Infrared Physics & Technology 52 (2009) 204207

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Infrared Physics & Technology

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

Characterization and application of cerium uoride lm in infrared antireection coating

Wei-tao Su a,*, Bin Li b, Ding-quan Liu b, Feng-shan Zhang b
a b

Institute of Material Physics, Hangzhou Dianzi University, 310018 Hangzhou, China Shanghai Institute of Technical Physics, Chinese Academy of Sciences, 200083 Shanghai, China

a r t i c l e

i n f o

a b s t r a c t
Cerium uoride (CeF3) thin lms were evaporated to the germanium substrates at different substrate temperature from 100 C to 250 C. Structural and optical properties were characterized by X-ray diffraction (XRD), scan electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The morphology of samples deposited at different temperature can be closely related to preferred orientation. The infrared optical constants were obtained by tting the transmission spectrum using Lorentz oscillator model. A simple example for fabrication of long-wave infrared broadband antireection coating was also presented. 2009 Elsevier B.V. All rights reserved.

Article history: Received 14 October 2008 Available online 24 July 2009 PACS: 78.30.Hv 78.20.Ci 78.20.Bh Keywords: CeF3 thin lm Morphology Infrared optical properties Broadband antireection coating

1. Introduction High quality broadband antireection coatings are required to reduce the surface reectivity for optical components used in the long-wave infrared up to 15 lm [1]. Some material properties, such as refractive index, weak absorption in long-wave infrared, good physical bonding compatibility and chemical stability, are essential to infrared coating materials. However, the design and deposition of long-wave broadband antireection coating have usually been limited because of the selection of coating materials, especially the low refractive index materials [1,2]. In the past two decades, more and more attentions have been paid to the rare earth uorides, such as LaF3 [36], PrF3 [7], YbF3 [5,6], YF3 [3,5,6,8]. CeF3 is an excellent uoride with a transparent range from visible to deep ultra violet (DUV) due to its large band gap [5,9]. CeF3 has a P 3C 1 crystal structure like LaF3 [7], which make it transparent up to 15 lm or even longer in the infrared. Although some physical properties of CeF3 have been investigated [36], the structural and infrared optical properties, in particular, the optical constants up to 15 lm have not been reported. In this paper, the structure and optical properties of CeF3 thin lms were investigated. An application of CeF3 into long-wave infrared broadband antireection coatings was also present in the experiment.
* Corresponding author. Tel.: +86 571 86919037; fax: +86 571 86919032. E-mail address: suweitao622@163.com (W.-t. Su). 1350-4495/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.infrared.2009.07.008

2. Experiments Granular CeF3 with purity of 99.99% was used as source material for deposition on Ge (1 1 1) substrates. Prior to deposition, the base pressure in chamber was pumped down to 3 103 Pa using an oil diffusion pump. The deposition rate was kept at about 2.5 nm per second, and the substrate temperature was changed from 100 C to 250 C. All thin lms have an identical optical thickness of 3.6 lm. The crystallographic structure of the thin lms were identied using D/max 2550 V X-ray diffractometer from 20 to 80 with step of 0.02 (Cu Ka1, k = 1.5406 ). The infrared transmission spectra were measured using Fourier transform infrared spectrometer (PerkinElmer GX90) from 5000 cm1 to 500 cm1 with spectrum resolution of 4 cm1. The surface and cross-section morphology of thin lms were measured on Hitachi S-4800 and Sirion 200 scanning electron microscope (SEM), respectively. The optical constants of CeF3 thin lms were calculated by tting the transmission spectrum using classical Lorentz oscillator model.

3. Results and discussions The XRD patterns of CeF3 thin lms deposited at different temperature are shown in Fig. 1. All thin lms show crystalline structure with different preferred growth orientation. The lms

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205

1400 1200 1000 800 600 400 200 0 3000 2500 2000 1500 1000 500 0 3000 2500 2000 1500 1000 500 0 3000 2500 2000 1500 1000 500 0 20

250C

Ge(111)

Table 1 Calculated lattice parameters of CeF3 lms deposited at different substrate temperature.

(110)

(211)

Temperature (C)

a () 7.1283 7.1188 7.1261 7.1236 7.114

(221)

ea (%)
0.2 0.06 0.17 0.13

c () 7.2493 7.3592 7.3679 7.4088 7.273

ec (%)
0.32 1.18 1.3 1.86

100 150 200 250 Standard (JCPDS-#721436)

200C

a
30 40 50 60 70 80

2theta ()
Fig. 1. XRD spectrum of CeF3 lms deposited at different substrate temperature: (a) 100 C; (b) 150 C; (c) 200 C and (d) 250 C.

deposited at 100 C and 150 C show apparent (2 1 1) preferential orientation. For lm deposited at 200 C, a weak peak

corresponding to (1 1 0) emerges, while the intensity for (2 1 1) peak is comparably strong. For the lm deposited at 250 C, it shows apparently (1 1 0) orientation, while the intensity for other peaks is comparably very weak. Preferred growth orientation will also lead to the different surface morphology, which will be discussed in the following. In Table 1, the crystal cell parameters are obtained based on the results from XRD. One can nd that all obtained value of a and c are larger than those of bulk material, which indicates there are tensile stress in all the samples. If the depositing temperature increases from 100 C to 250 C, the strain of a do not change apparently, while the strain of c increases from 0.32% to 1.86%, which indicates the tensile stress in thin lms also increases with the increase of deposition temperature. Moreover, ne cracks in tens of nanometer could be found in all of the samples, which are not shown in this paper. The shape and density of micro-cracks are dependent on depositing temperature. Further understanding of the microcrack and tensile stress is difcult for lacking of mechanical parameters. The surface morphology of CeF3 thin lms is shown in Fig. 2. The lms below 200 C are composed of irregular granular in the size of about 100 nm. These granular are indeed stacking up by much tinier layered particulates. All of the irregular granular and

100C

150C

Fig. 2. Surface SEM images of CeF3 lms deposited at different substrate temperature: (a) 100 C; (b) 150 C; (c) 200 C; (d) 250 C.

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Fig. 3. Cross-section SEM image of CeF3 lms deposited at different substrate temperature: (a) 150 C; (b) 250 C.

70
100C 150C 200C 250C

60

50

40

30

20 2 4 6 8 10 12 14 16 18 20

Wavelength (m)
Fig. 4. Infrared transmission spectrum of CeF3 lms deposited at different substrate temperature.

layered particulates grow up with the increase of deposition temperature. The lms deposited at 250 C, as shown in Fig. 2d, are composed by completely square granular in the size of about 50 nm, and it is much denser than those deposited at lower substrate temperature. The difference in surface morphology for the lms deposited at different temperature could be connected with preferred orientation. Thin lms deposited 100 C, 150 C and 200 C have (2 1 1) preferred orientation, while those deposited at 250 C keep (1 1 0) orientation. Different orientations may lead to different surface morphology. The cross-section images for the thin lms deposited at 150 C and 250 C are shown in Fig. 3. There are few apparent voids, which indicate the evaporated lms are much denser. Further study nds

the column size of thin lms deposited at 250 C is much smaller, which is compatible with the result from surface morphology. From (Figs. 2 and 3), it can be found that CeF3 thin lms deposited at 250 C have a better crystallographic structure and are much denser. The infrared transmission spectra of CeF3 lm deposited at different temperature are measured and shown in Fig. 4. The water absorption peaks located approximately at 3 lm and 6 lm are presented in all of the spectra, which are linked to the water incorporated in the voids of the lm because CeF3 does not dissolve in water. With the increasing of depositing temperature, the density of the lms is enhanced and the voids shrink, which lead to an alleviation of water absorption. For the lms deposited at 250 C, the water absorption peaks apparently dwindle owning to the improvement of the structural quality. The absorption beyond the spectral range of 10 lm can be due to the infrared lattice vibration absorption. In order to investigate its absorption in long-wave infrared region, the optical constants of CeF3 thin lms are extracted by tting the infrared transmission spectra using classical Lorentz oscillator model [7,10,11]. The refractive indices and extinction coefcients are shown in Fig. 5a and b, respectively. The enhanced density in thin lms leads to the increase of refractive index, which is conrmed by the results of the lms deposited at different temperature. The refractive index of CeF3 thin lm is about 1.2 at 15 lm when 5% calculation error is considered. The 0.5% measure error for the transmission will give 1020% error for the calculation of extinction coefcient at 15 lm. The extinction coefcient of CeF3 lms is about 0.05 at 15 lm while the error is 0.01. An example that CeF3 thin lms are applied into the manufacture of long-wave infrared broadband antireection is presented. CeF3 was used as low index materials (L) and a SUB/M H M L M/ AIR system was used as the initial design. Germanium and zinc sulphide were used as high (H) and middle (M) index material,

Transmission (%)

a 1.6
Refractive index
1.5 1.4 1.3 1.2 1.1 1.0 2 4 6 8 10 12 14

Extinction coefficient

100C 150C 200C 250C

b 0.08
0.06

100C 150C 200C 250C

0.04

0.02

0.00 16 2 4 6 8 10 12 14 16

Wavelength ( m)

Wavelength ( m)

Fig. 5. Infrared optical constants of CeF3 lms deposited at different substrate temperature: (a) refractive index; (b) extinction coefcients.

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207

100 90

Transmission (%)

80 70 60 50 40 30 6 7 8
As designed As measured

stants, which were obtained by tting the transmission spectrum using Lorentz oscillator model, indicated that the refractive index and extinction coefcient at 15 lm are about 1.2 and 0.05, respectively. An example of application of CeF3 into fabrication of longwave infrared broadband antireection coating has also been presented. Acknowledgements This work is supported by the National Natural Science Foundation of China (NSFC) (Grant No. 60678058) and Science Foundation of Zhejiang Education Committee (Grant No. Y200804801). References

Wavelength (m)

10

11

12

13

14

15
[1] H.A. Macleod, Optical Thin Film Filters, second ed., Adam Hilger Ltd., Bristol, 1986. [2] C. Cole, Broad Band Antireection Coatings for Spaceight Optics, Ph.D. Dissertation, University of Reading, 1990. [3] S.F. Pellicori, E. Colton, Fluoride compounds for IR coatings, Thin Solid Films 209 (1992) 109. [4] D. Smith, P. Baumeister, Refractive index of some oxide and uoride coating materials, Appl. Opt. 18 (1) (1979) 111. [5] L.J. Lingg, Lanthanide triuoride thin lms: structure, composition, and optical properties, Ph.D. Dissertation, University of Arizona, 1990. [6] J.D.T. Kruschwitz, W.T. Pawlewicz, Optical and durability properties of infrared transmitting thin lms, Appl. Opt. 36 (10) (1997) 2157. [7] Wei-tao Su, Bin Li, Ding-quan Liu, Feng-shan Zhang, Texture evolution and infrared optical properties of praseodymium uoride lms, Opt. Mater. 30 (2) (2007) 273. [8] D.F. Bezuidenhout, K.D. Clarke, R. Pretorius, The optical properties of YF3 lms, Thin Solid Films 155 (1987) 13. [9] H. Uhlig, R. Thielsch, J. Heber, N. Kaiser, Lanthanide tri-uorides: a survey of the optical, mechanical and structural properties of thin lms with emphasis of their use in the DUV-VUV-spectral range, in: Proceedings of the SPIE, 5963(2006), 59630 N-1. [10] E.D. Palik, Handbook of Optical Constants of Solids, rst ed., Academic Press, Orlando, 1985. [11] D. Poelman, P.F. Smet, Methods for the determination of the optical constants of thin lms from single transmission measurements: a critical review, J Phys. D: Appl. Phys. 36 (2003) 1850.

Fig. 6. Designed and measured transmission spectrum of the 6.515 lm broadband antireection coating composed by CeF3 lms.

respectively. The designed transmission curve is shown in Fig. 6. The absorption is also considered for all the coating materials in the design procedure. The transmission of this simple antireection coating is about 88% at 13 lm and 78% at 15 lm, which is also shown in Fig. 6. The deterioration of measured transmission can be due to the unstable deposition parameters and the absorption of germanium substrate. 4. Conclusions CeF3 thin lms were deposited on germanium substrate at different substrate temperature. It is found that the deposition temperature could change structural and optical properties notably. The thin lm deposited at 250 C shows (1 1 0) preferred growth orientation and denser microstructure, which differs from those deposited at lower substrate temperature. The infrared optical con-