10% Efficiency Solar Cells with 0.

5 m of CdTe
V. V. Plotnikov, DoHyoung Kwon, K. A. Wieland and A. D. Compaan Department of Physics and Astronomy and Wright Center for PV Innovation and Commercialization The University of Toledo, Toledo, OH 43606 USA tion of the heat-up and cool-down time was also estimated and taken into account. The back contact was our standard, thermally diffused Cu/Au bilayer deposited by thermal evaporation. The Au thickness was 15 nm and the thickness of the Cu layer was chosen to be either 30 , 20 or 10 . The Cu activation time ranged from 45 minutes o to 5 minutes at 150 C in the room air ambient. Each sample representing a unique combination of CdTe thickness / CdCl2 treatment time / back contact 2 scheme contained 35 dot cells of 0.062 cm area. Cells were subjected to J-V, AQE and J-V-T tests. RESULTS AND DISCUSSION

ABSTRACT Fabricating high-efficiency CdS/CdTe solar cells with ultra-thin (below 1m) absorber layers is a challenging yet highly desirable step in improving CdTe technology. Typically solar cell performance decreases due to shunting, incomplete absorption (deep penetration loss), fully depleted CdTe layers or interference between the main and the back contact junction when the CdTe layer thickness approaches a certain limit. While some of these losses are fundamental, others can be minimized by careful optimization of the fabrication steps. We present the results of such optimization.

Current density, mA/cm

INTRODUCTION Reducing the thickness of the CdTe layer is a natural step in CdTe solar cell technology. The University of Toledo has fabricated magnetron sputtered cells with 2.4 um of CdTe having typically 13% efficiency. Recently, we reduced the CdTe thickness down to 0.3 m. Cells with CdTe thicknesses of 1 m, 0.5 m and 0.3 m show efficiencies of 12%, 9.7% and 6.8% respectively. As the cells get thinner Voc, FF and Jsc are affected. Current-voltage (J-V), temperature dependent J-V (J-V-T) and apparent quantum efficiency (AQE) measurements provide valuable information for optimizing cell performance. EXPERIMENTAL DETAILS

Voltage, V 0 0.0 -5 -10 -15 -20 -25 0.2 0.4 1.5 m 1.8 m 2.0 m 2.6 m 0.6 0.8

Voltage, V
2

We prepared cells with variable thickness of the CdTe layer (from 2.6 m to 0.3 m) to determine the cell performance dependence on the absorber layer thickness. Cells were fabricated on 3 mm soda-lime glass substrates with SnO2:F/HRT (high resistivity transparent) coating. CdS layer thickness was chosen to be 60 nm which, according to our previous studies, allows for a good transmission of the window layer but at the same time assures strong electrical properties of the n-side of the junction. Thus the variations in cell performance are mainly due the properties of the CdTe and the back contact side of the device. We prepared a set of samples with the following CdTe thicknesses: 0.3 m, 0.5 m, 0.65 m, 0.8 m, 1.1 m, 1.45 m, 1.85 m, 2.2 m and 2.6 m. Thickness was measured by a DEKTAK3 profilometer. For each CdTe thickness we used four different combinations of CdCl2 treatment and back contact recipe. We varied the CdCl2 treatment time from 38 minutes to 5 minutes while keepo ing the temperature constant at 387 C. Treatment was done in a tube furnace flushed with dry air. The contribu-

Current density, mA/cm

0 0.0 -5 -10 -15 -20 -25

0.2 0.4 0.3 m 0.5 m 0.65 m 0.85 m 1.1 m

0.6

0.8

Figure 1. J-V characteristics of the cells with variable CdTe thickness. Thicker cells (top) and thinner cells (bottom). J-V characteristics of a typical good cell for each CdTe thickness are shown on the Figure 1. We found very little decrease of the cell performance for all thicknesses

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down to 1 micron if the post-deposition conditions are close to the optimum. This can be seen from Figure 2 where the efficiency of the best cell and average efficiency for the 35 sample set are plotted against the CdTe thickness. Overall we found that for the thicker cells (0.85 m and above) variations in the thickness of as-deposited Cu and Cu diffusion time make a greater difference than variations in the duration of the CdCl2 treatment. For instance using 30 of as-deposited Cu instead of 10 led to an increase of the average VOC by much as 50 mV in one case (1.85 m CdTe) and this trend was consistent throughout the whole range of thicknesses (0.85m to 2.6 m). A similar dependence was observed in the fill factor as well.

Overall we have fabricated cells with efficiency of 12.8% for the CdTe thickness of 1.1 m, 9.7 % for the 0.5 m CdTe and 6.8% for the 0.5 m CdTe. Conditions that yielded the best cell for each thickness are summarized in Table 1. Table 1. Best cell parameters and fabrication conditions that led to these results Cu CdTe Eff, JSC, VOC, FF, CdCl2, Cu diff, thickness, 2 min , % mA/cm mV % min m
2.6 2.2 1.85 1.45 1.1 0.85 0.65 0.5 0.3 13.3 13.7 13.2 13.3 12.8 11.0 11.3 9.7 6.8 24.3 25 24.4 25.0 24.4 23.4 22.2 21.1 17.5 840 805 824 824 803 776 776 735 708 68.3 68.5 67.2 68.7 68.1 65.9 66.4 62.2 56.0 38 34 23 18 18 13 7 5 5 30 30 30 20 10 10 20 10 10 45 45 45 30 20 15 10 7 5

14 12 10 Eff, % 8 6 4 2 0 0.0 0.5 1.0 1.5 2.0 2.5 CdTe thickness, m 3.0 Max Average

Figure 2. Best cell efficiency as a function of the CdTe thickness.

Voltage, V Current density, mA/cm

2

0 -5 -10 -15 -20

0.0

0.2

0.4

0.6

0.8

0.3 m CdTe 0.5 m CdTe 0.5 m CdTe

Figure 3. J-V characteristics of the best ultra-thin cells The situation gets more complicated for the thinner samples (below 0.85 m). We have not seen a clear dependence on either CdCl2 treatment duration or back contact scheme, yet certain benchmarks were established.

Figure 3 shows the J-V characteristics of three best ultra-thin cells. One cell is 0.3 m of CdTe and the two others are 0.5 m CdTe. We attribute the Jsc vs. Voc tradeoff after comparison of the 0.5 m cells to the difference in CdS layer thickness (60 nm for the cell represented with the dashed line and 30 nm for the cell represented with the dotted line). We believe that in the latter case Voc is limited by the n-side of the photovoltaic junction, while Jsc is slightly higher because of a higher transparency of the thin CdS layer. External AQE, done for five different voltage biases (1 V, -0.5 V, 0 V, 0.3 V and 0.5 V), reveals much stronger carrier collection dependence on applied bias for the thinner cells compared to the thicker ones. For example, 2.6 m cells show very little change in QEs obtained with both reverse and forward biases applied (Figure 4). Dependence on forward bias increases when the thickness of the CdTe layer approaches 1 m while reverse bias still does not have an effect on the QE shape. It becomes noticeable though when the CdTe thickness approaches 0.5 m. This interval of CdTe thicknesses (0.5 m to 1 m) is exactly where we start seeing a decrease in both the Voc and FF as well (see Figure 2). This leads us to a conclusion that a typical depletion width in UT sputtered cells is also of the same scale. In order to characterize the thin cells further and to explore the influence of the back contact we performed JV-T measurements of the thin cells using a bifacial illumination technique, similar to that described by Desai, et al[1], with the exception that we used white light for the glass-side illumination and monochromatic 405 nm light for both glass-side and back-side illumination. In the case of the back-side illumination we took advantage of approximately 50% visible range transmission of the 15 nm Au film used for the back contact. In all the cases the intensity of the incident light was adjusted to match a typical short-circuit current output of the tested cell under 1 sun 2 illumination conditions (typically from 19 mA/cm to 23 2 mA/cm depending on CdTe thickness). Cell temperature

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was varied within the range of 255 K to 315 K. A typical set of J-V curves obtained within this temperature range is presented in Figure 5.

1.5x10 1.0x10 Current, mA

-3

-3

100 80 QE, % 60 40 20 0

2.6 m CdTe

Temperature decreasing

5.0x10

-4

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V -0.5 V 1V 0.3 V 0.5 V

0.0 0.0 -4 -5.0x10 -1.0x10 -1.5x10

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0.8 1.0 Voltage, V

-3

500

600 700 800 Wavelength, nm

900

Figure 5. A set of J-V curves obtained at different temperatures (255 K to 315 K). After collecting the J-V data we plotted the Voc dependence on temperature and performed a linear extrapolation to 0 K to obtain a barrier height b (Figure 6). Figure 7 shows that highest b value of about 1.45 eV was obtained for a relatively fresh cell (dark storage time of about two weeks, in room air ambient). In this case b was close to the Eg/q value for CdTe (1.56 eV), indicating SRH as a dominating recombination mechanism. For all the aged cells (dark storage time of about 5 months in room air ambient) b values were found to be significantly lower which suggests that interfacial recombination through the defect states becomes a major factor limiting cell performance after a certain amount of storage time without encapsulation in room air ambient (296 K, about 30% relative humidity).

100 80 QE, % 60 40 20 0 500

1.1 m CdTe

-1 V -0.5 V 0V 0.3 V 0.5 V 600 700 800 Wavelength, nm 900

1.6
100 80 QE, % 60 40 20 0 500

0.5 m CdTe
Voc, V

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

900

-1V -0.5 V 0V 0.3 V 0.4 V 600 700 800 Wavelength, nm

50 100 150 200 250 300 350 Cell temperature, K

Figure 4. AQE of the 2.6 m, 1.1 m and 0.5 m cells.

Figure 6. Linear extrapolation of the Voc vs. T dependence to obtain b. White light glass side illumination. Another important observation from Figure 7 is that thinner cells in general have lower b (notice also a higher b for the fresh cell with 0.5 m CdTe). We hypothesize that this is a back-contact interface-related effect, more easily noticeable in thin cells. If CdTe is thin enough, the distance from the main junction to the back contact becomes comparable to the absorption depth for the pho-

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tons in the red and near-infrared parts of the solar spectrum. In this case a relatively large fraction of the electronhole pairs is generated in proximity to the back contact where a higher density of defect states and band bending associated with a Schottky barrier facilitating surface recombination is often observed. Therefore, it is plausible to expect that the back-barrier recombination will affect the performance of the thin cells to a greater extent than in the case of the thicker devices.

1.6 1.4 1.2

b, eV

Eg/q

hole pairs are generated within 0.25 m from the illuminated interface. Therefore, for the case of the glass-side illumination the influence of the back contact is minimal. And vice-versa, illumination from the back side dramatically emphasizes the effect of the back contact recombination. The difference between the three cases (405 nm, front; white light, front; and 405 nm, back) is illustrated in Figure 8. For all the thin (0.5 m CdTe or 0.65 m CdTe) studied we found that b extracted from data taken with 405 nm glass-side illumination is always higher than for the case of glass-side white light illumination; and both of these values are higher than the b value with 405 nm illumination from the back side.

CONCLUSION
We investigated the dependence of the cell performance over a wide range of CdTe thicknesses (0.3 m2.6 m). We find that an average efficiency of greater than 12% can be achieved for cells as thin as 1 micron with the appropriate post-deposition treatment and optimized back contact scheme. For CdTe thicknesses of one micron and above, we find the effect of the back contact scheme (asdeposited Cu thickness) to be more dramatic than variation in CdCl2 treatment time. Insufficient Cu caused an average VOC reduction of as much as 50 mV in some cases, while the use of adequate amounts of Cu yielded VOC greater of about 800 mV or above for all samples within this thickness range. We also found that further reduction of CdTe thickness leads to a gradual decrease in performance although 9.7% efficiency can be obtained with 0.5 micron CdTe. Recombination at the back contact was identified as a one of the mechanisms limiting performance of the thin cells.

1.0 0.8 0.6 0.4 0.2 0.0 0.5 1.0 1.5 2.0 2.5 CdTe thickness, m 3.0 "Aged" cells (5 months) "Fresh cells" (2 weeks)

Figure 7. b values for several cells tested. Cells differ in CdTe thickness (aged cells) as well as in dark storage time (fresh cells).

1.6 1.5 1.4

b eV

Eg/q 0.5 m 0.5 m 0.5 m 0.65 m

ACKNOWLEDGMENTS
This work was supported by the NREL Thin Film Partnership program and the DOE-SAI University Photovoltaic Process and Product Development program.

1.3 1.2 1.1 1.0 0.9 405 nm White light glass side glass side

REFERENCES
[1] D. Desai et al., How CdTe solar cells operate: Determining collection using bifacial device characterization, IEEE Fourth World Conference on Photovoltaic Energy Conversion, 1, 2006, pp 368-371.

405 nm back side

Figure 8. b values of four cells subjected to three different illumination conditions In order to test this hypothesis of back-barrier recombination we performed a J-V-T data analysis similar to that described above for the cases of glass-side illumination as well as a back-side illumination with monochromatic 405 nm light. In both cases about 99% of the electron-

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