# Reply to “Comment on ‘Inverse exciton series in the optical decay of an excitonic molecule’ ”

## Abstract

As a reply to the Comment by I.S. Gorban et al. (Phys. Rev. B, preceding paper) we summarize our criticism on their claim of the first observation of the $`M`$ series in $`\beta `$-ZnP<sub>2</sub>. We support our analysis by reporting the first observation of inverse polariton series from the excitonic molecules selectively generated at $`𝐊_m\mathrm{𝟎}`$ in a CuCl single crystal. This observation and its explanation within the bipolariton model complete our proof of the biexcitonic origin of the inverse series.

A monocrystal CuCl is a prototype material in the physics of excitonic molecules, due to the polarization isotropy of the optical transitions to the excitonic states and due to the large binding energy of the molecules $`ϵ^m`$ 32 meV . In a recent paper  we reported the observation of the $`M`$ series, which originates from the optical decay of the molecules into the excitonic states $`1s`$, $`2s`$, $`3s`$, $`4s`$, and $`\mathrm{}s`$. The lines $`M_{n2s}`$ are extremely weak and their detection requires a very modern spectroscopic technique and a high-quality CuCl single crystal. In our paper we explained briefly why the claim by Gorban et al.  to the observation of the $`M`$ series in $`\beta `$-ZnP<sub>2</sub> is not justified (see reference  of Ref. ). By their Comment  the authors force us to present a more detailed criticism of their experiments.

Monoclinic zinc diphosphide ($`\beta `$-ZnP<sub>2</sub>) is an optically highly-anisotropic semiconductor with eight molecules per unit cell, which give rise to $`72`$ phonon modes. As a result, the excitonic spectra are very complicated and strongly depend on the excitation and polarization geometry. Thus the correct interpretation of the optical spectra of $`\beta `$-ZnP<sub>2</sub> requires a very accurate experiment, a high-quality sample, and a critical analysis of the experimental data. The first reports  on the observation of the inverse hydrogen-like series in $`\beta `$-ZnP<sub>2</sub> attribute the series to a bielectron-impurity complex. To the best of our knowledge, these results have never been confirmed. The next reports  on the inverse series ascribe the photoluminescence (PL) spectra of highly-excited $`\beta `$-ZnP<sub>2</sub> to the $`M`$ series. Even without commenting on Gorban et al.’s experiments, we will show below that their interpretation of the PL spectra in terms of the $`M`$ series is self-contradictory and incorrect.

Firstly, from their experimental data Gorban et al. conclude that the biexciton binding energy $`ϵ^m`$ in $`\beta `$-ZnP<sub>2</sub> is unusually high, i.e., $`ϵ^m=14.9`$ meV ($`0.32`$ of the excitonic Rydberg $`ϵ^x`$). In order to explain this result the authors claim without any justifications that the relevant electron and hole effective masses in $`\beta `$-ZnP<sub>2</sub> are given by $`m_e=1.7m_0`$ and $`m_h=21.3m_0`$ ($`\sigma =m_e/m_h=0.08`$) . This strongly contradicts the Kane model, which basically requires $`m_hm_0`$, and the first experiments  on excitonic polaritons in $`\beta `$-ZnP<sub>2</sub> which yield the effective excitonic mass $`M_x=m_e+m_h3m_0`$. The latest high-precision experiments by two-photon and magneto-optical spectroscopies  indicate the high anisotropy of $`\beta `$-ZnP<sub>2</sub> single crystals with $`m_e=0.7m_0`$, $`m_h=1.1m_0`$ along the $`a`$-axis, $`m_e=1.1m_0`$, $`m_h=1.4m_0`$ along the $`b`$-axis, and $`m_e=0.18m_0`$, $`m_h=0.20m_0`$ along the $`c`$-axis, respectively. These values clearly demonstrate that the effective masses chosen by Gorban et al. are irrelevant. Furthermore, with reference to $`\sigma =0.08`$ the authors claim that their $`ϵ^m=0.32ϵ^x`$ “corresponds to the variational calculations of Refs. ” (see p. 339 of Ref. ). This is a misinterpretation of the theoretical results of Refs. . An inspection of Fig. 1 of Ref.  and Fig. 3 of Ref.  shows that the mass ratio $`\sigma =0.08`$ yields $`ϵ^m0.12ϵ^x`$. As a result, even for the above incorrect value of the ratio $`m_e/m_h`$ the molecule binding energy should be only $`ϵ^m=`$ 5.64 meV rather than 14.9 meV.

Secondly, the intensity ratio between two main replicas of the series reported by Gorban et al. is too high to be ascribed to the $`M`$ series. The intensity ratio of two lines marked by $`M_1`$ and $`M_2`$ in Fig. 1 of Ref.  is given by $`I_{M_2}/I_{M_1}1/3`$ ($`I_{M_1}=I_{M_{1T}}+I_{M_{1L}}`$). In Ref.  the authors explain that the above ratio should be corrected due to the saturation of the $`M_{1T}`$ line and that the true value is $`I_{M_2}/I_{M_1}1/9.08`$ as shown in the intensity dependence in Fig. 2 of Ref. . The bipolariton model  with the Akimoto-Hanamura trial wave function  yields $`I_{M_2}/I_{M_1}1/5000`$ for excitonic molecules in CuCl (the electron-hole mass ratio $`\sigma =0.28`$). This value is in agreement with our experiments, which indicate $`I_{M_2}/I_{M_1}1/7000`$. Using a precise wave function of the hydrogen molecule , we find $`I_{M_2}/I_{M_1}1/800`$ in the limit $`\sigma =0`$. Thus, within the uncertainty in the value of $`\sigma `$ in $`\beta `$-ZnP<sub>2</sub>, we estimate, for excitonic molecules in this semiconductor, $`I_{M_2}/I_{M_1}1/1000`$. The latter value is at least two orders of magnitude smaller than that reported by Gorban et al. . Note that in the Comment  the authors have corrected their intensity ratio as $`I_{M_2}/I_{M_1}1/230`$ referring to the $`new`$ intensity dependence in Fig. 2 of the Comment, but this intensity dependence contradicts that reported in Fig. 2 of Ref. .

The low-temperature PL spectra of $`\beta `$-ZnP<sub>2</sub> single crystals at moderate optical excitations have been studied in Ref. . According to Ref. , the $`M_1`$ emission band indeed develops at an optical excitation power of about 10 kW/cm<sup>2</sup>, however, without any indications of the $`M`$ series. Instead, below the $`M_1`$ band another PL line arises (at 1.523 eV), which grows quadratically with the excitation intensity and has a comparable intensity with the $`M_1`$ band. This $`M`$-like emission line is attributed to excitonic molecules trapped by surface defects, because a similar spectral line is presented in the reflection spectra but is absent in the absorption spectra. Furthermore, the line is not reproducible from sample to sample but found only for a few samples. Note that the above described $`M`$-like emission at 1.523 eV exactly coincides with the PL line labeled by $`M_2`$ in Fig. 1 of the Comment (see also Fig. 1 of Ref. ). According to Ref. , the molecule energy is 3.1102 $`\pm `$ 0.0002 eV. Therefore the inverse $`M_2`$ emission should arise at 1.519 eV, rather than at 1.523 eV in the Gorban et al.’s data.

Because of its extremely weak intensity, the confirmation of the inverse series requires many severe experimental checks. The two-photon resonant generation of excitonic molecules with translational momentum $`\mathrm{}𝐊_m`$ is crucial for unambiguous discrimination of the $`M`$ series in our experiments. In Fig. 1 we compare the PL spectra of a high-quality CuCl single crystal (sample $`No.1`$) recorded under the selective excitation of the molecules at $`𝐊_m=2𝐤_0`$ (solid curve) and under the interband excitation (dashed curve). Here $`𝐤_0`$ is the wave vector of the pump polaritons. In the latter case the $`M_T`$ and $`M_L`$ emission lines are absent because of weak cw-laser excitation, but only $`1s`$ exciton emissions and the relavant bound exciton lines are present. As shown by the solid curve, even under the two-photon excitation of the molecules, bound exciton structures similar to those in the dashed curve grow quadratically with the excitation intensity together with the $`M`$ series. They originate from the secondary excitons generated by the molecule decay. As shown by the dashed curve, an emission from impurity-bound excitons occurs at 3.082 eV. Therefore, the line marked by $`M_{Z_{1,2}}`$ cannot be attributed to the inverse series, although its energy coincides with the molecule emission leaving the longitudinal $`Z_{1,2}`$ exciton behind . On the other hand, our samples are free from any impurity emissions at the spectral position of the $`M_{2s}M_\mathrm{}s`$ lines. Thus we assign these lines to the inverse $`M`$ series. Furthermore, we checked the reproducibility of the $`M_{2s,3s,4s}`$ series for several high-quality samples of a CuCl single crystal. Figure 2 shows the PL spectrum of sample $`No.2`$ under resonant generation of excitonic molecules at $`𝐊_m=2𝐤_0`$. The period of interference pattern of sample $`No.2`$ is different from that of sample $`No.1`$. However, the characteristics of the $`M`$ series are identical for both samples.

At the present time we have improved the experimental setup and can observe the optical decay of excitonic molecules selectively excited at various $`𝐊_m`$ ($`0K_m2k_0`$). Figure 3 shows the inverse emission series from excitonic molecules with $`𝐊_m\mathrm{𝟎}`$. Now the molecule cannot decay into the pure excitonic states $`1s`$, $`2s`$, …, but resonantly dissociates into two outgoing polaritons associated with the corresponding optical transitions. Thus the $`M`$ series of Fig. 3 is described as an inverse polariton series. Because the main contribution to the series is due to the resonant dissociation of the molecule into the lower dispersion branch polaritons, we designate the series by $`LP_{ns}`$. Note that the intensity ratio $`I_{LP_{2s}}/I_{LP_{1s}}`$ is about $`1/100`$, i.e., by two orders of magnitude larger than $`I_{M_{2s}}/I_{M_{1s}}`$ corresponding to the molecules initially photogenerated at $`𝐊_m=2𝐤_0`$ . With the bipolariton model of an excitonic molecule , both of the inverse series, $`M_{ns}`$ of Fig. 1 and $`LP_{ns}`$ of Fig. 3, are explained self-consistently using the same trial molecule wave function . This completes our proof of the biexcitonic origin of the inverse series observed in CuCl single crystals. The use of a weak selective resonant excitation of the molecules allows us to avoid the nonlinear reabsorption processes and a thermal distribution of the molecules which considerably changes the intensity ratios of the inverse series.

In their experiments, Gorban et al. have used only the interband excitation of $`\beta `$-ZnP<sub>2</sub>. Such an excitation is not suitable for the discrimination of the $`M`$ series as we have shown above. Furthermore, while the authors do not observe their $`M`$ series at moderate interband excitations of $`\beta `$-ZnP<sub>2</sub> (Ar-laser of a few kW/cm<sup>2</sup> intensity), they describe a corresponding rich PL spectrum mainly in terms of the optical decay of nonlocalized excitonic molecules (see the lines marked by $`M_1`$, $`C`$, and $`G`$ in Fig. 3 of Ref. ). According to Gorban et al., the $`G`$-band is due to the degenerate two-photon radiative annihilation of biexcitons with $`𝐊_m\mathrm{𝟎}`$ and the $`C`$-line is due to a “dielectric liquid” of excitonic molecules. We consider this interpretation as absolutely speculative and unjustified. In particular, the $`M_{1s}`$ band of thermally distributed excitonic molecules is not expected to show any fine structure due to the degenerate two-photon annihilation of the molecules . Finally, if the nonlocalized biexcitons are mainly responsible for the complicated PL spectrum plotted in Fig. 3 of Ref. , as the authors incorrectly interpret, it is not understandable why in this case they do not observe their $`M`$ series.

Once the inverse $`M`$-series is observed , the question on the reconstruction of the internal molecule wave function naturally arises. Here, the relevant theoretical questions are how the molecule decays radiatively to the $`ns`$ exciton states and how the relative intensities of the $`M_{ns}`$ replicas relate to the molecule wave function. The theory of the optical decay of an excitonic molecule presented by Gorban et al.  is incorrect.

Firstly, the use of Wang’s trial wave function, Eq. (1) of Ref. , means that the biexciton is identified with the hydrogen molecule. The Wang wave function is suitable for H<sub>2</sub> due to the adiabatic approximation, which requires $`(m_e/m_h)^{1/4}1`$. The latter inequality definitely does not hold even for the incorrect ratio $`m_e/m_h=0.08`$ used by the authors for biexcitons in $`\beta `$-ZnP<sub>2</sub>. In other words, an envelope wave function for the relative motion of two constituent excitons is absent in Eq. (1) of Ref. . However, the authors ignore the above standard arguments and take the results of the well-known calculations  on the hydrogen molecule with the same values of the fitting parameter ($`Z=1.166`$) and binding energy ($`0.31`$ Rydberg). The Wang wave function is irrelevant for excitonic molecules. The corresponding evaluation of the molecule binding energy within the four-particle Schrödinger equation, claimed by the authors, cannot be reproduced.

Secondly, Eq. (2) of Ref.  proposed for the intensities of the $`M_{ns}`$ replicas is incorrect, because (i) two of the arguments of the molecule wave function are fixed by $`r_{a1}=0`$ and $`r_{b1}=a_{biex}`$, (ii) one additional integral convolution with the ground-state excitonic envelope wave function is absent (the integration over $`d𝐫_{a1}`$). As a result, the authors end up with an incorrect conclusion, that “the probability of the two-photon radiative transition is $`(a_{biex}/a_{ex})^6`$, in contrast to the probability of the two-photon absorptive one which is $`(a_{biex}/a_{ex})^3`$”. Furthermore, Eq. (2) of Ref.  does not include the polariton effects, i.e., the both crucial factors, the density of states and Hopfield’s coefficients, are omitted.

Thirdly, the expansion of the molecule wave function given by Eq. (3) of Ref.  makes little sense, because (i) the biexciton wave function is assumed to be dependent only on two coordinates $`𝐫_{a1}`$ and $`𝐫_{b2}`$, while the correct wave function should be specified by three independent vector coordinates, (ii) the r.h.s. of Eq. (3) is not symmetric with respect to the permutation of two electrons or holes. The correct expansion of the molecule wave function is given by Eq. (5) of Ref. .

In order to assign the $`M`$-like emissions to the inverse exciton series one needs a severe critical analysis of the experimental data. While the observation of the $`M`$ series in CuCl requires a highly sensitive detection technique and a high-quality sample free from impurity emissions, our results are very stable and reproducible. Furthermore, $`𝐤`$-selective excitation of excitonic molecules is crucial both for the final evidence of the observation of the $`M`$ series and for the reconstruction of the molecule wave function. The bipolariton model allows us to describe self-consistently a continuous, smooth change of the intensities and spectral positions of the $`M_{ns}`$ replicas with the total molecular wavevector $`𝐊_m`$ decreasing from $`2𝐤_0`$ towards $`𝐊_m=\mathrm{𝟎}`$ (compare Fig. 1 and Fig. 3). From the criteria discussed above we conclude that Gorban et al. have not yet presented a convincing set of the experimental data on the $`M`$ series in $`\beta `$-ZnP<sub>2</sub>.