SPHERICAL SILICON SOLAR CELLS FABRICATED BY HIGH SPEED DROPPING METHOD

Takashi Minemoto , Yoshihiro Akashi , Chikao Okamoto , Satoshi Omae , Yukio Yamaguchi , Mikio Murozono , 1 1 Hideyuki Takakura and Yoshihiro Hamakawa 1 Faculty of Science and Engineering, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan 2 Clean Venture 21 Co., 2-8-1 Tsuda-yamate, Hirakata, Osaka, 573-0128, Japan 3 The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo, 113-8656, Japan - voltage (J-V) characteristics and quantum efficiency measurements.
1 2 1 1 3 2

ABSTRACT A spherical Si solar cell with semi-concentration system has been successfully fabricated based on a Si sphere fabricated by a high speed dropping method. The Si sphere is multicrystalline and typically shows the etch pit 5 2 density of around 10 cm with spatial distribution. Our baseline process (not fully optimized yet) have produced the spherical Si solar cell with 10.4 % efficiency. Quantum efficiency and laser beam induced current measurements revealed that an optimization in the optical design of the cell and the quality improvement of spherical Si crystals are needed for further high efficiency. INTRODUCTION Spherical silicon solar cells have gathered much attention as a promising candidate for high efficiency and low cost solar cells [1-4]. We proposed the new type of a spherical silicon solar cell with semi-concentration reflector system as shown in Figure 1 [5]. The solar cell consists of the spherical Si solar cell and the concentration mirror. The great merits of the solar cell are followings: 1) The Si sphere fabrication method of a dropping method eliminates cutting and polishing processes commonly utilized in Si wafer fabrication which causes Si material loss. The dropping method, therefore, reduces the Si material loss, which leads cost reduction by the reduction of Si material use. 2) The concentration reflector with 4-6 times concentration enhances open circuit voltage (Voc) comparable to that in a conventional crystalline Si solar cell made by a Si wafer. Here, a precise design in the reflector system is needed to achieve high short circuit current (Jsc). The comparable efficiency to the conventional cell, therefore, is expected in the spherical Si solar cell with lower cost. In this paper, the fabrication of Si spheres by the dropping method and our baseline process of a spherical Si solar cell fabrication are reviewed. We discuss the crystal quality of Si spheres by etch pit density (EPD) measurements, and the solar cell performance and the optical efficiency of the reflector system by current density

Spherical Si solar cell (1mm)

reflector (2.2~2.7mm)

Fig. 1. Schematic image of the spherical Si solar cell with semi-concentration system. EXPERIMENTAL Silicon sphere fabrication Figure 2 shows the schematic image of Si sphere fabrication apparatus of the dropping method. The apparatus consists of a dropping furnace and a free-fall tower. In the dropping furnace, a starting material of boron doped p-type Si is melted in a crucible having a dropping nozzle at the bottom, and then inert gas pressure is applied to instill the small droplets of molten Si from the nozzle. A production speed of Si spheres is controllable by inert gas pressure; a typical speed is 1,000 spheres/second/nozzle. In the free-fall tower with the height of 11.5 meter connected directly under the furnace, the droplets of molten Si takes spherical shape by surface tension and solidifies and crystallizes during free-fall. The ambient in the free-fall tower is inert gas, which prevents contamination form ambient and controls the cooling rate of Si spheres. The crystal qualities of Si spheres were evaluated by etch pit density of the cross section of the spheres with Secco etch [6].

0-7803-8707-4/05/$20.00 2005 IEEE.

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Inert gas pressure

Dropping furnace

Molten silicon Crucible Heater

Free-fall Tower (11.5m high)

Spherical Silicon

and Ag/Al paste, respectively. Here, the performance of spherical Si solar cells can be inspected. 5) If necessary, a hydrogen passivation is done in a R. F. plasma system to passivate electronically active defects such as dislocation and point defects in Si grains and grain boundaries. 6) An antireflective (AR) coating such as ZnO and SnO2 is formed by liquid phase deposition which realizes a uniform AR coating over the spherical Si solar cell. 7) Finally, the spherical Si solar cell is mounted on a reflector made by an Ag electroplated Al substrate. The solar cells were characterized by J-V 2 measurements under 100 mW/cm AM1.5 illumination at o 25 C and quantum efficiency measurements. RESULTS AND DISCUSSIONS Crystal quality The crystal qualities of Si spheres were evaluated by etch pit density after Secco etch. Si spheres were grinded to expose cross section and then they were soaked in Secco etch solution, i.e., 0.15 molar solution of K2Cr2O7 in distilled H2O and HF (49%), for 3 minutes with ultrasonic agitation. Ultrasonic agitation leads to an improved surface appearance. EPD was determined by the number of etch pits in the area of 100 m x 100 m counted from the scanning electron micrograph (SEM) of the spheres. Figure 4 shows the SEM images of the cross section of a spherical Si after Secco etch. The sphere has spatial 5 distributions of EPDs. Area a has the EPD of 4.9 x 10 2 4 cm whereas area b has ten times lower EPD of 5.0 x 10 2 cm . There are some spheres which have obviously high EPDs in the center of the sphere compared to the surface side. Moreover, some Si spheres with poor crystal quality large voids in the center of the sphere (not

Fig. 2. Schematic im age of the dropping method. Solar cell fabrication Figure 3 shows our baseline process of the spherical Si solar cell fabrication. The fabrication process is following: 1) p-type Si spheres are fabricated by the dropping method. The diameter of the spheres is around 1 mm. 2) A pn junction is formed by the vapor diffusion of phosphorus. A typical junction depth is around 0.5 m. 3) A part of the Si sphere is grinded to expose p-layer. 4) n- and pelectrodes are formed by printing and firing of Ag and Ag/Al paste, respectively. Here, the performance of a spherical Si solar cell can be inspected. 5) If necessary, a hydrogen passivation is done in a R. F. plasma system to passivate(1) As dropped electronically active defects(2) pn junction such as dislocation and point defects in Si grains and grain boundaries. 6) An (p-type) formation antireflective (AR) coating such as ZnO and SnO2 is (vapor diffusion of P) formed by liquid phase deposition which realizes a uniform AR coating over the spherical Si solar cell. 7) Finally, the spherical Si solar cell is mounted on a reflector made by a silver electroplated Al substrate. p-Si p-Si The solar cell was characterized by J-V measurements 2 o under 100 mW/cm AM1.5 illumination at 25 C and n-Si quantum efficiency measurements.

(3) pn separation
(grinding)

(4) Electrode formation

(printing/firing)

(7) Mounting on reflector

ARC n-Si

Incident light
Reflector (n-electrode)

(6) AR coating

(5) Defect passivation

(liquid phase deposition) (H plasma treatment)

p-Si

p-electrode

Fig. 3. Fabrication process of the spherical Si solar cell with semi-concentration system.

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has large voids in the center of the sphere (not shown in this paper). There seems to be some relationships between EPD and the position inside the sphere; further investigations on the crystal growth mechanism of Si spheres and their crystal quality are needed.

Using the value of the Rs, A and J0 can be obtained from the slope and intercept of the semi-logarithmic plot of J+Jsc vs V-RsJ. Diode parameters of the solar cell -9 obtained through this calculation are J0 of 4.24 x 10 2 2 A/cm , A of 1.42, Rs of 1.63 cm , and G of 0.167 2 mS/cm . In these parameters, Rs is noticeably poor; A typical value for a high performance solar cell is less than 0.5 cm 2). The origin of the high Rs will be the connection between the spherical Si solar cell and the reflector, which will be solved soon.

a b

30 25 20 15

500 m
a
EPD= 4.9 x 10xcm 2 EPD= 4.9 5 10 5

EPD= 5.0 x 10xcm2 EPD= 5.0 4 10 4

10 5 0 0.0

Effi. : 10.4 % Jsc : 27.2 mA/cm2 Voc : 569 mV FF : 67.3 % Area: 0.042cm2
0.1 0.2 0.3 0.4 0.5 0.6

100m

100m

100m

100m

Voltage (V)
Fig. 4. SEM image of the cross section of a spherical Si after Secco etch. Solar cell performance Figure 5 shows the J-V characteristics of the typical spherical Si solar cell with semi-concentration system. The 2 efficiency of 10.4 % [Jsc, 27.2 mA/cm ; Voc, 569 mV; fill factor (FF), 67.3 %] was demonstrated by the dropping method and our baseline process for the solar cell fabrication. The J-V data was analyzed by a standard diode equation
q J = J 0 exp (V R s J ) J 0 JL + GV , AkT

Fig. 5. Current-voltage characteristics of the spherical Si 2 solar cell measured under 100 mW/cm AM1.5 illumination o at 25 C Figure 6 shows the external quantum efficiency (EQE) of the solar cell. The peak value of 0.76 at the wavelength of 690 nm is significantly low for achieving high Jsc. LBIC measurements (not shown in this paper) revealed that the light directly enter the reflector contribute to JL, however there is some area to produce poor JL. This indicates the optimization on the reflector design is needed to realize high optical efficiency of the reflector system. On the other hand, a gradual decrease in EQE in the long wavelength region (> 700 nm) revealed the poor minority carrier diffusion length LD of the solar cell. The crystal quality distribution indicated by EPD measurements may cause the low LD because even a small part of a poor quality crystal may act as a recombination sink in the solar cell based on indirect bandgap semiconductor which generally have longer LD than direct bandgap one. These results indicate that the optimization in the reflector system and the improvement in crystal quality of the Si spheres are essential to achieve higher efficiency.

(1)

where J0 is the forward current, A is the diode quality factor, JL is the light generation current, Rs is the series resistance, and G is the shunt conductance. For the solar cell in this work, G obtained by the slope of J-V curve at a 2 reverse bias region is lower than 1 mS/cm and can be neglected. Rs was determined from the intercept of a plot -1 of the derivative dV/dJ vs (J+Jsc) , since, according to Eq. (1) with JL=Jsc:
dV AkT (J + J sc )1. = Rs + dJ q

(2)

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1.0 0.8 0.6 0.4 0.2

ACKNOWLEDGEMENTS The authors would like to thank H. Funato, T. Kaino, D. Hironiwa, T. Mizuta, T. Ikuta, T. Tsunemi, and K. Tsujiya at Ritsumeikan University and T. Nakamura at Clean Venture 21 Co. for numerous technical assistances and helpful discussions. The authors also would like to thank Prof. T. Fuyuki and H. Kondo at Nara Institute of Science and Technology for LBIC measurements. This work was partly supported by NEDO as Investigation for Innovative PV Technology Project and Nisshin Electric Co, Ltd. REFERENCES

0.0 300

600

900

1200

Wavelength (nm)
Fig. 6. External quantum efficiency of the spherical Si solar cell. CONCLUSIONS The Si spheres which act as the substrate of solar cells were successfully fabricated by the high speed dropping method. The SEM observations of the Si sphere after Secco etch revealed that relatively high crystal quality Si 5 2 spheres have the EPD of around 10 cm with spatial EPD distribution. Our baseline process (not fully optimized yet) has successfully produced the spherical SI sol ar cell with semi-concentration system having 10.4% efficiency. EQE and LBIC measurement revealed that the quality improvement of spherical Si crystals and the design optimization in the reflector system are needed to achieve high efficiency.

[1] J. D. Levine et al., Basic Properties of The Spheral TM Cell, Twenty-second IEEE PVSC, 1991, pp. Solar 1045-1048. [2] R. R. Schmit et al., Recent Progress in The Design TM and Fabrication of Spheral Solar Modules, Twenty-third IEEE PVSC, 1993, pp. 1078-1081.
TM [3] R. R. Schmit et al., Spheral Solar Cell Fabrication and Performance, Twelfth European PSEC, 1994, pp. 737-740.

[4] G. Stevens et al., Latest Developments in Spheral TM Solar Cell Process and Design, Nineteenth European PSEC, 2004, pp. 1270-1273. [5] T. Minemoto et al., Design Strategy and Development of Spherical Silicon Solar Cell with Semi-concentration Reflector System, Fourteenth PVSEC, 2004, pp. 207-208. [6] F. Secco dAragona et al., Dislocation Etch for (100) Planes in Silicon, J. Electrochem. Soc. 119, 1972, pp. 948-951.

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