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# Symmetry Analysis of ZnSe(100)/Air Interface By Second Harmonic Generation

## I INTRODUCTION

Optical Second Harmonic Generation(SHG) has matured to be an effective surface- and interface-sensitive technique for probing a large variety of surface- and interface-properties. This technique is a non-destructive. It can be used for in-situ measurements in almost any environment, provided that we have optical access to the sample . The method bases on the idea that generally a surface and a bulk have different structural symmetry. Materials with inversion symmetry, such as Si- and Ge- single crystals have no bulk electric-dipole contribution. Electric quadrupole and magnetic dipole contributions originate the leading source in SHG from the bulk. However, a surface or an interface breaks the inversion symmetry and produces an electric-dipole contribution. Generally the SHG-intensity from a surface or an interface can be compared to be much greater than that from the bulk, depending on the material, the photon energy, and the geometry of the experiment. On the other hand, noncentrosymmetric materials like crystals with the zincblende structure as, e.g. the compound semiconductors GaAs and ZnSe, have intense bulk electric-dipole contributions to the SHG, thus hampering surface observations. Stehlin et al  illustrated possible combinations of the polarization of incident and SHG output light and of crystal azimuths for which only the surface contribution may be deduced for typical low index surface, e.g. (001), (110), and (111) and used SHG as effective surface probe with submonolayer sensitivity to monitor the adsorption of Sn on GaAs(001) surface. Later, S. R. Armstrong et al  investigated by means of SHG a GaAs(100)/air interface. Similar experiments performed by C. Yamada and T. Kimura  firstly observed the twofold rotational angledependence (rotation anisotropy) of SHG in the reflected light from a well prepared and by RHEED characterised noncentrosymmetric single crystal surface of GaAs(100). They interpreted it as the interference of surface SHG and dipole-allowed bulk SHG having fourfold symmetry results in twofold anisotropy, whereby the degree of rotational anisotropy monitors the surface reconstruction. Galeckas et al  showed that SHG in reflection is a sensitive and practical method to invesigate the departure from perfect crystalline ofder at the surface by studying the SHG rotational anisotropy of crystalline, polycrystalline and amorphous silicon carbide surfaces. Bottomley et al  determined to within $`\pm 0.1^{}`$ the orientation of vicinal GaAs(001) and Si(111) single crystal wafers using second and third harmonic generation. M. Takebayash et al  demonstrated the SHG-measurement of the tilt angle $`\theta `$ of the crystallographic axis of a vicinal GaAs(100) wafer towards a direction $`\xi `$ that characterises step direction and step height and forms an angle $`\psi `$ with respect to -axis and found that the $`s`$-incident polarization is useful in the determination of this tilt angle. C. Jordan et al  used the azimuthal rotational anisotropy of the SHG for in-situ finger print characterisation of various polytypes of SiC and compared with X-ray diffraction (XRD) and identify defect regions in big samples by observating the spatially resolved dependence of the SH-intensity.

In recent years, there has been big interest in wide-band gap II-VI compound semiconductors. In particular, ZnSe is being actively studied due to their electroluminescent properties in blue-light-emitting laser diodes \[Haase\]. These devices are fabricated by epitaxial growth on GaAs substrates. The replacement of GaAs substrates by ZnSe ones may decrease the concerntration of defects and increase the lifetime of the device. This can be one possible way to improve ZnSe-based laser characteristics. An recent observation in ZnSe/ZnCdSe laser diodes grown onto ZnSe substrates indicates that the growth rate of the defects is much smaller than for layers grown onto GaAs substrates . For the successful growth of II-VI epilayers onto ZnSe layers is very importment to have well ordered substrate surfaces. However, the superiority of ZnSe substrates over GaAs one has not been realised yet, mainly because it is difficult to obtain high-quality ZnSe substrates.

SHG has been successfully applied to the study of semiconductor surfaces semiconductor/semiconductor heterostructures and interfaces, and semiconductor-oxide interfaces

and provides a powerful tool for understanding the energetics of various defect formations and surface reconstructions. Although these experiments have been performed mostly for GaAs surface  or SiC surface , similar symmetric studies were not extend to many other non-centrosymmetric materials, such as ZnSe.

In this paper, we have measured the SH intensity from ZnSe(100) as a function of the light polarization and as a function of the azimuthal angle. We have also calculated the intensity of SHG from the surface electric dipoles and the the second-order nonlinear polarization arising from the bulk response. We use optical SHG to determine the macroscopic symmetry properties of the ZnSe(100)/air interface. The remainder of the paper is organized as follows. In Sec. II, the theory for SHG in reflection from the bulk and surface of nonsymmetric crystals is briefly introduced. Then the experimental apparatus is described in Sec. III, and finally the results are analyzed in terms of symmetry.

## II THEORY

### A General

We can express the induced nonlinear surface polarization at an interface in the following manner:

$$𝐏_{eff}(2\omega )=𝐏_{surf}+𝐏_{bulk}F(\omega )F(2\omega )L_{eff},$$
(1)
where $`F(\omega )`$ and $`F(2\omega )`$ are the Fresnel factors for the incident input and output fields, and $`L_{eff}=(W+2w)^1`$ is the effective phase-matching distance of the substrate with $`W=k_{\omega ,z}`$ and $`2w=k_{2\omega ,z}`$ representing the $`z`$ component of the wave vectors of the fundamental and SH light, resepectively, $`𝐏_{surf}`$ is the surface nonlinear polarization of the interfacial layer, and $`𝐏_{bulk}`$ is the bulk nonlinear polarization in medium.

The bulk nonlinear polarization can generally be expressed by a series of multipole terms:  :

$$𝐏_{bulk}(2\omega )=𝐏^{(2)}(2\omega )𝐐^{(2)}(2\omega )+\frac{c}{2i\omega }\times 𝐌^{(2)}(2\omega ),$$
(2)
where $`𝐏^{(2)},𝐐^{(2)},`$and $`𝐌^{(2)}`$ describe the electric-dipole polarization, electric-quadrupole polarization and magnetic-dipole polarization respectively. Up to the first derivative in $`𝐏_{eff}^{(2)}`$, the three polarization sources are the following:

$$𝐏^{(2)}(2\omega )=\chi ^D:E(\omega )E(\omega )+\chi ^P:E(\omega )E(\omega ),$$
(3)
$$𝐐^{(2)}(2\omega )=\chi ^Q:E(\omega )E(\omega ),$$
(4)
$$𝐌^{(2)}(2\omega )=\chi ^M:E(\omega )E(\omega ).$$
(5)
We neglect $`𝐌`$ and higher-order multipole in our discussion here, because these contributions are thought to be orders of magnitude smaller than the electric dipolar contribution. The second terms in eq. (2) and (3) arises from the gradient of the field $`E(\omega )`$. Since the penetration depth in crystals ($``$100Å) is much smaller than the spatial variation of the field ($``$10,000Å for optical frequencies), this bulk contribution is small under nonresonant conditions.

The surface contribution of the SH field arises from two effects. First, at the interface between the dissimilar media, inversion symmetry is broken for centrosymmetric crystals and symmetry is changed for noncentrosymmetric crystals, and so a dipolar contribution to SHG can exist. In addition, there is a discontinuity in the fundamental electric field normal to the surface. This can generate a sizable SH contribution through higher-order multipole terms. So the surface contribution to the nonlinear polarization can be expressed as:

$$P_{surf}^{(2)}(2\omega )=\chi ^D:E(\omega )E(\omega )+\chi ^D:E(\omega )E(\omega )\chi ^Q:E(\omega )E(\omega ).$$
(6)
Since the tangential components of the incident electric field are continuous across the interface, all terms in eq. (6) involving a gradient that can be neglected when describing an in-plane surface response and only the first term should be considered:

$$P_{surf}^{(2)}(2\omega )=\chi ^D:E(\omega )E(\omega ).$$
(7)
If the nonlinear susceptibilities are all defined in terms of the input field $`𝐄(\omega )`$, in the interfacial layer by $`𝐏(\omega )=\chi ^{(2)}:E(\omega )E(\omega )`$, then from (2), the corresponding effective surface nonlinear susceptibility is given by

$$\chi _{eff}^{(2)}=\chi _{surf}^{(2)}+\chi _{bulk}^{(2)}L_{eff}F(\omega )F(2\omega ),$$
(8)
where $`\chi _{surf}^{(2)}`$ and $`\chi _{bulk}^{(2)}`$ are the surface and bulk nonlinear susceptibility tensors, respectively. The tensorial properties of $`\chi _{eff}^{(2)}`$ can be exploited as: if the SH intensity is recorded as a function of azimuthal angle of rotation, the variation in intensity reflects the overall symmetry of the surface of interface.

A tensorial expression for the second-order polarization can be written as:

$$\left(\begin{array}{c}P_x(2\omega )\\ P_y(2\omega )\\ P_z(2\omega )\end{array}\right)=\left(\begin{array}{cccccc}\chi _{xxx}& \chi _{xyy}& \chi _{xzz}& \chi _{xyz}& \chi _{xxz}& \chi _{xxy}\\ \chi _{yxx}& \chi _{yyy}& \chi _{yzz}& \chi _{yyz}& \chi _{yxz}& \chi _{yxy}\\ \chi _{zxx}& \chi _{zyy}& \chi _{zzz}& \chi _{zyz}& \chi _{zxz}& \chi _{zxy}\end{array}\right)\times \left(\begin{array}{c}E_x(\omega )E_y(\omega )\\ E_y(\omega )E_y(\omega )\\ E_z(\omega )E_z(\omega )\\ 2E_y(\omega )E_z(\omega )\\ 2E_x(\omega )E_z(\omega )\\ 2E_x(\omega )E_y(\omega )\end{array}\right),$$
(9)
This is the general expression describing the interaction of the two EM driving fields being coupled throuth a dyadic product.

### B Bulk contribution

We now define a new set of coordinates $`(\widehat{𝐱}^{},\widehat{𝐲}^{},\widehat{𝐳}^{})`$ for each of the three crystal orientations such that $`z`$ axis is perpendicular to each crystal face. For the (111) crystal face, we therefore have, in terms of the standard crystal axes $`(\widehat{𝐱},\widehat{𝐲},\widehat{𝐳})`$

$$\left(\begin{array}{c}\widehat{𝐱}^{}\\ \widehat{𝐲}^{}\\ \widehat{𝐳}^{}\end{array}\right)=R_1\left(\begin{array}{c}\widehat{𝐱}\\ \widehat{𝐲}\\ \widehat{𝐳}\end{array}\right)=\left(\begin{array}{ccc}2/\sqrt{6}& 1/\sqrt{6}& 1/\sqrt{6}\\ 0& 1/\sqrt{2}& 1/\sqrt{2}\\ 1/\sqrt{3}& 1/\sqrt{3}& 1/\sqrt{3}\end{array}\right)\left(\begin{array}{c}\widehat{𝐱}\\ \widehat{𝐲}\\ \widehat{𝐳}\end{array}\right),$$
(10)
where the new $`\widehat{𝐱}^{}`$ axis is projected on to the original crystal $`\widehat{𝐱}`$ axis in the plane of the crystal surface, and $`(\widehat{𝐱},\widehat{𝐲},\widehat{𝐳})`$ represents the principal-axis system of the crystal (, , ). For the (100) face we simply choose the $`\widehat{𝐱}`$ axis to lie normal to the surface, the transformation matrix can be expressed by

$$R_1=\left(\begin{array}{ccc}0& 1/\sqrt{2}& 1/\sqrt{2}\\ 0& 1/\sqrt{2}& 1/\sqrt{2}\\ 1& 0& 0\end{array}\right),$$
(11)
and for the (110) face crystal

$`R_1=\left(\begin{array}{ccc}1/\sqrt{2}& 1/\sqrt{2}& 0\\ 0& 0& 1\\ 1/\sqrt{2}& 1/\sqrt{2}& 0\end{array}\right).`$

We can define a set of unit vectors for the incident light beam $`\widehat{𝐬},`$ $`\widehat{𝐤},`$and $`\widehat{𝐳}`$ such that $`\widehat{𝐬}`$ and $`\widehat{𝐤}`$ lie on the crystal face, perpendicular and parallel to the plane of incidence, respectively, and $`\widehat{𝐳}=\widehat{𝐳}^{}`$ is the surface normal,

$$\left(\begin{array}{c}\widehat{𝐬}\\ \widehat{𝐤}\\ \widehat{𝐳}\end{array}\right)=R_0\left(\begin{array}{c}\widehat{𝐱}\\ \widehat{𝐲}\\ \widehat{𝐳}\end{array}\right)=\left(\begin{array}{ccc}\mathrm{sin}\varphi & \mathrm{cos}\varphi & 0\\ \mathrm{cos}\varphi & \mathrm{sin}\varphi & 0\\ 0& 0& 1\end{array}\right)\left(\begin{array}{c}\widehat{𝐱}\\ \widehat{𝐲}\\ \widehat{𝐳}\end{array}\right).$$
(12)
Here $`\varphi `$ is the angle between $`\widehat{𝐤}`$ and $`\widehat{𝐱}`$, the azimuthal angle.

In many of the experiments, the single surface is rotated about its azimuthal angle $`\varphi `$ and the SH response is analyzed with respect to the beam coordinates. Therefore, one needs to transform $`\chi ^{(2)}`$ from crystal coordinates into beam coordinates, as shown in figure 1, with the appropriate transformation operations. The transformation rule for third rank tensors is the following:

$$\chi _{ijk}=\underset{l,m,n}{}R_{il}R_{jm}R_{kn}\chi _{lmn},$$
(13)
where $`R=R_0R_1`$ is the transformation operator from the crystal $`(\widehat{𝐱},\widehat{𝐲},\widehat{𝐳})`$ to beam $`(\widehat{𝐬},\widehat{𝐤},\widehat{𝐳})`$ coordinates.

Wide-gap zinc-blende II-VI semiconductors with symmetry $`T_d(\overline{4}3m)`$ are optically isotropic, but do not possess a center of inversion. The bulk second-order susceptibility tensor has only one component, $`\chi _{xyz}=\chi _{yzx}=\chi _{zxy}=d`$. Using the rule in Eq. (13), this tensor for the (100) face in beam coordinates can be written as

$$\chi _{bulk}^{(2)}(\varphi )=\left(\begin{array}{cccccc}0& 0& 0& \mathrm{sin}(2\varphi )d& \mathrm{cos}(2\varphi )d& 0\\ 0& 0& 0& \mathrm{cos}(2\varphi )d& \mathrm{sin}(2\varphi )d& 0\\ \mathrm{cos}(2\varphi )d& \mathrm{cos}(2\varphi )d& 0& 0& 0& \mathrm{sin}(2\varphi )d\end{array}\right),$$
(14)
and for (111) face we have

$$\chi _{bulk}^{(2)}(\varphi )=\left(\begin{array}{cccccc}\sqrt{\frac{2}{3}}\mathrm{sin}(3\varphi )d& \sqrt{\frac{2}{3}}\mathrm{sin}(3\varphi )d& 0& 0& d/\sqrt{3}& \sqrt{\frac{2}{3}}\mathrm{cos}(3\varphi )d\\ \sqrt{\frac{2}{3}}\mathrm{cos}(3\varphi )d& \sqrt{\frac{2}{3}}\mathrm{cos}(3\varphi )d& 0& d/\sqrt{3}& 0& \sqrt{\frac{2}{3}}\mathrm{sin}(3\varphi )d\\ d/\sqrt{3}& d/\sqrt{3}& 2d/\sqrt{3}& 0& 0& 0\end{array}\right).$$
(15)
The components of the fundamental field in the medium expressed in the beam coordinate axes are

| $`E_st_s,`$ |
| --- |
| $`E_k=f_cE_pt_p,`$ |
| $`E_z=f_sE_pt_p,`$ |

(16)
where $`f_{c,s}`$ are the Fresnel factors and $`t_{s,p}`$ are the linear transmission coefficients for the fundamental field, given by

$$f_s=\frac{\mathrm{sin}\theta }{n(2\omega )},f_c=(1f_s^2)^{1/2},t_s=\frac{2\mathrm{cos}\theta }{\mathrm{cos}\theta +nf_c},t_p=\frac{2\mathrm{cos}\theta }{n\mathrm{cos}\theta +f_c},$$
(17)
with $`f_c`$ taken such that Im $`f_c0,`$ and Re $`f_c0`$ if Im $`f_c=0`$; $`n(\omega )`$ is the complex refractive index of the medium in which the beam is propagating. $`\theta `$ is the angle of the beam propagation in this medium. For the SH field, the coressponding $`F_{s,}F_c,T_s,T_p`$ are similar with refractive index $`N(2\omega )`$ of SH light.

Through combining Eq. (9) and Eqs. (14)-(17), one obtains the second-order polarization from the (100) face crystal,

$`P_s^{bulk}`$ $`=`$ $`2d[\mathrm{sin}(2\varphi )f_cf_st_p^2E_p^2\mathrm{cos}(2\varphi )f_st_pt_sE_pE_s],`$ (18)
$`P_k^{bulk}`$ $`=`$ $`2d[\mathrm{cos}(2\varphi )f_cf_st_p^2E_p^2+\mathrm{sin}(2\varphi )f_st_pt_sE_pE_s],`$ (19)
$`P_z^{bulk}`$ $`=`$ $`d[\mathrm{cos}(2\varphi )t_s^2E_s^2\mathrm{cos}(2\varphi )f_c^2t_p^2E_p^22\mathrm{sin}(2\varphi )f_ct_pt_sE_pE_s],`$ (20)
and for the (111) crystal,

$`P_s^{bulk}`$ $`=`$ $`\sqrt{{\displaystyle \frac{2}{3}}}d[\mathrm{sin}(3\varphi )t_s^2E_s^2\mathrm{sin}(3\varphi )f_c^2t_p^2E_p^2+2(\mathrm{cos}(3\varphi )f_c+\sqrt{2}f_s)t_pt_sE_pE_s],`$ (21)
$`P_k^{bulk}`$ $`=`$ $`\sqrt{{\displaystyle \frac{2}{3}}}d[t_s^2\mathrm{cos}(3\varphi )E_s^2+(\sqrt{2}f_cf_s\mathrm{cos}(3\varphi )f_c^2)t_p^2E_p^22\mathrm{sin}(3\varphi )f_ct_pt_sE_pE_s],`$ (22)
$`P_z^{bulk}`$ $`=`$ $`{\displaystyle \frac{d}{\sqrt{3}}}[t_s^2E_s^2(f_c^22f_s^2)E_p^2].`$ (23)
The SH fields generated by polarization are decomposed into s- and p-polarized components,

$`E_s^{bulk}=A_s\mathrm{\Omega }L_{eff}P_s^{bulk}`$

and

$$E_p^{bulk}=A_p\mathrm{\Omega }L_{eff}[F_sP_z^{bulk}F_cP_k^{bulk}]$$
(24)
where $`\mathrm{\Omega }=2\omega /c`$ is the magnitude of the wave vetor of the SH light. $`A_s`$ and $`A_p`$ (given in Ref. ) are independent of the angle of rotation, but are dependent on the incident angle and the optical frequency through a change in the index of refraction. The SH intensity is propotional to the absolute square of $`E(2\omega )`$, which for either s- or p-polarized pump beam, from (100), (110) and (111) face crystals are found from Table I (only the bulk susceptibility is included).

TABLE I. The second-harmonic field for bulk contibution    (100) face  $`E_{p,s}=2d\mathrm{\Omega }L_{eff}f_cf_st_p^2\mathrm{cos}(2\varphi )A_sE_p^2`$  $`E_{p,p}=d\mathrm{\Omega }L_{eff}f_ct_p^2(2f_sF_cf_cF_s)\mathrm{cos}(2\varphi )A_pE_p^2`$  $`E_{s,s}=0`$  $`E_{s,p}=d\mathrm{\Omega }F_sL_{eff}t_s^2\mathrm{cos}(2\varphi )A_pE_s^2`$  (110) face  $`E_{p,s}=\frac{1}{2}d\mathrm{\Omega }L_{eff}[(3\mathrm{cos}(2\varphi )1)f_c^22f_c^2]\mathrm{cos}(\varphi )A_sE_p^2`$  $`E_{p,p}=d\mathrm{\Omega }L_{eff}[3\mathrm{cos}^2\varphi f_c^2F_cf_s^2F_c+2f_cf_sF_s]\mathrm{sin}(\varphi )A_pE_p^2`$  $`E_{s,s}=3d\mathrm{\Omega }\mathrm{cos}\varphi \mathrm{sin}^2\varphi A_sE_s^2`$  $`E_{s,p}=\frac{1}{4}d\mathrm{\Omega }L_{eff}F_c[\mathrm{sin}\varphi 3\mathrm{sin}(3\varphi )]A_pE_s^2`$  (111) face  $`E_{p,s}=\sqrt{\frac{2}{3}}d\mathrm{\Omega }L_{eff}f_c^2t_p^2\mathrm{sin}(3\varphi )A_sE_p^2`$  $`E_{p,p}=\sqrt{\frac{1}{3}}d\mathrm{\Omega }L_{eff}[\sqrt{2}f_c^2F_c\mathrm{cos}(3\varphi )+f_c^2F_s2f_cf_sF_c2f_sF_s]t_p^2A_pE_p^2`$  $`E_{s,s}=\sqrt{\frac{2}{3}}d\mathrm{\Omega }L_{eff}t_s^2\mathrm{sin}(3\varphi )A_sE_s^2`$  $`E_{s,p}=\sqrt{\frac{1}{3}}d\mathrm{\Omega }L_{eff}[\sqrt{2}F_c\mathrm{cos}(3\varphi )F_s]t_s^2A_pE_s^2`$

The SH intensity is proportional to the absolute squre of $`E(2\omega )`$. Figure 2 shows the rotation-angle dependence of the SH intensity $`P_{in}S_{out}`$ for singular ZnSe(100) and ZnSe(111) with only the bulk suscetptibility. For ZnSe(100), the SH intensity distribution shows a fourfold symmetry, but for ZnSe(111) a full sixfold symmetry.

### C Surface or Inrerface Contribution

The surface or interface nonlinear susceptibility $`\chi _{surf}^{(2)}`$ is a third rank tensor with 27 elements, which reflect the symetry of the interface. For SHG the last two indices may be permuted at will, thus, the nonlinear susceptibility tensor may have a maximum of 18 independent nonvanishing elements( e.g. $`C_1`$), and higher symmetries lead to a reduction in the number of independent and nonvanishing tensor elements. Table II summarizes the results for the form of the surface nonlinear susceptibility tensor $`\chi _{surf}^{(2)}`$ for various symmetry classes.

TABLE II. Independent nonvanishing elements of $`\chi _{surf}^{(2)}`$ for continuous  point group for a surface in the $`\widehat{𝐱}\widehat{𝐲}`$ plane. Where mirror planes exist,  one of them is assumed to lie perpendicular to the $`\widehat{𝐲}`$-axis.  Point Group  Nonvanishing independent tensor elements    $`C_11`$  xxx,xyy,xzz,xyz=xzy,xzx=xxz,xxy=xyx,yxx,yyy,yzz,yyz=yzy,    yzx=yxz,yxy=yyx,zxx,zyy,zzz,zyz=zzy,zzx=zxz,zxy=zyx  $`C_sm`$  xxx,xyy,xzz,xzx=xxz,yyz=yzy,yxy=yyx,zxx,zyy,zzz,zxz=zzx  $`C_22`$  xyz=xzy,xxz=xzx,yxz=yzx,yzy=yyz,zxx,zyy,zzz,zxy=zyx  $`C_{2v}mm2`$  xxz=xzx,yyz=yzy,zxx,zyy,zzz  $`C_33`$  xxx=-xyy=-yxy=-yyx,yyy=-yxx=-xxy=-xyx,    xxz=xzx=yyz=yzy,zxx=zyy,xyz=xzy=-yxz=-yzx,zzz  $`C_{3v}3m`$  xxx=-xyy=-yxy=-yyx,xzx=xxz=yzy=yyz,zxx=zyy,zzz  $`C_44,C_66`$  xxz=xzx=yyz=yzy,zxx=zyy,xyz=xzy=-yxz=-yzx,zzz  $`C_{4v}4mm`$  xxz=zxx=yzy=yyz,zxx=zyy,zzz  $`C_{6v}6mm`$  xxz=zxx=yzy=yyz,zxx=zyy,zzz

We use the symble $`\chi _{xyz}^{surf}`$ to denote the surface(dipolar) second-order susceptibility, and $`P_{x,y,z}^{surf}`$ for surface polarization, e.g.,

TABLE III. Rotation-angle dependences of the second-order susceptibility tensor  components for different symmetry.    Surface Tensor elements $`P_{in}P_{out}`$ $`P_{in}S_{out}`$ $`S_{in}P_{out}`$ $`S_{in}S_{out}`$  symmetry (100) face xyz a cos$`(2\varphi )`$ cos$`(2\varphi )`$ cos$`(2\varphi )`$    (111) face xyz a cos$`(3\varphi )`$ sin$`(3\varphi )`$ cos$`(3\varphi )`$ sin$`(3\varphi )`$  $`C_{4v},C_{6v}`$ xxz=yyz,zzz isotropic      zxx=zyy isotropic  isotropic   $`C_{3v}^b`$ xxx cos$`(3\varphi )`$ sin$`(3\varphi )`$ cos$`(3\varphi )`$ sin$`(3\varphi )`$  $`C_3^b`$ xxx cos$`(3\varphi )`$ sin$`(3\varphi )`$ sin$`(3\varphi )`$ sin$`(3\varphi )`$   yyy sin$`(3\varphi ),`$sin$`\varphi `$ cos$`\varphi `$ cos$`(3\varphi ),`$sin$`\varphi `$ cos$`(3\varphi ),`$cos$`\varphi `$  $`C_{2v}`$ zxx+zyy isotropic  isotropic    xxz+yyz isotropic      xxz-yyz sin$`(2\varphi )`$ sin$`(2\varphi )`$     zxx-zyy sin$`(2\varphi )`$  sin$`(2\varphi )`$    zzz isotropic     $`C_s^b`$ xxx,xyy,yyx cos$`(3\varphi ),`$cos$`\varphi `$ sin$`(3\varphi ),`$sin$`\varphi `$ cos$`(3\varphi ),`$cos$`\varphi `$ sin$`(3\varphi ),`$sin$`\varphi `$   xxz,yyz cos$`(2\varphi )`$ sin$`(2\varphi )`$     xzz cos$`\varphi `$ sin$`\varphi `$    $`C_1^b`$ xxx,xyy,yyx cos$`(3\varphi ),`$cos$`\varphi `$ sin$`(3\varphi ),`$sin$`\varphi `$ cos$`(3\varphi ),`$cos$`\varphi `$ sin$`(3\varphi ),`$sin$`\varphi `$   yyy,xyy,yyx sin$`(3\varphi ),`$sin$`\varphi `$ cos$`(3\varphi ),`$cos$`\varphi `$ sin$`(3\varphi ),`$sin$`\varphi `$ cos$`(3\varphi ),`$cos$`\varphi `$   xyz,yxz sin$`(2\varphi )`$ cos$`(2\varphi )`$     zxy sin$`(2\varphi )`$  sin$`(2\varphi )`$    xzz sin$`\varphi `$ sin$`\varphi `$      a Only the bulk susceptibility is included.  b The isotropic terms are not shown.

$$P_x^{surf}=\chi _{xyz}^{surf}E_yE_z,etc.,$$
(25)
in the $`(x,y,z)`$ system. The transformation rule Eq. (13) is used to transfer the tensor $`\chi _{xyz}^{surf}`$ from crystal coordinates to beam coordinates $`\chi _{skz}^{surf}`$. Following Sipe , the SH field induced by the sheet of polarization can be written as

| $`E_s^{surf}=A_s\mathrm{\Omega }P_s^{surf},`$ |
| --- |
| $`E_p^{surf}=A_p\mathrm{\Omega }[F_s\epsilon (2\omega )P_z^{surf}F_cP_k^{surf}],`$ |

(26)
where $`\epsilon (2\omega )`$ is the dielectric constant at frequency $`2\omega `$.

We assume for simplicity that the surface has a simple unreconstructed structure, and thus for a particular face it has the same symmetry as the bulk. Therefore we use $`C_{3v}`$ symmetry for the (111) surface and $`C_{4v}`$ symmetry for the (100) face . In fact, there exist many local microscopic structures, even in a nominally single surfaces, and in such cases, the microscopic symmetry of the structures, such as monoatomic steps, etc. would allow some specific tensor element to exist. That is, we may observe a lower symmetry than expected if the newly introduced tensor is of different symmetry. Table III summarizes the results in cases where surface susceptibility is presented.

From Table III, we see that there are always plural tensor elements which cause the same rotational symmetry. Therefor, the determination of the relevant tensor elements must depend on other sources of information, which may be obtained experimentally. Note that because SHG is described by a third rank tensor, all surface symmetries higher than $`C_{3v}`$ yield an isotropic response.

## III EXPERIMENTAL METHODS

The experimental setup for SHG measurement is shown in Fig. 3. The light source of the fundamental frequency is a picosecond mode-locked Nd:YAG (yttrium aluminum garnet) laser (Light Conversion Ltd. EKSPLA 2143A) with light pulses of wavelength 1.06$`\mu `$m, duration time 20 ps, and repetion rate 10 Hz. The linear polarization of the fundamental beam is rotated to the desired angle by the combination of the half wave plate ($`\lambda /2`$) and the input Glan-Taylor polarizer prism P1. The polarized beam is focused into a spot of 3 mm diameter on the sample surface at an incident angle of $`45^{}`$. In order to avoid damaging the sample, the pulse energy was set to about 0.5-0.3mJ per pulse throughout the experiment. The visible-cut filter F1 situated immediately before the sample surface removes the visible light component, especailly SH signals which are generated in the preceding polarizer and lens. The reflected fundamental beam and the SH signal from the surfaceare are collinear beyond the sample surface, and the former is eliminated from the beam by an IR-cut filter F2 and an interference filter F3 (Melles Griot 03FIB008, $`\lambda =550`$ nm, FWHM=70 nm). The linear polarization of the SH signal to be measured by the detection system was selected by rotation of the analyzer P2. The signal was finally detected by a photomultiplier (Hamamatsu R1464). About 4% of the reflected laser beam is directed through the reference arm containing a crystalline quartz plate. The SH intensity from quartz plate can be used for providing a reference to remove laser intensity fluctuations.This signal is detected by another photomultiplier (Hamamatsu R928) through an interference filter F3. Both electronics signals from the two PMT outputs were fed into a BOXCAR (SRS 250) averaged over 50 pulses and then recorded using a computer.

The ZnSe(100) and ZnSe(111) crystals grown by the Markov method were commericailly purchased from Ma Teck Material Technologie & Kristalle GmbH, Germany . Their surfaces are chemical and mechanically polished. The samples were mounted on a rotation stage, with the surface normal set parallel to the rotating axis of the stage and could be rotated freely.

## IV RESULTS AND DISCUSSION

In Figure 4(a)-(d), the intensity from ZnSe(100) is shown as a function of the azimuthal orientation for the four different polarization combinations: $`P_{in}P_{out},P_{in}S_{out},S_{in}P_{out},S_{in}S_{out}`$. All experiments were made under the same conditions which makes it possible to compare the intensities of the different combinations. Fig. 4(a) \[Fig. 4(b)\] displays the the $`p`$\- \[$`s`$-\]polarized SH intensity $`I_{pp}`$ \[$`I_{sp}`$\] with $`p`$-\[$`s`$-\] polarizedincident light, whereas Fig. 4(c) \[Fig. 4(d)\] shows the $`s`$-polarized SH intensity $`I_{ps}`$ \[$`I_{ss}`$\] with $`p`$-\[$`s`$-\] polarized incident light. All plots clearly exhibit twofold symmetry. It seems to be consistent with a $`C_s`$ symmetry. A more detailed analysis of the experimental reuslts (see below) shows the interference of the surface $`C_s`$ symmetry with the underlying $`C_{4v}`$ symmetry of the ZnSe(100). The data for the four cases are fit by the trigonometric function square plus a constant, this small constant can be due to light at other frequencies leaking through the filters. We might be able to obtain relative values for the surface and bulk contributions if the function of the incident angle multiplying the different surface and bulk contributions would change significantly with $`\theta `$ (see Eq. (17) and TABLE I ). However, with the experimental conditions used here, changing from normal to grazing incidence decreases $`f_c`$ and $`F_c`$ by $`5\%,`$ whereas $`f_s`$ and $`F_s`$ remain small. Hence any attempt to seperate bulk and surface contribution by the use of this method seams to be inappropriate. It is for this reason that in all experiments a fixed angle of incidence of $`45^{}`$ was used.

For simplicity we concentrate on the $`s`$-polarized SHG response for an $`s`$-polarized pump beam, becuase this signal only contains anisotropic terms and will be most sensitive for the surface symmetry. This conclusion arises because the bulk contribution is forbidden, as seen in Table III. According to , for the (100) face, we see that the surface in general has $`C_{4v}`$ symmetry. However, such a mechanism should lead no $`\varphi `$-angle dependence. Even though we replace the symmetry$`C_{4v}`$ with lower symmetry $`C_{2v}`$, we cannot obtain any $`\varphi `$-angle dependent signal. Thus we must allow the effective symmetry of the surface to lower from $`C_{2v}`$ to $`C_s`$, corresponding to the observed symmetry of the rotation angle dependence. From Table III, for $`C_s`$ symmetry only the following components of surface or interface nonlinear susceptibility do not vanish

$$\chi _{xxx},\chi _{xyy},\text{and }\chi _{yxy}=\chi _{yyx}.$$
(27)
And a similar experssion for the $`S_{in}S_{out}`$ case is derived as

$$E_{s,p}(2\omega )/E_s^2(\omega )A_p\chi _{xxx}\mathrm{sin}^3\varphi (\chi _{xyy}+2\chi _{yyx})\mathrm{sin}\varphi \mathrm{cos}^2\varphi .$$
(28)
The solid line in Fig. 4(d) is a least-squares fit of SHG intensity to the data, from which we obtain the ratio

$$\frac{\chi _{xxx}}{\chi _{xyy}+2\chi _{yyx}}=0.276,$$
(29)
the agreement with experimental reuslt justifies our choice of $`C_s`$ symmetry. There is a large scatter in the data for $`S_{in}S_{out}`$ polarization combination, because its absolute SH intensity is small, thus we cannot obtain a complete fit to every data point in this configuration. In Ref. , value of $`\chi _{xxx}\mathrm{}(\chi _{xyy}+2\chi _{yyx})=1.10`$ was obtained from the NaCl(100)-air interface. This difference is not surprising given the fact that the absorption depth in the oxide layers of the NaCl(100) is more that of ZnSe(100) in our experiment.

This $`C_s`$ symmetry may be caused by (1) the interface between oxide absorbate and sample , (2) a nonideal cut of the crystal, the domain formation with different symmetry axis . When one only consider the bulk susceptibility, $`\varphi `$ dependence for $`S_{in}S_{out}`$ is very sensitive to the miscut angle of the crystal axis, even its absolute SH intensity is very small. If we consider that the surface tensor elements $`\chi _{xxx},\chi _{xyy},`$and $`\chi _{yxy}`$ have relevance to the miscut angle of ZnSe(100) crystal, which is less than $`0.5^{}`$ , the response of $`S_{in}S_{out}`$ is determined to be more than an order of magnitude smaller than other corresponding cases . C. Yamada and K. Kimura  found it was very difficult to measure $`S_{in}S_{out}`$ rotational-angle dependence because the signal was poor under UHV condition. However, we observed that the output was about half of the other cases. So we concluded that in our experiment the interface plays an impoartant role for producing the anisotropic in $`S_{in}S_{out}`$ configuration. This is supported in part by similar measurements made for GaAs(100) surfaces contaminated with carbon and oxygen which revealed a high degree of anisotropy in the SHG signal . The anisotropiy cannot be ascribed to any particular surface symmetry. One possible explanation may be suggested: the anisotropy may arise due to variations in oxide layer thickness which could be regarded as generating a stepped buried ZnSe(100)/oxide layer interface.

For three configurations ($`P_{in}P_{out}`$, $`S_{in}P_{out}`$, $`P_{in}S_{out}`$), the SHG intensity distribution shows a $`C_{4v}`$ symmetry if we only consider the bulk susceptibility. Further, we notice that the oxide layer interface would lower the effective symmetry of the surface from $`C_{4v}`$ to $`C_{2v}`$. In Fig 4.(a)-(c), we observe twofold symmetries not fourfold for three configurations, which is the result of interference of bulk SHG with surface SHG. Threfore, the observed rotation-angle dependence can be described as

$$I_{s.p}\left|A+B\mathrm{cos}(2\varphi )+C\mathrm{sin}(2\varphi )\right|^2,$$
(30)
where $`A`$ represents the isotropic surface contribution, $`B`$ is the bulk dipole term and $`C`$ the surface anisotropic term. We least-square fitted the observed rotation-angle dependence for three configurations by Eq. (30) with $`A,`$ $`B`$ and $`C`$ used as adjustable parameters. These fitting parameters are summarized in Table IV for the SHG data. As shown in Fig. 4(a)-(c), the fit was satisfactory.

TABLE IV. Values obtained for fitting parameters in Eq. (30)

| Configuration |  | A |  | B |  | C |
| --- | --- | --- | --- | --- | --- | --- |
| $`P_{in}P_{out}`$ |  | -0.034 |  | 0.203 |  | 1.201 |
| $`P_{in}S_{out}`$ |  | 0.046 |  | 1.200 |  | -0.126 |
| $`S_{in}P_{out}`$ |  | 0.062 |  | 0.039 |  | 1.150 |

In the $`P_{in}P_{out}`$ combination (Fig 5.), the peak at $`\varphi =135^{}`$ is higher than that at $`\varphi =45{}_{}{}^{},`$ and the peak at $`\varphi =315^{}`$ is higher than that at $`\varphi =225{}_{}{}^{}.`$ These diffrences arise from the interference between the isotropic surface SHG and the bulk SHG. The signs of the nonlinear susceptibility components for the exciting electric fields in the (011) and (0$`\overline{1}`$1) planes are opposite. This is because the bulk Zn-Se-Zn-Se- chain along the  has Zn atoms higher than Se atoms and Zn-Se-Zn-Se- chain alone \[0$`\overline{1}`$1\] has Se atoms higher than Zn atoms. This phase difference of $`180^{}`$ between the electronic wave functions of the two bulk chains leads to the diffrence in the interference between the bulk and surface SHG and to the change of the SHG peak intensities.

## V SUMMARY

We have developed a phenonmenological model and performed experiments to determine the symmetry of the noncentrosymmetric semiconductor crystal ZnSe(100) covered with an oxide layer. Under the four combinations of fundamental and harmonic linear polarization states considered, the harmnic intensity can be experessed as a function of the light polarization and as a function of the azimuthal angle. Using the caclulated sensitivity to rotation angle of the SHG signal from the bulk and surfaces, we have been able to deduce the symmetry of the noncentrosymmetric crystal surfaces. We found that the measurement using $`S_{in}S_{out}`$ is particularly useful in determining the symmetry of the oxdized layer interface, which would lower the effective symmetry of the surface from $`C_{4v}`$ to $`C_{2v}.`$ The separation between bulk and interface or surface SHG demonstrated here is promising for the application of this technique to the study of surface and interfacial properties. This way can be used to detect the quality of the substrate surface for growth of II-VI epilayers on ZnSe layers.

In addition, we have shown that the  and \[0$`\overline{1}`$1\] directions can be distinguished through the analysis of $`p`$-incident and $`p`$-output confugration.

###### Acknowledgement 1

We would like to thank Dr. Yudan Cheng for helpful discussion, Hao Yin from Physics Department at Uppsala Univ. for technical assistance, and Dr. Emad Mukhtar from Department of Physical Chemistry at Uppsala Univ. for BOXCAR equipment. Wolfgang Seibt, Dr. Duc Tran Chinh and Bo Carman are gratefully acknowledged.