Development of High Performance C-Rich a-SiC Semiconductors with Narrow-Optical Gap By Control of Its Phase Structure
Authors: Honda Kensuke , Matsumoto Akari 
Published: December 2020

1. Introduction

For the expansion of application fields (ex. tailor-made photocatalysts and high-efficiency laser) of semiconductor, novel semiconductor materials with variable optical gaps in the range from 1.2 to 3.0 eV is necessary to be developed. The promising candidate of these semiconductor is carbon-rich amorphous silicon-carbon alloy (C-rich a-SiC).[1] The optical gaps (Eog) of C-rich a-SiC can be changed from 1.2 to 2.7 eV by changing the Si/C ratio. Hetero-junction solar cell comprising N-doped C-rich a-SiC with Eog = 2.7 eV and p-type Si have been reported to show the function of photon to electron conversion.[2] However, solar cells comprising N-doped C-rich a-SiC with Eog from 1.2 to 1.7 eV showed extremely lower conversion efficiencies. Therefore, all of these C-rich a-SiC with Eog from 1.2 to 2.7 eV may not be applied to photoelectronic devices. The objective of this study is to realize C-rich a-SiC with lower Eog (frim 1.2 to 1.7 eV) that have higher semiconductor property and are able to be applied to photoelectronic devices. a-SiC has a multiphase structure in which amorphous Si-C network (Si:C = x:1-x), sp2-hybridized carbon cluster (sp
2 clusters), and silicon-like clusters (Si-cluster) coexist. It has been reported that excess sp2 cluster worked as a recombination center of photoexcited carries. It results in the degradation of efficiencies of photon to electron conversion. In order to realize C-rich a-SiC with lower Eog and higher photon to electron conversion efficiency, the synthesis method that can enhance of ratio of C/Si in amorphous Si-C network and suppress the formation of sp
2 clusters in C-rich a-SiC is necessary to be developed. In this study, CVD synthesis using high-frequency and lower power r. f. plasma was tried to be adopted to induce two types of structural change at C-rich a-SiC. High-frequency and lower power r. f. plasma can avoid the formation of sp
2 clusters in C-rich a-SiC. It results in the semiconductor materials with lower Eog and higher photon to electron conversion efficiency.

2. Experimental

Nitrogen-doped C-rich a-SiC thin films were synthesized by radio frequency plasma enhanced chemical vapor deposition system (RF-PeCVD) (13.56 MHz, SAMCO Co., Ltd. Model BPD-1) using tetramethylsilane, 1,1,3,3-tetrametyldisilazane and n-hexanes as source materials. C-rich a-SiC thin films were deposited on glass plate and boron-doped silicon (100) substrate (resistivity of 2 W cm) after an in-situ sputter cleaning with argon ions. Substrate temperature was kept at 160 degree C during CVD deposition. The frequency of r.f. power supply was set at 60 MHz and r.f power were changed from 5 to 26 W. The deposition time was 80 minutes. Transmission spectra of N-doped C-rich a-SiC deposited on glass substrates were examined by UV-Vis spectrophotometer (JASCO Co., Ltd. V-670). The performance of heterojunction solar cells was investigated by current-voltage (I-V) measurement (KEYSIGHT, B2901A) with simulated AM 1.5 sunlight (ASAHI SPECTRA, HAL-320).

3. Results and Discussion

Eog estimated from transmission spectra (Fig. 1) of resulting N-doped C-rich a-SiC were found to be in the range from 1.40 to 2.96 eV, as shown in Table 1. Eog was able to be controlled to lower value (1.4 eV) thorough the change of the S/C ratios in C-rich a-SiC (by changing the volume ratio of n-hexane in source materials). All hetero-junction solar cells comprising N-doped C-rich a-SiC with various Eog and p-type Si crystal were confirmed to show the function of photon-to electron conversion (Table 1). The improvement of function of photon to electron conversion at C-rich a-SiC with lower Eog (ca. 1.4 eV) might be caused by the suppression of the recombination of photo-exited electrons and holes. In Figure 1, the absorption peak of sp
2 clusters was observed at 1.1 eV and was clearly separated from the absorption peak of amorphous Si-C network (observed at 2.6 eV). The intensity decrease and peak shift to lower energy side of the absorption of sp
2 clusters in Fig. 1 indicates the decrease of the amount of sp
2 clusters and the enlargement of size of sp
2 clusters. These structural change might cause the suppression of recombination of photo-carriers. The relation between Eog and open circuit voltage of solar cell was consistent with estimated value from electronic structure of C-rich a-SiC. It was summarized that the development of C-rich a-SiC semiconductors with lower Eog (in the range from 1.4 to 1.7 eV) that are able to be applied to photo-electronic devices was successfully achieved.

4. References

[1] K. Honda et al., ECS J. Solid State Sci. Technol.
5, 590 (2006).

[2] H. Naragino et al., ECS Trans. 75, 153 (2016).

Figure 1