Infrared Physics & Technology 52 (2009) 193195

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Infrared Physics & Technology

journal homepage: www.elsevier.com/locate/infrared

Design and fabrication of ultra broadband infrared antireection hard coatings on ZnSe in the range from 2 to 16 lm
Yongqiang Pan a,b,*, Lingxia Hang a, Zhensen Wu b, Yongbai Yin c
a

Shaanxi Province Thin Film Technology and Optical Test Open Key Laboratory, Xian Technological University, Xian 710032, China School of Science, Xidian University, Xian 710071, China c Applied Physics Group, Physics School, University of Sydney, UNSW 2006, Australia
b

a r t i c l e

i n f o

a b s t r a c t
In conventional infrared multilayer antireection coatings (MLAR) materials of uoride and chalcogenide types are used, which are disadvantaged due to their low mechanical strength and poor stability against humidity and environmental impacts. In this paper, we show that high performance ultra broadband and hard infrared multilayer antireection coatings on ZnSe substrates in the wavelength range from 2 to 16 lm can be designed and fabricated. Diamond-like carbon (DLC) hard coating as a mechanical and environmental protection layer was proposed and deposited onto MLAR surfaces (MLAR + DLC) using a pulsed vacuum arc ion deposition technique. The thickness of the high optical quality DLC can be optimized in the design simulation to achieve a practically best antireection and surface protection performance. We show that a germanium thin lm (15 nm) between the MLAR and DLC surfaces can be used as a transition layer for optical and material match. The average transmission of the fabricated MLAR+DLC surfaces was 93.1% in the wavelength range between 2 and 16 lm. The peak transmission was about 97.6%, close to the simulated values. The durability and stability against mechanical impacts and environmental tests was improved signicantly compared with the conventional infrared windows. 2009 Elsevier B.V. All rights reserved.

Article history: Received 10 May 2009 Available online 18 July 2009 Keywords: Diamond-like carbon (DLC) lm Multilayer antireection (MLAR) coatings Zinc selenide (ZnSe) Ion beam assisted deposition (IBAD) Infrared broadband windows

1. Introduction Zinc Selenide is a material widely used in optical transmission applications for windows, lenses and prisms in the range from 0.6 to 16.5 lm. The refractive index of this material is about 2.42 with a very low absorption coefcient. This material is particularly useful in high power density infrared laser optical circuitry. Due to its relatively high refractive index, however, the transmission windows and lenses using Zinc Selenide need an antireection layer [1,2] to increase the transmission. Materials of infrared multilayer antireection coatings for optical components include commonly uorides (PbF2, ThF4, BaF2), chalcogenides (Sb2S3, ZnSe, PbS), oxides (TiO2, ZrO2, Y2O3), and germanium (Ge). It is known that chalcogenides and especially uorides do not have sufcient mechanical strength with very poor environmental durability. Multilayer antireection (MLAR) coatings using these materials require upper protective layers to improve the mechanical stability. Oxide lms have better mechanical properties but typically have very high absorption in the infrared region from 2 to 16 lm, which is a serious concern
* Corresponding author. Address: Shaanxi Province Thin Film Technology and Optical Test Open Key Laboratory, Xian Technological University, Xian 710032, China. Tel.: +86 29 83208006; fax: +86 29 83208210. E-mail address: pyq_867@163.com (Y. Pan). 1350-4495/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.infrared.2009.07.006

in design a high performance infrared antireection components. Though germanium has a very low absorption in the infrared region, its refractive index is rather high thus it cannot be used along or as an upper protection layer. New materials for overcoming above disadvantages of the conventional MLAR are demanded. Diamond-like carbon (DLC) lm offers an alternative for the protective layers [37]. The concept proposed in this work to use a DLC lm as a protective layer of MLAR coatings is attractive considering the possibility of varying its refractive index and other physical and chemical properties over a wide range of wavelength [811]. The aim of this work to investigate the possibility of obtaining a high performance optimized optical design and to show the fabrication feasibility of achieving the designed performance by including the DLC protection layer on the top of MLAR coatings.

2. Theory and design Antireection coatings to enhance transmission in infrared region often require a complicated coating design of multilayers [12,13] as well as very low absorption coefcient of antireection coating materials. For simple applications with narrow wavelength range without requiring high performance transmission, theoretical and practical solutions are well established. For example, when an antireection coating is required for a single wavelength only,

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one can simply use a single-layer reection coating or a V-coating. For a broadband antireection coating, the W-coating [12] method may be used. However, the W-coating method cannot easily satisfy the requirements for high performance broadband antireection coating designs. The antireection coating design are more and more complicated and particularly more and more challenging or impossible in fabrication of the complicated designs as the requirements of the performance become increasingly higher and higher in order to meet the demands of applications [14]. In such high performance designs, a renement procedure in design simulation typically converges to a local minimum near a starting design and cannot reach its true optimized structure of the targeted multilayers. The W-coating method can provide a good solution to the problem only if a good starting design is known. In many cases, a non-local design method, known as the needle technique proposed by Tikhonravov [15], is necessary. In this method a thin or needle layer of material is systematically inserted between layers and the performance merit is calculated after each insertion. The process is repeated until any insertion of a needle layer does not reduce further the merit function. However, while the method may give a good or excellent solution, it cannot be easily fabricated or is practically impossible as the excellent solution may contain a large number of layers and large total thickness. Considering the design trade-off of total lm thickness, the number of layers, and the choice of coating materials one needs to reduce the coating complexity and fabrication cost without compromising signicantly the performance. Fig. 1 shows two simulated transmission spectra of a 7-layer MLAR coatings on ZnSe substrate in 216 lm wavelength region using the needle method for single-side coated (dashed curve) and double-side coated (solid curve) surfaces, respectively. The design of the MLAR coating is ZnSe substrate/YF3/ZnSe/YF3/ZnSe/YF3/ ZnSe/YF3/air. The physical thickness of this MLAR coating is 2346 nm. The merit function is equal to 1.926. In the design simulation process, we found that the merit function could be less than 1.926, but the number of layers and the total thickness would increase signicantly. For example, when a 11layer design was reached, the total physical thickness was 3246 nm while the merit function was 1.611. Therefore, the 7-layer MLAR design was fabricated and analysed in this work and shown in this paper below by considering the technological feasibility and simplicity. Fig. 2 shows the simulated transmission spectra with a DLC lm coated on MLAR and using Ge lm as transition layer for refractive index match between the soft MLAR and hard DLC layers. The design was optimized by selecting a 15 nm thick Ge transition layer.

Fig. 2. Optimized simulated transmission curves of MLAR + DLC coatings on ZnSe substrate.

ion beam

substrate

shutter ion source

PVAID setup pump EB gun

Fig. 3. Schematic diagram of the MLAR + DLC coating deposition system.

Fig. 1. Optimized theoretical transmission curves of MLAR coatings on ZnSe substrate.

Fig. 4. Measured transmission spectra of MLAR and MLAR + DLC coatings and ZnSe substrate.

Y. Pan et al. / Infrared Physics & Technology 52 (2009) 193195 Table 1 Environmental and durability tests. Sample # DLC thickness (nm) Test Adhesion Abrasion Temperature cycle Humidity Test specication 1 pull by scotch tape 40 rubs by cheese cloth 4 h each at 40 3 C and 50 3 C 24 h; 96 1% (RH); 48 2 C 1# 0 2# 30 3# 50 Ok Ok Ok 4# 80 Ok Ok Ok

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5# 100 Ok Ok Ok Ok

The thickness of the DLC lm was 100 nm. The structure of the optimized design is ZnSe substrate/YF3/ZnSe/YF3/ZnSe/YF3/ZnSe/ YF3/Ge/DLC/air. 3. Experimental details Fig. 3 shows schematically the customer-designed optical coating system. The system was equipped with a broad beam cold cathode ion source, which enabled the system to operate at the ion beam assisted deposition (IBAD) mode. The design of the cold cathode ion source was reported previously [16]. The ZnSe substrates were discs of 25 mm in diameter and 3 mm in thickness. Prior to the deposition, the substrates were bombarded using Ar+ ions for 10 min to improve the adhesion and surface quality. The ZnSe, YF3 and Ge layers were deposited using an electron beam evaporator with the IBAD with Ar+ ion energy of 800 eV and current density of 0.1 mA/cm2. DLC lm was deposited using a pulsed vacuum arc ion deposition (PVAID) set-up in the deposition chamber. Film thickness was monitored during deposition using both the extreme values of interference method and the quartz crystal thickness monitoring technique. The base vacuum pressure and operating pressure were 4.0 103 Pa and 1.0 102 Pa, respectively. The substrates were two-axis rotated during deposition to improve the uniformity. The temperature of substrates was maintained at 200 C during the deposition using a radiant heater at the backside of the substrate holder. Infrared transmission spectra were measured using a P.E. Fourier transform infrared (FTIR) spectroscopy in the wavenumber range from 400 to 4000 cm1. 4. Results and discussion A 2.346 lm thick ultra broadband IR multilayer antireection (MLAR) coating and a 1.712 lm thick MLAR + DLC hard coating were fabricated. The antireection coatings were deposited onto double sides of 3 mm thick ZnSe substrates. Fig. 4 shows the measured transmission spectra in the infrared range. The average transmission of the MLAR and MLAR + DLC coatings were 93.4% and 93.1%, respectively, in the wavelength range from 2 to 16 lm (or wavenumber range 5000625 cm1). The maximums at wavenumbers equal 4960 cm1, 3720 cm1, 2480 cm1 and 1230 cm1 were above 97.6%, close to the simulated values. The optical performance of the two coatings was similar. Consider that the total thickness of the MLAR + DLC was signicantly less (about 30% thinner), the MLAR + DLC design is practically preferred. The results of the mechanical and environmental durability tests are summarized in Table 1. The sample of 1# is the MLAR

coating sample (no DLC). The samples 2#, 3#, 4# and 5# are MLAR + DLC coatings (with Ge transition layer) as a function of DLC thickness. The result shows that by adding 100 nm DLC onto MLAR coatings we can achieve excellent protective effect against the mechanical impacts and environmental tests.

5. Conclusions We proposed to use DLC material as a protective layer for ultra broadband infrared antireection applications. Ultra broadband (216 lm) infrared multilayer antireection surfaces on ZnSe substrate with a DLC protective-coating layer (MLAR + DLC) were designed and fabricated. We showed that the MLAR + DLC surface could be optimized by adding a thin (100 nm) layer of DLC via a transition layer (15 nm) of Ge and that the total thickness of the antireection coatings was reduced signicantly. The optical performance of the fabricated broadband infrared transmission MLAR + DLC windows was close to the simulated result. The mechanical and environmental durability properties of the MLAR + DLC surfaces were improved signicantly. Acknowledgment The authors acknowledge nancial support by the National Natural Science Foundation of China (No. 60878032). References
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