, mechanical properties of Y2 O 3 and underlying BaF2 films have been analyzed. The hard and brittle oxide film deposited onto soft BaF2 , has been destroyed by the indenter at a depth of 10 nm. Consequently, the indenter sharply descends to a depth of 30 nm and then penetrates into soft fluoride. Once failed, the oxide film does not affect indenter penetration. The low nanohardness Ž0.55 GPa. at a depth of 50 nm and the unloading curve shape point to this fact. The unloading curve demonstrates slight elastic recovery of the indent depth that is typical for such a soft material as BaF2 . The elastic recovery of oxide films is much greater. Thus, the protective properties of the Y2 O 3 films appear to be poor. The films fail even at a load of 0.005 mN. A DLC film deposited onto a MLC has significantly improved mechanical properties of the sample surface ŽFig. 2.. In this case, penetration to a depth of 50 nm requires 10 times higher loading. The nanohardness at this depth has increased to 3.6 GPa. Also, the essential increase of the indent depth elastic recovery has been observed during unloading. Almost all of the indenter displacement during the test is due to elastic deformation of the sample surface. 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. The dependence of nanohardness on indenter displacement is shown in Fig. 3. For the initial MLC sample, the nanohardness was approximately 0.5 GPa in the displacement range from 500 to 1000 nm. The

Electron-beam deposited polycrystalline ZnSer BaF2rY2 O 3 films were used as the MLC standard for comparison. Silicon and germanium wafers Žwhich are optically transparent in the IR region. were used as substrates. The thickness of the quarter-wave layers of ZnSe and BaF2 was approximately 2 ␮ m; the thickness of the protective Y2 O 3 layer was approximately 50 nm. DLC films from 50 to 100 nm in thickness have been deposited at low substrate temperatures Ž300 ᎐ 330 K. by plasma-enhanced chemical vapor deposition ŽPECVD. in the methane ᎐ hydrogen atmosphere. Bias voltage was y300 V and methane concentration varied in the range of 30 ᎐ 70 vol.% w3x. To measure the mechanical properties of multilayer coating, depth-sensing nanoindentation tests were used. Tests were performed on a Nano Indenter II device ŽMTS, USA. using a Berkovich indenter w4 ᎐ 6x. The Oliver and Pharr technique is the most widespread for the analysis of the load-displacement curve w7x. It allows one to find the average contact pressure ŽACP. in the indent ŽMeier hardness. only at peak loads. Nanohardness at the peak loads for MLC will average the values for layers having different properties. To measure nanohardness as a function of depth using the loading segment data, we applied the technique proposed in w8x. Measurements at a peak load of 120 mN allow us to study the mechanical behavior of MLC to a depth of approximately 2000 nm. Nanohardness tests performed at a minimal load of 0.3 mN Žat an indent depth of approx. 50 nm. give information on mechanical properties of the upper layer. The wear resistance tests were carried out according to the industrial requirements for optical coatings; 3000 revolutions of a rubber tip Žradius of a spherical surface of 3.0 mm. covered with a cambric cloth. Loading on the tip was 200 g. A Digital Instrument ŽUSA. atomic force microscope ŽAFM. was used to study variations of surface morphology in the MLC. The IR transmission spectra in the wavelength range of 2.5 ᎐ 20.0 ␮ m were recorded by a Carl Zeiss Specord M80 ŽGermany. spectrophotometer. The stability of MLC covered with a DLC film ŽMLC q DLC. under the action of climatic factors Ženhanced humidity, i.e. a relative humidity of 98% at 35 and 100ЊC; action time was 40 and 1 h, respectively., organic solvents Žacetone, toluene, carbon tetrachloride, isopropyl spirit boiling for 30 min. and ultraviolet irradiation Ža UV light flux of 60 Wrm2 power; irradiation time s 240 h. was assessed by comparing the optical transmission of the MLC q DLC sample before and after the tests.

Fig. 1. Load ᎐ displacement curve for MLC.


O.M. Kutsay et al. r Diamond and Related Materials 10 (2001) 1846 ᎐ 1849

Fig. 2. Load ᎐ displacement curves for MLC and MLC q DLC.

observed surface nanohardness increase is due to the influence of the Y2 O 3 film at a depth - 500 nm. At displacement greater than 1000 nm, the indenter begins to penetrate into the ZnSe layer, which is harder than the BaF2 layer. As a result, the nanohardness at a depth ) 1000 nm begins to increase. The DLC film deposition increases abruptly the hardness at a depth of - 500 nm. The influence of the DLC film is observed to the 1500-nm depth. At a greater depth, the nanohardness of the DLC-coated sample differs only slightly from that of the uncoated sample. 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, the characteristic X-ray radiation of Zn, Y and Ba was used. The YL ␣-radiation intensity profile for the 50-nm deep indent is evidence that the protective DLC coating prevents the MLC from being damaged. It is confirmed by the fact that at maximal loading Ž150 mN., DLC decreases the indent depth. The ZnK ␣-radiation from the bottom layer of ZnSe has not been detected. This fact confirms that the indenter destroys only the upper layers.

Fig. 4. Optical images of MLC and MLC q DLC surfaces after wear test: MLC q DLC Žtop.; and MLC Žbottom..

The results of the wear resistance tests are shown in Fig. 4. The surface of a sample with MLC q DLC Žthe top of the image. exhibits no mechanical damages even after increasing the total number of wearing tip revolutions up to 15 000. The traces of failure of the surface of MLC without a DLC film could be seen in Fig. 4 Žbottom of the image.. The failure of the MLC q DLC has been observed only after adding diamond micron powder Žgrain size s 2 ᎐ 3 ␮ m. to the contact zone. Even after processing by the micron powder, the MLC q DLC showed less mechanical damage than the MLC ŽFig. 5.. 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. The results of preliminary testing of these properties of the DLC-coated surface of the monocrystalline

Fig. 3. Hardness of MLC and MLC q DLC vs. displacement of the indenter.

Fig. 5. Optical images of MLC and MLC q DLC surfaces after wear test wdiamond micron powder Žgrain size s 2 ᎐ 3 ␮ m. in the contact zonex: MLC q DLC Žtop.; and MLC Žbottom..

O.M. Kutsay et al. r Diamond and Related Materials 10 (2001) 1846 ᎐ 1849


sure of the MLC q DLC system to these environmental factors. Surface morphologies of the MLC before and after DLC film deposition are shown in Fig. 6. The quantitative parameters of the roughness Žaccording to the ASME B46.1 standard. were obtained from statistical analysis of the frontal image for a scanning area of 5.0 = 5.0 ␮ m. After DLC deposition, the MLC rootmean-square ŽRMS. roughness was reduced from 30 to 20 nm. This is indicative of the ability of DLC films to reduce the roughness of a polycrystalline surface.

4. Conclusions The possibility of improving the mechanical properties of MLC by DLC deposition has been studied. Multilayer coatings are necessary for parts made of materials with high refraction indices ŽSi, Ge and GaAs. to increase optical transparency. Considerable improvement of MLC mechanical properties Žincreased combined nanohardness of the coatings from 0.5 to 3.6 Gpa. whilst retaining their optical characteristics, could be achieved by DLC film deposition.

Acknowledgements This work was supported by the Science and Technology Center in Ukraine ŽSTCU project no. 1356.. The authors thank P.V. Lytvyn for AFM images of sample surfaces. References
w1x J.C. Angus, C.C. Hayman, R.W. Hoffman, Proc. Soc. Photo-Opt. Instrum. Eng. 969 Ž1989. 2. w2x N. Savvides, Mater. Sci. Forum 52r53 Ž1989. 407. w3x A.G. Gontar, A.A. Doroshenko, A.M. Kutsay, S.I. Khandozhko, J. Chem. Vapor Deposition 4 Ž1. Ž1995. 15. w4x J.B. Pethica, R. Hutchings, W.C. Oliver, Phil. Mag. A. 48 Ž1983. 593. w5x M.F. Doerner, W.D. Nix, J. Mater. Res. 1 Ž1986. 601. w6x E. Soderlund, D.J. Rowcliffe, J. Hard Mater. 5 Ž1994. 149. w7x W.C. Oliver, G.M. Pharr, J. Mater. Res. 7 Ž1992. 1564. w8x N.V. Novikov, S.N. Dub, Yu.V. Milman, I.V. Gridneva, S.I. Chugunova, J. Superhard Mater. ŽAllerton Press Inc. New York. 18 Ž3. Ž1996. 32. w9x N.V. Novikov, M.A. Voronkin, S.N. Dub et al., Diam. Relat. Mater. 6 Ž1997. 574. w10x N.V. Novikov, A.G. Gontar, S.I. Khandozhko et al., Diam. Relat. Mater. 9 Ž2000. 792.

Fig. 6. AFM images of MLC surfaces: initial Ža. and with a DLC film Žb. Scale: x , y s 0.2 ␮ mrdiv; and z s 100.0 nmrdiv.

Ge and Si are reported in w10x. The MLC are characterized by a polycrystalline structure and have some disadvantages, such as porosity and low stability to the environmental influence. Thus, 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. For this purpose, we have examined the MLC q DLC samples exposed to enhanced humidity, organic solvents and ultraviolet irradiation. No changes have been observed in optical transmission after expo-