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

## Abstract

Tokunaga et al. \[Phys. Rev. B 59, R7837 (1999)\] claim the first successful observation of the inverse exciton $`M`$ series in the emission spectrum of excitonic molecules. We assert that actually such a series was observed as early as 1989 in the $`\beta `$-$`ZnP_2`$ crystal. We show that the objections of Tokunaga et al. against the biexciton nature of the inverse exciton series in $`\beta `$-$`ZnP_2`$ are ungrounded. In particular, their estimations for the ratio of the intensities of $`M2`$ and $`M1`$ emission lines in this crystal give two order smaller value because they do not take into account the reabsorption of the $`M1`$ line photons. We report the observation of additional inverse exciton $`M^{}`$ series in the emission spectrum of excitonic molecules in $`\beta ZnP_2`$.

In the recent publication  Tokunaga et al. have reported an observation of the inverse exciton $`M`$ series in the emission spectrum of excitonic molecules in $`CuCl`$ crystal. They claim that their experiment is the first successful observation of such a series in semiconductors. The aim of our Comment is to show that the above claim is not actual.

To our knowledge the first observation of the emission $`M`$ series caused by two-electron radiative transitions in a biexciton was reported by some authors of the present Comment ten years ago.  In Ref.  such a series was observed in $`\beta ZnP_2`$ crystal (fig. 1). At two-electron transition one exciton of the molecule annihilates and the other stays in the ground state (line $`M1`$) or passes to excited (lines $`M2`$, $`M3`$, …) and ionized (line $`M\mathrm{}`$) states. Later, we described inverse exciton series in $`\beta ZnP_2`$ emission spectrum in Ref. . However, the authors of Ref.  disregarded above publications. Tokunaga et al. cited only the paper,  where the theoretical analysis of two-electron and two-photon radiative transitions in an excitonic molecule was made. However, they have objected the biexciton nature of the inverse exciton series in $`\beta ZnP_2`$.

First their argument is that the ratio of the intensities of $`M2`$ and $`M1`$ lines of the series in $`\beta ZnP_2`$ is too large for the biexciton $`M`$ series: $`I_2/I_110^1`$. We would like to point an attention of the authors of Ref.  to the following. Indeed, an experimental value of $`I_2/I_1`$ is $`1.1\times 10^1`$. Proceeding from the assumption of biexciton nature of the inverse exciton series in $`\beta ZnP_2`$, we obtained theoretically in Ref. : $`I_2/I_1=1.1\times 10^2`$. Numerical estimations of the authors of Ref.  give $`10^3`$ for $`I_2/I_1`$ in this material. However, as we have pointed out in Ref. , this disagreement between theory and experiment is clear enough. At high excitation of the sample by powerful pulse $`N_2`$ laser (excitation intensities $`10^6W/cm^2`$) the concentration of $`1S`$ excitons is high enough. In addition to this, in $`\beta ZnP_2`$ the lowest exciton state is the forbidden state of orthoexciton  that could raise the concentration of excitons in $`1S`$ state. Transitions from the $`1S`$ state of exciton into the molecule ground state cause reabsorption of $`M1`$ line photons ($`he_{1S}+\mathrm{}\omega _{M1}h_2e_2`$) and corresponding decrease of this line intensity. Concentration of excitons in the $`2S`$, $`3S`$, … states does not increase considerably because of their fast relaxation to the $`1S`$ state, and there is no saturation of the lines $`M2`$, $`M3`$ and $`M\mathrm{}`$. This our argument is based on the results of experimental study of the dependences of the intensities of inverse series lines on the excitation intensity $`I_{exc}`$ (fig. 2).  The second power increase of the $`M1`$ line intensity with $`I_{exc}`$ slows done at high excitation levels, and this effect becomes stronger with increase of the excitation intensity. Such saturation effect is not observed for other lines of the series. Let us extrapolate the $`M1`$ line intensity dependence on excitation intensity to the values of $`I_{exc}`$ at which an experimental value of $`I_2/I_1`$ is $`1.1\times 10^1`$ (fig. 2). Consequently, we obtain the value of $`I_2/I_1`$ in the case of the absence of reabsorption of $`M1`$ line photons and the respective absence of this line saturation. An extrapolation gives $`I_2/I_2=4.3\times 10^3`$. This value agrees with Ref.  estimations ($`10^3`$) which do not consider the reabsorption effect. Some disagreement between the value obtained from the extrapolation and our estimations made in Ref.  ($`1.1\times 10^2`$) is possibly due to rough wave function of biexciton that we have used in Ref. . For other lines of the inverse series in $`\beta ZnP_2`$ good agreement between experimental and theoretical values of the ratios of intensities takes place: $`(I_3/I_2)_{exp}=1.4\times 10^1`$ and $`(I_3/I_2)_{th}=1.3\times 10^1`$; $`(I_{\mathrm{}}/I_3)_{exp}=4.3\times 10^1`$ and $`((I_4+I_5)/I_3)_{th}=3.9\times 10^1`$, where $`I_{\mathrm{}}=_{n=4}^{\mathrm{}}I_n`$ is the total intensity of $`M4`$, $`M5`$, … lines which merge into the total $`M\mathrm{}`$line. In $`CuCl`$ the lowest exciton state is allowed. Biexcitons in Ref.  were resonantly created by two-photon absorption method and, therefore, excitons would be created only at the optical decay of biexcitons. Due to these two facts, the concentration of excitons would be insufficient for reabsorption of $`M1`$ line photons, and this line would not be saturated, i.e. an agreement between experiment and theory would take place for all lines of the inverse series in $`CuCl`$. Such an agreement was reported in Ref. .

$`M`$ series in $`\beta ZnP_2`$ is observed at considerably higher temperatures too (fig. 3). This fact confirms high binding energy of the biexciton in $`\beta ZnP_2`$ and rejects any possible impurity interpretation. $`\beta ZnP_2`$ is very remarkable in the following. If the direction of the wavevector of emitted photon $`𝐤`$ is parallel to axis $`b`$ of crystal ($`𝐤b`$) and photon polarization is $`𝐄a`$, another inverse exciton $`M^{}`$ series is observed in emission spectrum of this crystal (fig. 4). This additional series is symmetric to $`A`$ series of the free $`S`$ orthoexciton which is observed in absorption spectrum at $`𝐄a`$ and $`𝐤b`$.  Thus, $`M^{}`$ series is due to the radiative transitions from the excitonic molecule ground state to the $`S`$ states of orthoexciton. Main $`M`$ series is symmetric to $`C`$ series of the free $`S`$ paraexciton which is observed in absorption and emission spectrum at $`𝐄c`$.  Respectively, $`M`$ series is due to the radiative transitions from the biexciton ground state to the $`S`$ states of paraexciton.

Authors of Ref.  see the cause that the previous attempts of biexciton $`M`$ series observation “were unsuccessful” in fact that “the $`M_{n2}`$ lines are extremely weak in intensity, requiring for their observation a highly sensitive detection technique and a high-quality sample free from impurity emissions”. However, the fact of extremely weak intensities of $`M`$ series lines in $`CuCl`$ does not prove the impossibility of that in other materials these intensities can be considerably higher. Indeed, in $`CuCl`$ intensities of $`M_{n2}`$ lines are extremely small, since in this material: $`I_2/I_1=1.4\times 10^4`$; $`I_3/I_1=4.0\times 10^5`$; $`I_4/I_1=1.5\times 10^5`$. In $`\beta ZnP_2`$ we have more than one order higher values: $`I_2/I_1=4.3\times 10^3`$; $`I_3/I_1=6.0\times 10^4`$; $`I_4/I_1=2.6\times 10^4`$. This fact simplifies the observation of $`M`$ series in $`\beta ZnP_2`$. And finally, authors of Ref.  asserted that our experimental data were not confirmed in a similar experiment by K. Kondo (K. Kondo, M.S. thesis, Okayama University, 1998). However, they have answered by themselves on this point having written that the high-quality samples are required for biexciton $`M`$ series observation. Most likely, K. Kondo just did not have the samples of the required quality.

The authors of Ref.  determined the components $`C_n`$ of the exciton excited states $`n=2,3`$, and $`4`$ in the biexciton wave function in $`CuCl`$ from the relative intensities of $`M1`$, $`M2`$, $`M3`$, and $`M4`$ lines. This allowed them to reconstruct the internal molecule wave function. However, they did not say that this idea was proposed in Ref. . Only the reabsorption of $`M1`$ line photons and the respective saturation of this line did not allow us to reconstruct the biexciton wave function in $`\beta ZnP_2`$. However, taking for $`I_2/I_1`$ the extrapolation value obtained above, we can estimate the components $`C_n`$ of the exciton excited states in the biexciton wave function in $`\beta ZnP_2`$ as following: $`|C_2/C_1|^2=I_2/I_1=4.3\times 10^3`$; $`|C_3/C_1|^2=I_3/I_1=6.0\times 10^4`$; $`|C_4/C_1|^2=I_4/I_1=2.6\times 10^4`$.

In conclusion, we assert that the inverse exciton $`M`$ series in the emission spectrum of excitonic molecules was observed for the first time in $`\beta ZnP_2`$ crystal in 1989.  Besides this series, we have observed in this crystal an additional inverse exciton $`M^{}`$ emission series which is due to the radiative transitions from the biexciton ground state to the $`S`$ states of orthoexciton.