Reprinted from MATERIALS SCIENCE & — Materials Science anal Engoneering, A140 (1991 Ion-assisted deposition with a new plasma source K, Matl, W. Klug and A. Zoller R&D Deparment for Optical Coatings, Leybold AG. Slemenssraye 100, Ws Aiconm (FRG) ELSEVIERMATERIALS SCIENCE AND ENGINEERING A ‘The journal provides an international medium for the publication of theoretical and experimental studies and reviews of the properties and behavior of a wide range of materials, related both to their structure and to their engineering application. The varied topics comprising materials science and engineering are viewed as appropriate for publication: these include, but are not limited to, the properties and structure of crystalline and non-crystalline metals and ceramics, polymers and composite materials. [ASSOCIATE EDITORS (MSE A) A.J. Arsenault USA) Tlksmna open) T.Sakume (Japan) LH Bannatt (US.A) ¥.G. Kim Kore VK Sain USA) ©. Brandon (sree H. Kimura Wapant LL Seige USA) HK DH. Bhadeshis (UK) 6. 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U.S. and Canadian customers may obtain information from the following, Journal information Center Elsevier Science Publishers 155 Avenue of the Americas New York, NY 10010, US.A, Telephone [22| 633 3750 Telex: 420 669 AEP Ul Telefax: +1 (212) 699 3764 Abstracting and/or Indexing Services AMERICAN CERAMIC SOCIETY: CAMBRIDGE SCIENTIFIC ABSTRACTS; CHEMICAL ABSTRACTS; CURRENT CONTENTS; ENGINEERING INDEX; FIZ KARLSRUHE; GLASS TECHNOLOGY ABSTRACTS; METALS ABSTRACTS; PASCAL (Centre National do Ia Recherche Seientiique); INSPEC/PHYSICS ABSTRACTS: PHYSIKALISCHE BERICHTE; RESEARCH ALERT™; SCIENCE CITATION INDEX. Ma Tor K.n R&D mate with evap, Prop ones Fj the L ated (Ein and « inves tion ion s entra high ducin Pr soure neces 0921-3Mavrils Science and Engineering, A140 (1991) 523-527 33 Jon-assisted deposition with a new plasma source K. Matl, W. Klug and A. Zoller R&D Department for Optical Coatings, Leybold AG., Siemenssirae 1M, W-N7S5 Alzenau (FR.G) Abstract Ion-assisted deposition is a well-known technique to improve the properties of hin fi technology is the small useful substrate area compared to conventional evaporation. There- tage of s. One disadvan fore we have developed a new plasma source which is able to irradiate large substrate holders (1 m diameter) with a high plasma current density. The principle of operation and some details ofthe plasma source are described. The experiments were done in a conventional coating system. The pla hhas been operated up to 80 V discharge voltage and up to 70 A discharge current, For single layers of TiO, we have found two different modifications with refract lensity. The spectral curves exhibit no shift after keeping samples under water and after baking 50°C} 1. Introduction Thermal evaporation is the most commonly used process for the production of optical coat- ings. The struciure and the achieved properties of thermally evaporated thin films are quite different from the respective bulk material [1]. The typical columnar structure of many metals and oxides has been investigated by various authors [1, ‘The low packing density implies optical constants and mechanical properties such as adhesion and hardness which are inferior to those of the bulk material. Deposition processes using particles with higher kinetic energies than by thermal evaporation can improve the above-mentioned properties (3). lon-assisted deposition (IAD) is one such technique. Figure 1 shows the principle of operation of the IAD process. A growing thermally evapor- ated film is bombarded by an energetic ion beam (Eq 100-800 eV). A wide range of materials and completed layer systems has already been investigated by many laboratories (4-6). In addi- tion to the limited ion beam size of the available ion sources, they use hot filament cathodes and extraction grids with limited lifetime in the case of high emission currents and especially when intro- ducing oxygen into the ion source [7]. Previous investigations with conventional ion sources have shown that activated oxygen necessary for many coating materials in order to (0921-5093/91/83.50 indices of 2.37 and 2.6 with a high pack- get fully oxidized films with low absorption losses, and a high packing density. Because of the above-mentioned reasons, we have developed a new plasma source which is able to irradiate a large area substrate holder with a high current density. 2. Prineiple of operation of the plasma-IAD process For the plasma-IAD process one can use a standard box-coating system with conventional 1 AL, Ny Fi, 1. Schematic diagram ofthe IAD process ‘© Elsevier Sequoia/Printed in The Netherlands524 electron beam evaporators inside. A plasma source, which is located in the centre of the coat- ing chamber bottom, is directed to the substrate holder (Fig. 2). Inside the source there is a cylin- drical LaB, cathode surrounded by a cylindrical anode tube (50 mm diameter). One creates a glow discharge d.c. plasma witha hot electron emitter supplied with a noble gas, usually argon. A solenoid which surrounds the source causes the conductivity of the electrons creating the plasma to be strongly increased in the axial direc- tion of the source and strongly suppressed in the radial direction. The electrons spiral along the magnetic field lines and therefore the plasma is ‘extracted into the coating chamber. At the upper wall of the coating chamber above the substrate holder a ring-shaped magnetic coil with an inner diameter bigger than the diameter of the substrate holder is located. The magnetic fields from the solenoid and the ring magnet superimpose to a guiding field for the electrons from the cathode and the whole plasma between the plasma source and the substrate holder. It is possible to capture the plasma between the source and the substrate holder. in front of the substrate holder a plasma sheet is created. Because the potential of the sub- Strate holder is negative relative to the plasma potential, ions are extracted from the plasma sheet and bombard the growing film. One main advantage in comparison to conventional LAD with an ion source located. at the bottom of the coating chamber is that the ions which are accelerated over a small distance in the plasma sheet do not have to travel a long path to reach the substrate holder. Therefore the ions from the etn om tar Fig. 2. Schematie diggram ofthe plasma-IAD process, plasma sheet are not affected by scattering pro- cesses and energy losses. Furthermore, the plasma is extended in the whole area between the plasma source and the substrate holder, so in Principle the “ion source” covers the same area as the substrate holder. With a conventional ion source with grid extraction one needs nearly the same extraction grid area as the irradiated sub- strate area, The reactive gas is introduced directly into the coating chamber. Owing to the plasma inside the chamber it becomes partly ionized and activated. ‘The evaporated material also has to cross the plasma in front of the substrate holder, so that ionization and activation of the evaporant take place. The complete source is electrically isolated relative to the coating chamber. Besides the applied discharge voltage one gets a potential di ference between the source and the chamber. The source takes a positive floating potential relative to the chamber, while the substrate holder stays at nearly the same potential as the chamber. The ion energy will be determined, as well as the plasma potential, through the potential difference between the anode tube and the substrate holder, The floating potential of the source depends on the discharge voltage, the partial pressures of the ‘gas constituents and the strength of the magnetic field. Because of the positive floating potential, an electrical field is created which reflects the electrons between the source and the substrate holder. If they do not hit the anode tube, they will be reflected at the cathode potential and can ‘move again to the outside of the source and so on. One obtains oscillatory electron paths with an effective ionization and excitation of the gas atoms and molecules. Because of the repelling effect due to the electric fields near the anode, the plasma in front of the substrate holder is dominated by the ions. This can be seen from the floating potential of the substrate holder, which is typically 3-5 V with respect to the chamber wall. The achieved discharge parameters are up to 80 V discharge voltage, 70 A discharge current and 5 kW plasma power. The corresponding pressure range is (1-8) 10~* mbar with a ratio O,:r of up to 4:1. The operation of the source as a “reflex arc” source allows one to separate the plasma- creating process from the evaporation process. All starting materials such as oxides and fluorides can be evaporated, in contrast to ion-plating pro- ‘cesses used in this field.3. Experimental results The first investigations of the plasma-IAD process were done with single layers of TiO,. We obtained two different modifications of TiO, The spectral curves of the first modification are shown in Fig, 3. We obtained a refractive index of 2.37 at 550 nm. Figure 4 shows a scanning electron microscopy (SEM) picture of this modi fication, It demonstrates that the film is com- pletely amorphous. The transition between the substrate and the TiO, layer ean be made visible only after a chemical etching of the sample. The spectral curves of the second modification of TiO; that we obtained are shown in Fig. 5, For this modification the refractive index at 550 nm is 2.6. The SEM picture shows that the thin film is structured (Fig. 6). It is known that a conven- tionally electron-beam-gun-evaporated TiO. film exhibits a “columnar” structure (Fig. 7), The layer has a refractive index of 2.3. If one makes an ion- assisted deposition with a Kaufman-type ion 100.0 or ese Wavelength fom} 76a 860 Fig. 3. Singlesayer TiO; deposited with _plasma- (nssy=237, d=235 nm) transmittance ("5 =~, reflectance 525 beam source and increases the ion energy (E,oe=100-800 eV) and ion current, the columnar structure starts to disappear and the refractive index increases up to 2.5, while the film becomes amorphous (Fig. 8). A test method for s000 800 60.0 400 200 00. 00476 «672 668764 080 Wavelength trem Fig.S. Singlelayer TiO, deposited with plasma-LAD (n=26, d=300 nm: ——, transmittance ( felleetanes (%) Fit 6 Sielayer TO; deposted with plavme-tAD n= 2.6) $,Sodolyer THO, deposed with plama-t4D 7) Fig. 7. Single-layer TiO, deposited with conventional ectron beam gun evaporation526 Fig. 8, Single-lyer TIO, deposited with IAD. ‘Tranamitance 100.0 800 0 00 500. 360476672 668 768060 Wovelength [nm] Fig. 9. Single-yer TiO, electcon beam gun ev T= 300°C): water [2h ——— alter baki deposited with conventional the packing density and structural stability is to Keep the sample under water, eg. for 2h. A further test is to bake the sample, eg. at 250°C for 3h Figure 9 shows the transmission curves of a conventionally evaporated TiO; film with heated substrate during the deposition after keeping under water and after baking, The optical thick- ness was shifted by 2% after keeping under water and by 1.5% after baking, In the respective curves for the first modifica- tion of TiO, with a refractive index of 2.37 deposited with the plasma-IAD process there no shift visible in the transmission spectra (Fig. 10}. One gets the same result for the second modification with a refractive index of 2.6 (Fig. 11). The facts that the TiO, modification with a refractive index of 2.6 has a higher refractive index than that of a film manufactured with the Kaufman-type source and that the spectral curves do not show any shifts after keeping the sample Wavelength fom] 50°C ‘Tranamittance 1000 soo 00 700 00 100 am, ——, alter coating: keeping under water (2 hy ——— ater baking (3h, 250°C under water and baking show that the packing density is high and indicate a erystalline modifi tion, 4. Conclusions We have developed a new plasma source for plasma-IAH processes. The source can be operated with a plasma power of up to 5 kW ina stable reliable mode. The first coating results were very promising and have demonstrated the ability to produce dielectric layers with a high packing density. Future work will be focused on the examination of other evaporation materials standard in the production of optical thin films. Also, the production of alternating H-L layers and complete layer systems will be investigated in the future, References | HLA, Macleod, Microstructure of eptial thin films, Pro2 KH Guenther, D. J. Smi (1986) 2, 3 P.J. Marin and R. P, Neterfild, Optical films produced by ionbased techniques, in E.’Wolf (ed), Progress in Optics XXII, Elsevier, Amsterdam, 1986, Chapter 3. 4 PJ. Manin, H. A. Macleod, RP. Netefild, C. G. Pacey and W. G. Sainy, fon-beam-asisted deposition of thin films, Appl. Ope, 22(1983) 178-184, 5. J.D. Torgove, J.P-Lehan, LJ. Ling, M.A. Macleod, J. A. Learia and L. C. Melniyte, Jt, lon-asssted deposition of ‘and B, Liao, Proc. SPIE, 678 327 lanthanum Nuoride thin flms, Appl. Opt, 26(1987) 3733, F. Flory, C. Amra, M. Commandré, E. Pelletier and G. Albrand, Comparative study of ion techniques used to ‘manufacture optical coatings, Proc. In. Sp. on Optical Coatings, Shanghai, May 1989, International Academic Publishers. 134. H.R. Kaufmann, J.J. Cuomo and J, M. 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