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Microdome InGaN-Based Multiple Quantum Well Solar Cells

§ 4-1 Introduction

To date, InGaN-based MQW SCs have drawn much research attention due to

their favorable photovoltaic (PV) characteristics, including direct and tunable

bandgaps covering nearly the entire solar spectrum, high absorption coefficient, high

mobility, superior radiation resistance, and additional control of the light absorption

through the quantized energy levels.1,2 Despite these promising characteristics, the

conversion efficiencies of InGaN-based MQW SCs are still unsatisfactory. To

improve the PV performances of InGaN SCs, much research has been reported.3-7 In

order to mitigate the abrupt change in refractive indices from GaN (or ITO) to air,

which blocks a great portion of photons propagating through the air-GaN (or air-ITO)

interface,5a variety of roughened structures have been employed on the top of InGaN

MQW SCs.3,6,7 Periodic subwavelength structures can be fabricated with various

techniques, such as the anodic aluminum oxide templates8 and the nanosphere

lithography.9,10 For the practical applications, the interests in the subwavelength

structures have been extended to disordered structures.3,11,12However, the processing

complexity and the mechanical robustness of the additional roughened structures on

the top of SCs might be a limit to PV applications.

Among various roughened structures, the microdomes (or lens-like

microstructures) have been used for increasing the light escape cone in InGaN

light-emitting diodes (LEDs),13-15resulting in improved light extraction efficiency and

engineered far-field.15 Recently, the use of colloidal microlens arrays had also been

implemented for increasing the light extraction in organic light-emitting diodes,16 as

well as improving the light collection in SCs.17 Additionally, it is found that

roughened p-GaN structures in InGaN LEDs can effectively reduce reflectance loss in

GaN,18 and provides an effective way to make p-metal contact deposition without

using a filling process with the insulating materials in the air gaps caused by

nanostructing/microstructing processes at the device surface, which is required for the

axial p-n nanorod devices to form electrical connection.19 Moreover, the roughened

p-GaN also leads to a reduction of piezoelectric field and improved crystal qualities

due to the relaxation of in-plane strain.20,21Roughening p-GaN is expected to benefit

the PV performances of InGaN MQW SCs since numerical studies have demonstrated

the detrimental effects of strain-induced piezoelectric polarization, forcing the

photocurrent to the opposite direction and thus resulting in low Jsc and open-circuit

voltage (Voc).22 Thus, the pursuit of microdome/lens-like structure via roughening

p-GaN is of great importance for increasing the critical angle and collection efficiency

in InGaN SCs.

In this study, we realize the p-GaN microdome surfaces with the attempt to boost

the conversion efficiencies (η) of InGaN MQW SCs. Compared with flat p-GaN, the

p-GaN microdomes not only generate additional photocurrents (from 0.43 to 0.54

mA/cm2) by suppressing surface reflections considerably but also exhibit an improved

fill factor (from 44 % to 72 %), indicating the strain relaxation and the piezoelectric

field reduction. Accordingly, the p-GaN microdome leads to a 102 % enhancement of

η. The optical enhancement is confirmed using the simulation based on

finite-difference time-domain (FDTD) analysis, reflection measurements and external

quantum efficiency (EQE) measurements. The internal quantum efficiency (IQE)

measurements indicate the possible improvement in photocarrier separation/collection

due to the strain relaxation. The concept of the microdome directly grown during SC

growth preserving mechanical robustness and wafer-scale uniformity without any

additional process represents a viable, promising path toward high-efficiency SCs.

§ 4-2 Experiment

The multiple quantum well (MQW) solar cells (SCs) were grown by

metal–organic chemical vapor deposition on c-plane sapphire substrates. The layer

structures consist of fifteen periods of intentionally undoped In Ga N (2.4

nm)/GaN (14 nm) MQWs, sandwiched by a 2.5-μm n-type (Si-doped) and a 0.2-μm

p-type (Mg-doped) GaN layer. The free carrier concentrations for n-type and p-type

GaN are around 2×1018 cm-3 and 5×1017 cm-3, respectively. Ammonia (NH3),

trimethylgallium (TMGa) for n-GaN and p-GaN, triethylgallium for MQWs, and

trimethylindium were used as the precursors. Surface morphologies of p-GaN were

controlled by TMG flows and substrate temperatures during the p-GaN growth. In

device fabrication, ITO was deposited by electron beam evaporation on p-GaN to

form transparent ohmic contacts. The 1×1 mm2 mesas were then defined by

chlorine-based plasma etching. The contacting scheme consists of fingered

Ti/Al/Ni/Au metal grids with the thicknesses of 20/400/20/2000 nm deposited on the

ITO and the n-GaN.

§ 4-3 Results and Discussion

Surface morphologies of p-GaN were controlled by TMGa flows and substrate

temperatures during the p-GaN growth. For flat p-GaN, TMGa flow rate was 40-50

μmol/min and substrate temperature was in the range of 950-1100 °C. To fabricate the

micro-roughened p-GaN, TMGa flow rate was increased to more than 55 μmol/min

and substrate temperature was decreased to lower than 920 °C. Fig. 4.1 shows

scanning electron microscopy (SEM) images of the MQW SCs with p-GaN

microdome surfaces. The p-GaN microdomes are 530 250 nm in height and the base

of microdomes are 600370 nm in diameter. Fig. 4.2 is the specular reflection

spectra obtained on flat and microdome surfaces at the wavelengths ranging from 340

to 600 nm. One can see that the MQW SC with p-GaN microdome surfaces exhibits a

low reflectance for all studied wavelengths, demonstrating that surface reflectance can

be effectively suppressed by the p-GaN microdomes.

Figure 4.1 45 degree-tilted SEM image of the MQW SCs with p-GaN microdomes.

The inset shows the cross-sectional SEM image.

Figure 4.2 Specular reflection measured on the MQW SCs with flat and microdome surfaces. The p-GaN microdomes are 530 250 nm in height and the base

of microdomes are 600 370 nm in diameter. Fig. 4.2 is the specular reflection

spectra obtained on flat and microdome surfaces at the wavelengths ranging from 340

to 600 nm. One can see that the MQW SC with p-GaN microdome surfaces exhibits a

low reflectance for all studied wavelengths, demonstrating that surface reflectance can

be effectively suppressed by the p-GaN microdomes.

Figure 4.1 45 degree-tilted SEM image of the MQW SCs with p-GaN microdomes.

The inset shows the cross-sectional SEM image.

Figure 4.2 Specular reflection measured on the MQW SCs with flat and microdome surfaces. The p-GaN microdomes are 530 250 nm in height and the base

of microdomes are 600 370 nm in diameter. Fig. 4.2 is the specular reflection

spectra obtained on flat and microdome surfaces at the wavelengths ranging from 340

to 600 nm. One can see that the MQW SC with p-GaN microdome surfaces exhibits a

low reflectance for all studied wavelengths, demonstrating that surface reflectance can

be effectively suppressed by the p-GaN microdomes.

Figure 4.1 45 degree-tilted SEM image of the MQW SCs with p-GaN microdomes.

The inset shows the cross-sectional SEM image.

Figure 4.2 Specular reflection measured on the MQW SCs with flat and

For the incident wavelengths comparable or shorter than the geometric sizes of the

microdomes, the low reflectance can be caused by the light trapping effect due to

severe light scattering. As light impinges on the structured surface, it is diffracted to

several beams with different diffraction angles. The diffracted beams re-bounces

between the p-GaN microdomes, which prevents the light from escaping back to air,

and thus increases the opportunity of optical absorption by the underneath material. It

should be mentioned that the light trapping effect results in the suppressed reflectance

over not only a wide range of wavelengths but also a wide range of incident angles.

23,24

In order to reveal the light propagation across the surface structures, the

distributions of electromagnetic fields within the device structures were simulated by

FDTD analysis. We modeled two kinds of device surfaces: flat p-GaN and p-GaN

microdomes. Fig. 4.3 visualizes the time-averaged TE-polarized electric field

intensity distributions for the MQW SCs with two surface conditions at the incident

wavelength of 400 nm. All of the calculated values in Fig. 4.3 are normalized to those

of the excitation source. It can be seen that the light propagating in the MQW region

for the SC with p-GaN microdomes is strongly and widely scattered, as compared

with the case of flat surface. One can also notice that strong fields are confined within

the p-GaN microdomes. The normalized optical power integrated over the MQW

region as a function of times for the SCs with p-GaN flat and microdome surfaces is

shown in Fig. 4.3(c). The steady-state power values for the two devices are 0.65 and

0.75, respectively. These results indicate that the roughened p-GaN surface not only

helps light propagating across the interfaces but also widens the field distribution

within the device by increasing the light scattering on the surface. Strong light

scattering by the microdome surface is desired for improving the efficiencies of SCs

due to the increase in optical paths, which benefits the light absorption in MQW

regions.

Figure 4.3 Time-averaged and normalized TE electric field distribution simulated by FDTD analysis with two surface structures: (a) flat and (b) p-GaN region as a function of times for the SCs with p-GaN flat and microdome surfaces is

shown in Fig. 4.3(c). The steady-state power values for the two devices are 0.65 and

0.75, respectively. These results indicate that the roughened p-GaN surface not only

helps light propagating across the interfaces but also widens the field distribution

within the device by increasing the light scattering on the surface. Strong light

scattering by the microdome surface is desired for improving the efficiencies of SCs

due to the increase in optical paths, which benefits the light absorption in MQW

regions.

Figure 4.3 Time-averaged and normalized TE electric field distribution simulated by FDTD analysis with two surface structures: (a) flat and (b) p-GaN region as a function of times for the SCs with p-GaN flat and microdome surfaces is

shown in Fig. 4.3(c). The steady-state power values for the two devices are 0.65 and

0.75, respectively. These results indicate that the roughened p-GaN surface not only

helps light propagating across the interfaces but also widens the field distribution

within the device by increasing the light scattering on the surface. Strong light

scattering by the microdome surface is desired for improving the efficiencies of SCs

due to the increase in optical paths, which benefits the light absorption in MQW

regions.

Figure 4.3 Time-averaged and normalized TE electric field distribution simulated by FDTD analysis with two surface structures: (a) flat and (b) p-GaN

microdomes. (c) Normalized optical power, integrated over the MQW region, as a function of times for the two kinds of SCs at 400 nm wavelength.

Fig. 4.4 shows the measured current density–voltage (J–V) curves of the SCs with

two kinds of surfaces. PV characteristics obtained by the J–V curves are listed in the

inset table of Fig. 4.4. One can clearly see that the microdome surfaces lead to

enhanced Jsc, which confirms that the microstructured surface enhances light

absorption. It is also found that the fill factors are enhanced for the SCs with

microdome surfaces suspectedly due to the strain relaxation and the piezoelectric field

reduction caused by the roughened structure.18,20,21 Accordingly, for the SCs with

p-GaN microdomes, η is increased from 0.43 % (with flat surface) to 0.87 %, which is

an improvement of 102 %. The results prove that the microdomes are effective in

boosting the PV performances of the MQW SCs. Note that previous simulation works

focusing on wire SCs reported that increasing the wire length could lead to a constant

decrease in Voc in spite of increases in η.25,26 Consequently, a slight decrease in Voc is

also observed in the MQW SCs with microdome surfaces. We note that the

optimization considerations must be made in future with respect to the geometric

parameters of microdome structures due to the inverse behavior of Jscand Voc.25,26

Figure 4.4 J–V characteristics measured on the MQW SCs with two kinds of surface structures. The inset table shows PV characteristics of InGaN MQW SCs with two kinds of surface structures. FF is the fill factor of SCs, which is defined as the ratio of the actual maximum obtainable power, to the product of Jscand Voc.

To gain insight into the correlation between Jsc enhancement, optical absorption,

and carrier separation/collection efficiency in the active layer, EQE and IQE spectra

were investigated. Fig. 4.5(a) presents the EQE spectra for the two kinds of SCs,

showing the influence of p-GaN microdomes on PV performances. EQEs of the SCs

with microdomes are mostly improved in the region of 360–450 nm, which reveals

the enhancement in light collection efficiency and agrees with the suppressed

reflection on the microdome surface shown in Fig. 4.2. The results also echo with

those revealed by FDTD analysis in Fig. 4.3. Since E. Matioli et al. had found the Figure 4.4 J–V characteristics measured on the MQW SCs with two kinds of surface structures. The inset table shows PV characteristics of InGaN MQW SCs with two kinds of surface structures. FF is the fill factor of SCs, which is defined as the ratio of the actual maximum obtainable power, to the product of Jscand Voc.

To gain insight into the correlation between Jsc enhancement, optical absorption,

and carrier separation/collection efficiency in the active layer, EQE and IQE spectra

were investigated. Fig. 4.5(a) presents the EQE spectra for the two kinds of SCs,

showing the influence of p-GaN microdomes on PV performances. EQEs of the SCs

with microdomes are mostly improved in the region of 360–450 nm, which reveals

the enhancement in light collection efficiency and agrees with the suppressed

reflection on the microdome surface shown in Fig. 4.2. The results also echo with

those revealed by FDTD analysis in Fig. 4.3. Since E. Matioli et al. had found the Figure 4.4 J–V characteristics measured on the MQW SCs with two kinds of surface structures. The inset table shows PV characteristics of InGaN MQW SCs with two kinds of surface structures. FF is the fill factor of SCs, which is defined as the ratio of the actual maximum obtainable power, to the product of Jscand Voc.

To gain insight into the correlation between Jsc enhancement, optical absorption,

and carrier separation/collection efficiency in the active layer, EQE and IQE spectra

were investigated. Fig. 4.5(a) presents the EQE spectra for the two kinds of SCs,

showing the influence of p-GaN microdomes on PV performances. EQEs of the SCs

with microdomes are mostly improved in the region of 360–450 nm, which reveals

the enhancement in light collection efficiency and agrees with the suppressed

reflection on the microdome surface shown in Fig. 4.2. The results also echo with

those revealed by FDTD analysis in Fig. 4.3. Since E. Matioli et al. had found the

possible IQE change in roughened SCs and Wierer et al. had demonstrated that SC

performances including IQE can be further improved by optimizing the barrier

thickness of QWs,4,27 IQE measurements are then taken to evaluate the carrier

separation/collection occurring in the active region. EQE is converted into IQE

through

IQE = EQE/abs(λ) (1)

where abs(λ) the absorption spectra of the SCs, which is shown in Fig. 4.6. For

absorption spectrum measurements, by measuring reflection and transmission in the

spectral range from 360 to 540 nm, the absorption spectra can be obtained by

subtracting reflection and transmission from unity at every wavelength. Accordingly,

the obtained IQE in Fig. 4.5(b) may point out the possibility of IQE changes due to

p-GaN roughening. The variation in IQE after introducing p-GaN microdomes

indicates the possible change in carrier separation/collection efficiency resulted from

relaxation of in-plane strain and consequent reduction of piezoelectric fields during

p-GaN microdome growth.22 One should note that the possible inaccuracy in

determining the absorption spectra due to the difference in the surfaces for both SCs

might not enable one to provide accurate IQE comparison data for both devices. For

correctly determining the IQE for both devices, more detailed experiments in

providing conclusive comparison are required in future. In short, the p-GaN

microdome results in the increases in EQE, which are attributed to the suppressed

interface reflection and possibly efficient separation/collection of photocarriers.

Figure 4.5 (a) EQE curves and (b) IQE curves for the SCs with two kinds of surface structures.

Figure 4.6 The absorption spectra of InGaN MQW SCs with and without microdome structures.

microdome results in the increases in EQE, which are attributed to the suppressed

interface reflection and possibly efficient separation/collection of photocarriers.

Figure 4.5 (a) EQE curves and (b) IQE curves for the SCs with two kinds of surface structures.

Figure 4.6 The absorption spectra of InGaN MQW SCs with and without microdome structures.

microdome results in the increases in EQE, which are attributed to the suppressed

interface reflection and possibly efficient separation/collection of photocarriers.

Figure 4.5 (a) EQE curves and (b) IQE curves for the SCs with two kinds of surface structures.

Figure 4.6 The absorption spectra of InGaN MQW SCs with and without microdome structures.

§ 4-4 Summary

In conclusion, InGaN MQW SCs with microdome surfaces were fabricated. In

comparison with the flat surface, the microdome structures show improved fill factor

and Jsc, leading to the η enhancement by up to 102 %. The p-GaN microdomes exhibit

the enhanced optical absorption due to light trapping effects and possible

improvement of photocarrier separation/collection for the MQW SCs due to the strain

relaxation, resulting in enhanced EQE and IQE. With the advantages of the simple

process and the mechanical robustness, the microdomes grown during SC epitaxial

growth offer a viable way to boost solar efficiency of a variety of SCs.

§ 4-5 References

He, Appl. Phys. Lett. 100, 013105 (2012).

[7] G. J. Lin, K. Y. Lai, C. A. Lin, and J. H. He, Opt. Lett. 37, 61 (2012). and J. A. Smart, Nature Photonic 1, 176 (2007).

[13] Y. K. Ee, P. Kumnorkaew, R. A. Arif, H. Tong, H. Zhao, J. F. Gilchrist, and N.

[14] P. Kumnorkaew, Y. K. Ee, N. Tansu, and J. F. Gilchrist, Langmuir 24, 12150 K. S. Chung, Nano Lett. 4, 1059 (2004).

[20] Y. H. Sun, Y. W. Cheng, S. C. Wang, Y. Y. Huang, C. H. Chang, S. C. Yang, L. Y. and D. Wang, IEEE J. Sel. Top. Quant. 17, 1033 (2011).

[27] J. J. Wierer, Jr., D. D. Koleske, and S. R. Lee, Appl. Phys. Lett. 100, 111119 (2012).

Chapter 5 Efficient light harvesting scheme for InGaN-based quantum well solar cells employing the

hierarchical structure: SiO

2

nanorods/p-GaN microdomes

§ 5-1 Introduction

InGaN-based multiple quantum well (MQW) solar cells (SCs) have a direct and

tunable bandgap, which covers nearly the entire solar spectrum. In addition, they also

possess advantages as high absorption coefficients, high mobilities, and superior

radiation resistance, which allow the operation under harsh environments.[1-3]

Employing MQW structures can provide the independent design between the

short-circuit current (Jsc) and open-circuit voltage (Voc) [4], and also avoid the

undesired trade-off between solar response and crystalline quality [4-6]. However, the

conversion efficiencies (η) of InGaN-based SCs are still limited. Methods for either

internal quantum efficiency (IQE) or external quantum efficiency (EQE)

improvements of SCs have been devoted to boost their photovoltaic (PV)

performances.[7-9]

Recently, a variety of subwavelength structures (SWSs) have been demonstrated

to effectively suppress the undesired Fresnel reflections. These roughened structures

can be used as the light trapping layer with many superior antireflective (AR)

characteristics.[10-13] One efficient AR SWS is the subwavelength nanorod arrays

(NRAs) structure, which can be regarded as an intermediate medium with an effective

refractive index (neff) between the air and device surface.[14,15] This leads to the

suppressed interface reflection over a wide range of wavelengths due to the effective

medium effect.[16] To avoid the abrupt refractive index (n) change at air/device

interface, SiO2is an attractive candidate AR material due to its intermediate refractive

index (n=1.56) between air (n=1) and GaN (n=2.5). Since structuring techniques that

require a high-cost lithography process might be a limit to the practical use, a process

with the nature lithography is of great interest due to its simplicity and effectiveness.

Therefore, SiO2 NRAs fabricated by simple and photoresist-free techniques are

particularly attractive to SC applications.[17]

Besides utilizing the added AR SWSs to improve the performances of InGaN SCs,

surface texturing using the structured p-GaN is also under consideration. For

surface texturing using the structured p-GaN is also under consideration. For

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