Solid-State Electronics 48 (2004) 19171920 www.elsevier.

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A microstructural study of the CdTe/ZnTe lm morphology as related to the Si substrate orientation

W.L. Sarney *, G. Brill
Sensors and Electron Devices Directorate, US Army Research Laboratory, AMSRD-ARL-SE-EI, 2800 Powder Mill Road, Adelphi, MD 20783 1197, USA Received 10 December 2003; accepted 15 March 2004

Abstract A series of CdTe/ZnTe lms was grown by molecular beam epitaxy (MBE) onto Si substrates. We examine the relationships between the lm morphology, the ZnTe growth method, and the Si growth orientation. The substrates degree of miscut from the [1 1 1] direction ranged from 0 to 29.5. Transmission electron microscopy (TEM) and X-ray diraction (XRD) studies show that the substrate orientation is maintained by the ZnTe/CdTe epilayers only for low miscut angles. For higher miscut angles, the lm orientation does not match that of the substrate, and in some cases is dependent on the growth methods used to deposit the ZnTe buer layer. Published by Elsevier Ltd.
PACS: 81.05.Dz; 81.15.Hi; 61.16.B; 61.72.M Keywords: CdTe; Si; Transmission electron microscopy (TEM); Molecular beam epitaxy (MBE)

1. Introduction We examine CdTe/ZnTe lms grown by MBE onto {1 1 l}-type Si surfaces that are miscut from the (1 1 1) plane. CdTe/ZnTe/Si can act as a substrate for further epitaxial growth of HgCdTe (MCT), which would allow the integration of MCT with Si-based readout electronics. CdTe and Si have lattice constants of 6.482 and 5.431  To alleviate the mismatch, a thin buer layer of ZnTe A.  is deposited onto the Si (with lattice constant of 6.103 A) substrate before the CdTe is grown. Prior experiments show that reducing the lattice mismatch helps to preserve the lms orientation with respect to the substrate [1] and reduce the dislocation density. Twinning is a common defect due to applied stresses within a crystal. A twinned region is the mirror image of the primary crystal. We characterize twins with TEM

Corresponding author. Tel.: +1-301-394-5761; fax: +1-301394-2233/0310. E-mail address: wsarney@arl.army.mil (W.L. Sarney). 0038-1101/$ - see front matter Published by Elsevier Ltd. doi:10.1016/j.sse.2004.05.036

diraction patterns and high resolution lattice images. Symmetric X-ray measurements can not detect twinning across planes perpendicular to the growth direction. For example, twinning over (1 1 1) planes in a crystal with a [1 1 1] growth direction would not be detected by symmetric X-ray scans, but would be detected in TEM diraction patterns. These types of twins, known as lamellar twins, do not distort the crystal along the growth direction. However, extra X-ray peaks do arise from twinning over planes not perpendicular to the growth direction. If a crystal has a sucient density of non-lamellar twinned regions, then the X-ray peaks from the primary crystal may be weaker and substantially broader than expected. Films were grown onto Si substrates having the following growth directions: [1 1 1], [1 1 2], [1 1 2] tilted 5 away from [1 1 1] (we denote this surface as (1 1 2)a), and [1 1 3]. Fig. 1 shows a ball and stick model, a schematic of the step/terrace prole, and a schematic of the diffraction pattern for each Si orientation. The tilt angle between the (1 1 1) plane and the growth plane ranges from 0 for Si(1 1 1) to 29.5 for Si(1 1 3). The step density of the Si surface increases with h (Fig. 1). Prior

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W.L. Sarney, G. Brill / Solid-State Electronics 48 (2004) 19171920

[111]

=0
[112 ]

111 220 002 11 1

[1 1 0]

(a)
[112]

[111]

exposed to a Te2 ux, resulting in a Te-polar growth front. The MEE process is a four step sequence that includes: exposing the surface to a Zn ux, a period of no ux, a period of Te ux, followed by another period of no ux. This sequence is repeated until the ZnTe layer is grown to the desired thickness. For the BC method a compound ZnTe source was used to simultaneously deposit Zn and Te.

= 19.5
(b)
[113]

002 111 220

11 1

3. Results and discussion Table 1 lists the growth orientation of the ZnTe/ CdTe lms relative to the Si substrate, as determined by TEM and X-ray. All lms grown onto Si(1 1 1) maintained the substrates orientation regardless of the growth temperature or ZnTe growth method. Fig. 2 is a high resolution image of the ZnTe buer layer (deposited with MEE at 320 C) grown on Si(1 1 1). These lms have a high degree of lamellar twinning in and near the buer layer. Symmetric X-ray scans would not detect these lamellar twins because the growth planes of both the twinned and untwinned regions are of the {1 1 1} type. According to X-ray measurements the FWHM of the (3 3 3) peak for this sample is 12200 . Fig. 3 shows the ZnTe/Si interface for a sample grown on Si(1 1 2). The ZnTe was deposited by MEE
Table 1 Si growth orientation [1 1 1] [1 1 2] Si[1 1 2] 5 tilted away from [1 1 1] Si[1 1 2] 5 tilted away from [1 1 1] Si[1 1 3] ZnTe coverage method MEE/BC MEE/BC MEE BC MEE/BC ZnTe/CdTe orientation [1 1 1] [1 1 2] [1 1 3] 1 towards [1 1 1] [1 1 1] 5 towards [0 0 2] [1 1 1] 5 towards [0 0 2]

[111]

= 29 .5

113 002 111 220

11 1

1 1 1 002

(c)
Fig. 1. Ball and stick model, step/terrace prole, and diraction pattern schematic for Si oriented along the (a) [1 1 1], (b) [1 1 2], and (c) [1 1 3] directions.

experiments show that the Te coverage on As-passivated Si surfaces increases with the number of edge atoms [2]. Models discussed in a previous study [3] suggest that the step-edge sites on the Si surface act as the absorption sites for Te (these sites remain non-passivated despite exposure to the As4 ux). Therefore, the Te coverage increases with the step density, which increases with the surface tilt angle.

2. Experimental procedure Before introduction into the ultra-high vacuum (UHV) MBE chamber, the Si substrates were chemically cleaned to remove the native oxide and then hydrogen passivated. The substrates were mounted onto a customized block designed to hold four 2 2 cm2 Si wafers. This allows the simultaneous growth of four lms onto dierently oriented Si surfaces while maintaining identical growth conditions. After the wafer is inserted into the UHV environment, the H-passivated surface was thermally removed and the exposed surface was Aspassivated. Samples were grown with ZnTe growth temperatures of 300 and 320 C and CdTe growth temperatures of 300, 320, 350, and 400 C (as measured from a backside mounted non-contact thermocouple). Past experiments show that the lm orientation is independent of the CdTe growth temperature [2]. The ZnTe layer was nucleated by either migrationenhanced epitaxy (MEE) [4] or blanket coverage (BC). Before initiating MEE the As-passivated Si surface is

Fig. 2. ZnTe buer layer with twins across the (1 1 1) plane.

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and the CdTe and ZnTe growth temperatures were 320 C. The lm has a [1 1 2] growth direction. There is a high density of dislocations and stacking faults near the Si interface, but most defects annihilate at the ZnTe/ CdTe interface or within the rst few nanometers of the CdTe lm. No twinning was evident by either TEM or X-ray. The FWHM of the (4 2 2) X-ray peak was 10300 . Samples with BC-grown ZnTe (not shown here) also had the [1 1 2] growth direction. The lm morphology of samples grown on Si(1 1 2)a was dependent on whether the buer layer was deposited by MEE or the BC method. The lm grown with the BC method is oriented along the [1 1 1] direction tilted 5 towards [0 0 2]. It contains a high density of dislocations and lamellar twins in and near the buer layer. It also contains a high density of twins over the non-growth {1 1 1}-type planes. The FWHM of the (3 3 3) peak is 40000 . The lm grown with MEE has a lower dislocation density and no evidence of twinning. The growth direction for the lm is [1 1 3] tilted 1 towards the [1 1 1] direction. The FWHM for the (1 1 3) peak is 15600 . Fig. 4 shows the diraction patterns for these two samples. The diraction pattern for the sample having a ZnTe buer layer grown with the BC method clearly shows several extra spots due to twinning across the (1 1  1) plane. Both samples were grown with ZnTe and CdTe growth temperatures of 300 C. Samples grown on Si(1 1 3) for ZnTe buer layers deposited with MEE or BC are morphologically similar. Both samples had ZnTe and CdTe growth temperatures of 300 C. In both cases the lm is oriented along the [1 1 1] direction tilted 5 towards the [0 0 2] direction. Fig. 5 shows the BC-grown ZnTe/Si interface for a sample grown on Si(1 1 3). Edge dislocations are evident in the high resolution image. The lm has a high density of twins that propagate through the ZnTe and CdTe

Fig. 4. Diraction patterns for CdTe/ZnTe lms grown on Si(1 1 2)a. The ZnTe buer layer was deposited by BC in (a) and MEE in (b).

Fig. 5. ZnTe/Si interface for a sample grown on Si(1 1 3). The ZnTe was deposited with the BC method.

regions (Fig. 6). The FWHM of the (3 3 3) peak was 112500 for the sample having the BC-grown buer layer, and 120000 for the sample having the MEE-grown buer layer. These peaks are considerably broader than those obtained for samples grown on the Si substrates of other orientations. Preliminary X-ray measurements show

Fig. 3. ZnTe/Si interface for a sample grown on Si(1 1 2).

Fig. 6. CdTe/ZnTe lm grown on Si(1 1 3). The ZnTe was deposited with the BC method.

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that samples with MEE-deposited buer layers and higher CdTe growth temperatures (between 350 and 400 C) have narrower (3 3 3) peaks. X-ray measurements from these samples also show the presence of the (3 3 3) peak and a (1 1 3) peak tilted 10 from the [1 1 1] direction. The (1 1 3) peak corresponds to the growth direction of the crystal within the regions that are twinned over the (1 1  1) plane. Further investigation is needed to understand why the lm growth direction is sensitive to the ZnTe growth process only for Si(1 1 2)a substrates. It has been observed that [1 1 1]-oriented lms tend to nucleate on high Miller index {1 1 l} Si substrates when the adatom diffusion is reduced [2]. Si(1 1 3) surfaces have the highest step densities amongst the surfaces examined in this study. Therefore, Si(1 1 3) surfaces have a high density of step-edge nucleation sites, which naturally limits adatom diusion. Si(1 1 2)a surfaces are only separated from Si(1 1 3) surfaces by 5. The BC method results in much higher coverage and faster nucleation rates than possible for MEE, which limits diusion. It is possible that adatom diusion on the (1 1 2)a surface is suciently limited for BC method, resulting in a (1 1 1)-oriented lm. In a future experiment we plan to lower the MEEgrowth temperature for ZnTe nucleation on Si(1 1 2)a

substrates to see if (1 1 1)-oriented lms are obtained. 4. Conclusion Our results show that the growth direction of the lm is maintained when grown onto lower index substrates. This is true regardless of the growth temperature or the growth method used for depositing the ZnTe layer. For higher tilt angles (Si(1 1 2)a and Si(1 1 3)) we nd that the lms do not have the same orientation as the substrate, and that in the case of the lm grown on Si(1 1 2)a, the lm orientation depends on the growth method used for the ZnTe buer layer. References
[1] Smith S-C, Tsen Y, Chandrasekhar D, Crozier PA, Rujirawat S, Brill G, et al. Mater Sci Eng, B 2000;77:93. [2] Brill G, Chen Y, Dhar NK, Singh R. J Electron Mater 2003;32:717. [3] Dhar NK, Boyd PR, Martinka M, Dinan JH, Almeida LA, Goldsman NJ. J Electron Mater 2000;29:748. [4] Dhar NK, Wood CEC, Gray A, Wei HY, Salamanca-Riba L, Dinan JH. J Vac Sci Technol B 1996;12:2366.