Silicon quantum dot superlattice solar cell structure including silicon nanocrystals in a photogeneration layer
© Yamada et al.; licensee Springer. 2014
Received: 19 February 2014
Accepted: 3 May 2014
Published: 20 May 2014
The solar cell structure of n-type poly-silicon/5-nm-diameter silicon nanocrystals embedded in an amorphous silicon oxycarbide matrix (30 layers)/p-type hydrogenated amorphous silicon/Al electrode was fabricated on a quartz substrate. An open-circuit voltage and a fill factor of 518 mV and 0.51 in the solar cell were obtained, respectively. The absorption edge of the solar cell was 1.49 eV, which corresponds to the optical bandgap of the silicon nanocrystal materials, suggesting that it is possible to fabricate the solar cells with silicon nanocrystal materials, whose bandgaps are wider than that of crystalline silicon.
85.35.Be; 84.60.Jt; 78.67.Bf
KeywordsSilicon nanocrystals Silicon quantum dot Solar cells Quantum size effect
Over the past few years, many researchers have shown an interest in silicon nanostructures, such as silicon nanocrystals [1–4] and silicon nanowires [5–8] for solar cell applications. Since a silicon nanocrystal embedded in a barrier material can make carriers confined three-dimensionally, the absorption edge can be tuned in a wide range of photon energies due to the quantum size effect. Thus, it is possible to apply silicon nanocrystal materials or silicon quantum dot (Si-QD) materials to all silicon tandem solar cells , which have the possibility to overcome the Shockley-Queisser limit . Moreover, it has been found that the weak absorption in bulk Si is significantly enhanced in Si nanocrystals, especially in the small dot size, due to the quantum confinement-induced mixing of Γ-character into the X-like conduction band states . Therefore, Si-QD materials are one of the promising materials for the third-generation solar cells. Size-controlled Si-QDs have been prepared in an amorphous silicon oxide (a-SiO2) , nitride (a-Si3N4) , carbide (a-SiC) [14–17], or hybrid matrix [18, 19], which is called as silicon quantum dot superlattice structure (Si-QDSL). In the case of solar cells, generated carriers have to be transported to each doping layer. Since the barrier height of an a-SiC matrix is relatively lower than that of an a-Si3N4 or a-SiO2 matrix, the Si-QDSL using an a-SiC matrix has an advantage in carrier transport. Therefore, the development of the Si-QDSL solar cells using an a-SiC matrix is of considerable importance. There are a few researches fabricating Si-QDSL solar cells. Perez-Wurfl et al. reported that Si-QDSL solar cells with SiO2 matrix showed an open-circuit voltage (Voc) of 492 mV. However, the clear evidence of the quantum size effect has not been reported from Si-QDSL solar cells . In our previous work, Si-QDSLs with a-SiC matrix have been prepared by plasma-enhanced chemical vapor deposition (PECVD). The defect density in a Si-QDSL has been successfully reduced by hydrogen plasma treatment (HPT), and the shift of photoluminescence spectra from the Si-QDSLs has been confirmed by varying the diameter of the Si-QDs . Moreover, it has been revealed that the oxygen-incorporation into the a-SiC matrix can suppress the formation of the leakage paths . An Voc of 518 mV has been obtained in a Si-QDSL solar cell with an amorphous silicon oxycarbide (a-Si1 - x - yC x O y ) matrix .
In this paper, we report the effect of oxygen addition on the formation of Si-QDs in a-Si1 - x - yC x O y . Optical absorption coefficients of the Si-QDSL were also investigated. Si-QDSL solar cells were fabricated using the optimum oxygen concentration. In addition, the numerical analysis using the Bohm quantum potential (BQP) method was performed to simulate the electrical characteristics of fabricated solar cells.
The a-Si1 - x - yC x O y matrix was deposited on a quartz substrate to investigate the fundamental optical properties such as Raman scattering spectrum, transmittance, and reflectance. The fabrication method is referred as follows. A 40-period-multilayer with silicon-rich hydrogenated amorphous silicon oxycarbide layers and hydrogenated amorphous silicon oxycarbide barrier layers was prepared on a quartz substrate by very high frequency PECVD method (VHF-PECVD). The source gases were silane (SiH4), monomethylsilane (MMS), hydrogen (H2), and carbon dioxide (CO2). The flow rates of SiH4, MMS, and H2 + CO2; deposition pressure; substrate temperature; frequency; and plasma power were fixed at 3.3 , 1.3, and 47.4 sccm; 20 Pa; 60 MHz; 193 °C; and 13 mW/cm2, respectively. The flow rate of CO2 was varied from 0 to 3.7 sccm. The mass flow controllers for SiH4 and CO2 were calibrated by N2. A H2-calibrated mass flow controller was used for MMS. During the deposition of a-Si1 - x - yC x O y barrier layers, the flow of SiH4 gas was stopped. Subsequently, the samples were annealed at 900 °C for 30 min under a forming gas atmosphere to form Si-QDs in an a-Si1 - x - yC x O y matrix. The target size of Si-QDs and barrier width were 5 and 2 nm, respectively. The concentrations of Si, C, and O in the barrier layer were measured by X-ray photoelectron spectroscopy (XPS). The crystallinity of Si-QDs was investigated by Raman scattering spectroscopy. The absorption coefficient of a Si-QDSL was estimated by the transmittance and the reflectance of a sample. The samples with uniform thickness were selected for the measurements, and one measurement was carried out for each measurement method and for each sample.
Parameters of each layer for calculations
a-Si1 - x- yC x O y
Energy gap (eV)
Electron affinity (eV)
Carrier lifetime (s)
1 × 10-15
1 × 10-10
1 × 10-10
1 × 10-6
Electron mobility (cm2/Vs)
Hole mobility (cm2/Vs)
Donor concentration (cm-3)
1 × 1019
0 or 1 × 1017
Accepter concentration (cm-3)
1 × 1019
Results and discussion
Optical properties of Si-QDSLs
Concentrations of Si, C, and O in a-Si 1 - x - y C x O y films with several CO 2 /MMS flow rate ratios
These results indicate that the CO2/MMS flow rate ratio should be below approximately 0.3 to form Si-QDs in the silicon-rich layers. According to the , the CO2/MMS flow rate ratio should be higher than 0.3 to suppress the crystallization of a-SiC phase in the a-Si1 - x - yC x O y barrier layers and the increment of the dark conductivity for the annealing temperature of 900°C. Although there is a trade-off between the promotion of the crystallization of Si-QDs and the suppression of the crystallization of a-SiC phase, the CO2/MMS flow rate ratio of approximately 0.3 or the oxygen concentration of approximately 25 at.% is one of the optimal conditions. Therefore, the CO2/MMS flow rate ratio of 0.3 is adopted for the solar cell fabrication in this study.
I-V characteristics of the fabricated solar cells
Solar cell parameters of the fabricated Si-QDSL solar cells and the calculated by BQP method
Calculations of I-V characteristics and quantum efficiencies
The light I-V characteristics and the internal quantum efficiency of the Si-QDSL solar cells with a doped Si-QDSL layer and a non-doped Si-QDSL layer were simulated under AM1.5G illumination using the BQP method. The calculated solar cell parameters are shown in Table 3. Also, the calculated quantum efficiencies are shown in Figure 7. The simulated quantum efficiencies are multiplied by 0.12 for comparison with the experimental one. The calculated short-circuit current densities (Jsc) and quantum efficiencies are much higher than those of the experimental results. There are two possible reasons.
The first reason is due to the difference of the doping concentration in a Si-QDSL layer. In an actual solar cell, the phosphorus concentration in the Si-QDSL absorber layer is more than 1 × 1019 cm-3 due to the high-temperature annealing process . From the simulations, the Jsc and the quantum efficiency in the whole wavelength region becomes lower if the phosphorus concentration in the Si-QDSL layer increases. The phosphorus in the Si-QDSL layer degrades the Jsc due to the reduction of the electrical field in the Si-QDSL layer. Unfortunately, simulations were not possible when the dopant concentration in the Si-QDSL was higher than 1 × 1017 cm-3 due to the convergence problem of the BQP calculations. It is expected that Jsc will decrease more if the dopant concentration becomes higher. We previously reported that the quantum efficiency in the whole wavelength region decreases as the dopant concentration in the Si-QDSL increases from experiments and the simulations using classical model , which is similar to the results of the BQP method. The second reason is due to the optical losses in the n-type poly-Si layer. In this calculation, the surface roughness of the textured quartz substrate was not taken into account. The effective optical path length in the n-type layer of the simulated structure should be shorter than that of the actual solar cell structure. As a result, the simulated quantum efficiency in the short-wavelength region is higher than that of the experimental because of the low optical absorption loss in the n-type poly-Si layer.
Even though the Jsc mismatch, the absorption edge can be estimated from the simulated quantum efficiency. The calculated quantum efficiencies at the long-wavelength region are in agreement with those of the experimental one. This suggests that the absorption edge of the solar cell can be theoretically reproduced using this simulation. Moreover, the absorption edge was estimated to be 1.49 eV, which is quite similar to the absorption edge of the Si-QDSL estimated from the optical measurements. This indicates that the photogeneration in the Si-QDSL solar cell is thought to be the contribution from Si-QDs, and it is possible to fabricate the solar cells with silicon nanocrystal materials, whose bandgaps are wider than that of a crystalline silicon.
The fundamental optical properties of Si-QDSLs were investigated, and the solar cell structure using the Si-QDSL as an absorber layer was fabricated and characterized. From the measurements of the Raman spectra and the absorption coefficients of Si-QDSLs, it was revealed that the absorption coefficient is enhanced by the crystallization of the Si-QDs, and the crystallinity of Si-QDs is affected by the oxygen concentration in the superlattice. In addition, the solar cell characteristics were simulated by the BQP method. The absorption edge of the simulated Si-QDSL solar cell was in agreement with that of the fabricated one. Moreover, the absorption edge of the Si-QDSL solar cell was 1.49 eV, which is similar to the absorption edge estimated from the optical measurements. These results suggest that it is possible to fabricate the solar cells with silicon nanocrystal materials, whose bandgaps are wider than that of a crystalline silicon.
This work was supported in part by the New Energy and Industrial Technology Development Organization (NEDO) under the Ministry of Economy Trade and Industry of Japan.
- Yamada S, Kurokawa Y, Miyajima S, Yamada A, Konagai M: High open-circuit voltage oxygen-containing Si quantum dots superlattice solar cells. In Proceedings of the 35th IEEE Photovoltaic Specialists Conference. Honolulu; 2010:766.Google Scholar
- Kurokawa Y, Tomita S, Miyajima S, Yamada A, Konagai M: Photoluminescence from silicon quantum dots in Si quantum dots/amorphous SiC superlattice. Jpn J Appl Phys Part 2 2007, 46: L833. 10.1143/JJAP.46.L833View ArticleGoogle Scholar
- Kurokawa Y, Tomita S, Miyajima S, Yamada A, Konagai M: Observation of the photovoltaic effect from the solar cells using Si quantum dots superlattice as a light absorption layer. In Proceedings of the 33rd IEEE Photovoltaic Specialists Conference. San Diego; 2008:211.Google Scholar
- Perez-Wurfl I, Hao XJ, Gentle A, Kim DH, Conibeer G, Green MA: Si nanocrystal p-i-n diodes fabricated on quartz substrates for third generation solar cell applications. Appl Phys Lett 2009, 95: 153506. 10.1063/1.3240882View ArticleGoogle Scholar
- Tian BZ, Zheng XL, Kempa TJ, Fang Y, Yu NF, Yu GH, Huang JL, Lieber CM: Coaxial silicon nanowires as solar cells and nanoelectronic power sources. Nature 2007, 449: 885. 10.1038/nature06181View ArticleGoogle Scholar
- Tsakalakos L, Balch J, Fronheiser J, Korevaar BA, Sulima O, Rand J: Silicon nanowire solar cells. Appl Phys Lett 2007, 91: 233117. 10.1063/1.2821113View ArticleGoogle Scholar
- Sivakov V, Andrä G, Gawlik A, Berger A, Plentz J, Falk F, Christiansen SH: Silicon nanowire-based solar cells on glass: synthesis, optical properties, and cell parameters. Nano Lett 2009, 9: 1549. 10.1021/nl803641fView ArticleGoogle Scholar
- Jeon M, Kamisako K: Synthesis and characterization of silicon nanowires using tin catalyst for solar cells application. Mater Lett 2009, 63: 777. 10.1016/j.matlet.2009.01.001View ArticleGoogle Scholar
- Cnibeer G, Green M, Corkish R, Cho Y, Cho E-C, Jiang C-W, Fangsuwannarak T, Pink E, Huang Y, Puzzer T, Trupke T, Richards B, Shalav A, Lin K-I: Silicon nanostructures for third generation photovoltaic solar cells. Thin Solid Films 2006, 511–512: 654.View ArticleGoogle Scholar
- Shockley W, Queisser HJ: Detailed balance limit of efficiency of p-n junction solar cells. J Appl Phys 1961, 32: 510. 10.1063/1.1736034View ArticleGoogle Scholar
- Luo JW, Stradins P, Zunger A: Matrix-embedded silicon quantum dots for photovoltaic applications: a theoretical study of critical factors. Energy Environ Sci 2011, 4: 2546. 10.1039/c1ee01026cView ArticleGoogle Scholar
- Ficcadenti M, Pinto N, Morresi L, D'Amico F, Gunnella R, Murri R, Tucci M, Mittiga A, Serenelli L, Izzi M, Falconieri M, Sytchkova AK, Grilli ML, Pirozzi L: Si quantum dots for solar cell fabrication. Mater Sci Eng B 2009, 159–160: 66.View ArticleGoogle Scholar
- Rezgui B, Sibai A, Nychyporuk T, Lemiti M, Brémond G: Photoluminescence and optical absorption properties of silicon quantum dots embedded in Si-rich silicon nitride matrices. J Lunimescence 2009, 129: 1744.View ArticleGoogle Scholar
- Kurokawa Y, Miyajima S, Yamada A, Konagai M: Preparation of nanocrystalline silicon in amorphous silicon carbide matrix. Jpn J Appl Phys Part 2 2006, 45: L1064. 10.1143/JJAP.45.L1064View ArticleGoogle Scholar
- Song D, Cho E-C, Conibeer G, Huang C, Flynn C, Green MA: Structural characterization of annealed multilayers targeting formation of Si nanocrystals in a SiC matrix. J Appl Phys 2008, 103: 083544. 10.1063/1.2909913View ArticleGoogle Scholar
- Song D, Cho E-C, Cho Y-H, Conibeer G, Huang Y, Huang S, Green MA: Evolution of Si (and SiC) nanocrystal precipitation in SiC matrix. Thin Solid Films 2008, 516: 3824. 10.1016/j.tsf.2007.06.150View ArticleGoogle Scholar
- Moon JH, Kim HJ, Lee JC, Cho JS, Park SH OB, Cho EC, Yoon KH, Song J: Silicon quantum dots thin films and superlattice in SiC matrix by co-sputtering of silicon and carbon. In Proceedings of the 34th IEEE Photovoltaic Specialist Conference. Philadelphia; 2009:253.Google Scholar
- Di D, Perez-Wurfl I, Conibeer G, Green MA: Formation and photoluminescence of Si quantum dots in SiO2/Si3N4 hybrid matrix for all-Si tandem solar cells. Sol Energy Mater Sol Cells 2010, 94: 2238. 10.1016/j.solmat.2010.07.018View ArticleGoogle Scholar
- Ding K, Aeberhard U, Astakhov O, Köhler F, Beyer W, Finger F, Carius R, Rau U: Silicon quantum dot formation in SiC/SiOx hetero-superlattice. Energy Procedia 2011, 10: 249.View ArticleGoogle Scholar
- Perez-Wurfl I, Ma L, Lin D, Hao X, Green MA, Conibeer G: Silicon nanocrystals in an oxide matrix for thin film solar cells with 492 mV open circuit voltage. Sol Energy Mater Sol Cells 2012, 100: 65.View ArticleGoogle Scholar
- Kurokawa Y, Yamada S, Miyajima S, Yamada A, Konagai M: Effects of oxygen addition on electrical properties of silicon quantum dots/amorphous silicon carbide superlattice. Curr Appl Phys 2010, 10: S435. 10.1016/j.cap.2010.02.014View ArticleGoogle Scholar
- Bohm D: A suggested interpretation of the quantum theory of “hidden” variables. I. Phys Rev 1952, 85: 166. 10.1103/PhysRev.85.166View ArticleGoogle Scholar
- Bohm D: A suggested interpretation of the quantum theory of “hidden” variables. II. Phys Rev 1952, 85: 180.View ArticleGoogle Scholar
- Iannaccone G, Curatola G, Fiori G: Effective Bohm quantum potential for device simulators based on drift-diffusion and energy transport. In International Conference on Simulation of Semiconductor Processes and Devices: 2004, Munich. Edited by: Wachutka G, Schrag G. New York: Springer; 2004:275.View ArticleGoogle Scholar
- Giacomini R, Martino AM: Trapezoidal cross-sectional influence on FinFET threshold voltage and corner effects. J Electrochem Soc 2008, 155: H213. 10.1149/1.2833317View ArticleGoogle Scholar
- Kurokawa Y, Yamada S, Konagai M: Numerical approach to the performance of silicon quantum dots superlattice solar cells taking into account the quantum effect. Jpn J Appl Phys 2012, 51: 10NE09. 10.7567/JJAP.51.10NE09View ArticleGoogle Scholar
- Roulston DJ, Arora ND, Chamberlain SG: Modeling and measurement of minority-carrier lifetime versus doping in diffused layers of n+-p silicon diodes. IEEE Trans Electron Devices 1982, 29: 284.View ArticleGoogle Scholar
- Law ME, Solley E, Liang M, Burk DE: Self-consistent model of minority-carrier lifetime, diffusion length, and mobility. IEEE Electron Device Lett 1991, 12: 401.View ArticleGoogle Scholar
- Fossum JG, Lee DS: A physical model for the dependence of carrier lifetime on doping density in nondegenerate silicon. Solid-State Electron 1982, 25: 741. 10.1016/0038-1101(82)90203-9View ArticleGoogle Scholar
- Owens JM, Han DX, Yan BJ, Yang J, Lord K, Guha S: Micro-Raman studies of mixed-phase hydrogenated silicon solar cells. Mat Res Soc Symp Proc 2003, 762: 339.Google Scholar
- Nesbit LA: Annealing characteristics of Si-rich SiO2 films. Appl Phys Lett 1985, 46: 38. 10.1063/1.95842View ArticleGoogle Scholar
- Tauc J: Optical properties and electronic structure of amorphous Ge and Si. Mater Res Bull 1968, 3: 37. 10.1016/0025-5408(68)90023-8View ArticleGoogle Scholar
- Pi XD, Mangolini L, Campbell SA, Kortshagen U: Room-temperature atmospheric oxidation of Si nanocrystals after HF etching. Phys Rev B 2007, 75: 085423.View ArticleGoogle Scholar
- Yamada S, Kurokawa Y, Konagai M: High Thermostable and Conductive Niobium Doped Titanium Oxide for the Application to a Diffusion Barrier Layer of Silicon Quantum Dot Superlattice Solar Cell Structure. In Proceedings of the 37th IEEE Photovoltaic Specialists Conference. Seattle; 2011:002113.Google Scholar
- Yamada S, Kurokawa Y, Miyajima S, Konagai M: Improvement of electrical properties of silicon quantum dot superlattice solar cells with diffusion barrier layers. Jpn J Appl Phys 2013, 52: 04CR02. 10.7567/JJAP.52.04CR02View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited.