NREL is a national laboratory of the U.S. Department of Energy, Office of Energy 

Efficiency & Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

Contract No. DE-AC36-08GO28308

Novel R2R Manufacturable 

Photonic-Enhanced

Thin Film Solar Cells

January 28, 2010 — January 31, 2011

Dennis Slafer

Lightwave Power

Cambridge, Massachusetts

Vikram Dalal

Iowa State University

Ames, Iowa

Subcontract Report

NREL/SR-5200-54324

March 2012
NREL is a national laboratory of the U.S. Department of Energy, Office of Energy 

Efficiency & Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

National Renewable Energy Laboratory

1617 Cole Boulevard

Golden, Colorado 80401

303-275-3000 • www.nrel.gov

Contract No. DE-AC36-08GO28308

Novel R2R Manufacturable 

Photonic-Enhanced

Thin Film Solar Cells

January 28, 2010 — January 31, 2011

Dennis Slafer

Lightwave Power

Cambridge, Massachusetts

Vikram Dalal

Iowa State University

Ames, Iowa

NREL Technical Monitor: Harin S. Ullal

Prepared under Subcontract No. NEU-0-99010-05

Subcontract Report

NREL/SR-5200-54324

March 2012
This publication received minimal editorial review at NREL.

NOTICE

This report was prepared as an account of work sponsored by an agency of the United States government. 

Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, 

express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of 

any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately 

owned rights. Reference herein to any specific commercial product, process, or service by trade name, 

trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, 

or favoring by the United States government or any agency thereof. The views and opinions of authors 

expressed herein do not necessarily state or reflect those of the United States government or any agency thereof.

Available electronically at http://www.osti.gov/bridge

Available for a processing fee to U.S. Department of Energy

and its contractors, in paper, from:

U.S. Department of Energy

Office of Scientific and Technical Information

P.O. Box 62

Oak Ridge, TN 37831-0062

phone: 865.576.8401

fax: 865.576.5728

email: mailto:reports@adonis.osti.gov

Available for sale to the public, in paper, from:

U.S. Department of Commerce

National Technical Information Service

5285 Port Royal Road

Springfield, VA 22161

phone: 800.553.6847

fax: 703.605.6900

email: orders@ntis.fedworld.gov

online ordering: http://www.ntis.gov/help/ordermethods.aspx

Cover Photos: (left to right) PIX 16416, PIX 17423, PIX 16560, PIX 17613, PIX 17436, PIX 17721

Printed on paper containing at least 50% wastepaper, including 10% post consumer waste.
Table of Contents

1 SUMMARY ............................................................................................................................................. 1

1.1 Overall Program Results......................................................................................................1

1.1.1 Summary of Results by Quarter: Q1..........................................................................1

1.1.2 Summary of Results: Q2 ............................................................................................1

1.1.3 Summary of Results: Q3 ............................................................................................1

1.1.4 Summary of Results: Q4 ............................................................................................1

2 INTRODUCTION .................................................................................................................................... 2

2.1 Background ..........................................................................................................................2

2.1.1 Scattering Matrix Simulations ....................................................................................4

2.1.2 Fabrication of Nano Array Substrate ..........................................................................4

2.1.3 Fabrication of solar cell devices .................................................................................8

3 OBJECTIVES....................................................................................................................................... 11

3.1 Tasks and Results...............................................................................................................11

4 REVIEW OF MILESTONES & DELIVERABLES ................................................................................ 17

5 SUMMARY OF RESULTS ................................................................................................................... 18

APPENDIX A .............................................................................................................................................. 19

APPENDIX B .............................................................................................................................................. 24

APPENDIX C .............................................................................................................................................. 26

REFERENCES............................................................................................................................................ 36
1 

1 SUMMARY

1.1 Overall Program Results

The goal of this program was to produce tandem Si cells using photonic bandgap enhancement 

technology developed at ISU and Lightwave Power that would have an NREL-verified efficiency of 

7.5% on 0.25 cm2 area tandem junction cell on plastic substrates. This goal was met and exceeded 

within the timeframe and budget of the program. On smaller area cells, the efficiency was even 

higher, ~9.5% (not verified by NREL). Appropriate polymers were developed to fabricate photonic 

and plasmonic devices on stainless steel, Kapton and PEN substrates. A novel photonic-plasmon 

structure was developed which shows a promise of improving light absorption in thin film cells, a 

better light absorption than by any other scheme. Various aspects of this work have also been 

included in a paper in Appendix D. 

1.1.1 Summary of Results by Quarter: Q1

The work carried out during the first quarterly reporting period, 28 January, 2010 to 27 April, 2010 

included the design of the Photonic Band Gap (PBG) nanostructure for enhanced light trapping at 

the back of the PV cell, the fabrication of soft and hard tooling required to replicate the PBG 

structure, and production of flexible polymeric substrates having this structure, and the initial 

depositions of a-Si PV layers on PBG films. Contract Deliverable #1 was also successfully 

completed in Q1. 

1.1.2 Summary of Results: Q2

During the second quarterly reporting period, 28 April 2010 through 27 July 2010, the principal 

technical efforts included the formation and optimization of flexible substrates having the PBG 

nanostructure using the soft and hard tooling that was described in the previous Report. A number 

of a-Si PV devices were fabricated using the PBG substrate. Contract Deliverable #2 

(“Intermediate/Due 7/28”) was also successfully completed in this reporting period and delivered 2 

months early (NREL Test Results for 5/17/10, appended). 

1.1.3 Summary of Results: Q3

During the third quarterly reporting period, 28 July 2010 through 27 October 2010, technical efforts 

included fabrication of tandem junction solar cells and continued improvement of the nanoimprint 

process for forming flexible substrates having a PBG-enhanced substrate.

1.1.4 Summary of Results: Q4

For the fourth and final quarter of the program, running from 28 October 2010 through 31 January 

2011, the main technical focus was the fabrication of tandem junction cells on a PBG polymer 

substrate. Tandem junction solar cells, measured at NREL, showed an efficiency of ~7.6%, 

exceeding the target of 7.5%. Small area cells, measured at Iowa State but not at NREL, had even 

higher efficiency, between 8.5 and 9.0%. 

Unless otherwise noted, all images in this work are property of the authors.
2 

2 INTRODUCTION

2.1 Background

Photovoltaic energy conversion is a rapidly growing industry that amounted to about 2.8 GW of 

production in 2007, and has grown at an annual growth rate of approximately 40% over the last 5 

years [1]. It is now producing electricity at ~20c/kWh [2]. To be cost-competitive, the levelized cost 

of electricity (LCOE) produced has to be below 10 c/kWh. The current PV industry is based about 

90% on crystalline Si technology, using Si wafers. The remaining 10% is thin films, divided 

between thin film Si (both amorphous and microcrystalline or nano Si), CdTe and CIGS. Because 

of the high cost of Si wafers, the thin film market segment is growing very rapidly, with many 

industries having announced GW size manufacturing plants, including for both amorphous Si (a-Si) 

and nanocrystalline thin film Silicon (nc-Si)[3-5]. 

However, it is very clear that to achieve low cost LCOE, it is necessary to have both low cost and 

reasonable conversion efficiency. The present day a-Si based modules are only in the 8-9% range, 

and this lower efficiency has a detrimental impact on LCOE because the area related costs become 

too high. Nano Si panels with a tandem cell module based on amorphous/nano Si cell design exhibit 

efficiencies in the 10% range. To achieve lower LCOE, one has to increase efficiencies of thin film 

modules to the same range as efficiency of multi-crystalline Si modules, namely15%. To do this, it 

will be necessary to increase conversion efficiencies of tandem junction cells based on thin-film Si 

to 19-20% range from the present 15% [6]. This will require major changes in cell designs and 

architecture. Our project proposes a revolutionary new design that can achieve such higher 

efficiencies in the future.

One of the major disadvantages of any thin film Si technology is that the material has to be thin. In 

nano Si, the diffusion length is of the order of a few micrometers [7], which forces the thickness of 

the i layer in a p-i-n cell in nano Si to be of the order of 1-2 micrometer. Since Si is an indirect 

bandgap material, such a thin layer does not allow for efficient photon absorption. Therefore, one 

needs to enhance light absorption in the material. One way to do this is to use texturing leading to 

light trapping [8]. A popular texturing method is to use textured silver back reflector [9] followed 

by a ZnO layer, the combination of which increases light trapping. However, surface plasmons 

generated in textured silver limits this scheme to a factor of ~5 optical enhancement. To overcome 

this, we suggest a very novel scheme. The strategy is to use a photonic bandgap (PBG) as the back 

reflector (see Fig. 1 for a schematic diagram of the periodic PBG structure that we have invented). 

It consists of a periodic array of a conducting material such as ZnO, which acts as a 2 dimensional 

PBG diffraction grating, forcing incoming light to bend sideways. This light is totally internally 

reflected at the top surface, thereby creating light trapping and multiple light absorption. Computer 

simulations [10] indicate that such a PBG structure can enhance absorption by about a factor of 20 

(see Fig.2). The factor of 20 is far higher than a factor of 4-5 that is typical of textured Ag. 

To make such a structure, we have invented a new method--nano-imprinted plastic substrates coated

with a thin layer of silver followed by ZnO (see Fig. 3 for our new device geometry). The precisely 

formed nano-imprinted structure, coated with Ag/ZnO, act as a photonic bandgap. Note that our 

structure is revolutionary, in that we plan to use roll-to-roll (R2R) nano-imprinting technology on 

plastic substrates, a very different scheme from the normal way of making PBG structures which 
3 

relies on very high cost optical or e-beam lithography (see Fig. 4 for SEM of one of our PBG arrays 

etched into Si). We also plan to use a very low cost plastic substrate to deposit our nano-Si cell. 

Other approaches use a very expensive Kapton (polyimide) substrate, which limits its general 

applicability. In contrast, the goal of this program is to use PEN, which is a much lower cost 

substrate, and capable of reaching a ~230 °C working temperature. PEN can also easily support 

nano-imprinting. Thus, our eventual objective is to produce stable, high efficiency (19-20%) 

tandem junction cells based on a-Si/nano Si combination on low cost plastic substrates using an 

inexpensive roll-to-roll manufacturing technique. 

Fig 1. A photonic array for efficient back reflection

Fig 2. Calculated enhancement in light absorption (blue curve) using photonic reflector
4 

 

Fig 3. Our new proposed photonic PBG Fig 4. SEM of A photonic reflector array

array on PEN etched into Si wafers at Iowa State

2.1.1 Scattering Matrix Simulations

Summary

• Maxwell’s equations were solved in Fourier space 

• E, H fields were expanded in plane waves

• Both polarizations of the incident wave were calculated

• Structure (e.g. Solar cell) was divided into layers

• Within each layer, reflection and transmission were calculated

• All layers were put together and the reflection, transmission and absorption of the entire 

structure was calculated

• Fully parallelized– each frequency was sent to a different processor

The advantages of this approach over real space methods in that it can deal with very thick 

substrates and large variations of E, H fields. Another advantage is that it can analyze any number 

of layers, each with its own n and k values. The details of this work have been presented in several 

papers [11-13] and the interested reader is referred to these papers for details.

2.1.2 Fabrication of Nano Array Substrate

In order to form the photonic nanostructures required to trap incident light, a novel technology for 

producing such patterns in on polymeric substrates was used. This technology, called Advanced 

Surface Nanoforming (ASN), is capable of molding nano-array patterns on flexible films by a rollto-roll process. In this process, a master template is formed using 3-beam laser interferometry [14] 

to form a 3-axis standing wave interference pattern onto the surface of a photoresist-coated 

substrate, and development of the photoresist produces a hexagonal array of cells/pillars. This 

interference technique is capable of forming such patterns over large areas in a single exposure. 
5 

Control of the beam convergence angles and exposure/development conditions allows adjustment of 

the pitch and duty-cycle of the interference pattern (constructive and destructive optical field), 

shown schematically in Fig. 5. 

Fig 5. Use of multibeam laser interferometry to produce photonic array master pattern in a single 

exposure. 3-D pattern is formed after development of exposed photoresist

In order to form the photonic nanostructures over very large areas and inexpensively, a novel 

technology for producing such patterns in on polymeric substrates was used. This technology, 

called Advanced Surface Nanoforming (ASN), was developed for molding nano-array patterns on 

flexible films by a roll-to-roll process. Direct-write techniques, such as e-beam lithography, are 

used to form a single master template having the desired 3-D nano photo-plasmonic structures. The 

master template can be positive or negative (bumps or depressions), as the multi-generational 

replication process is capable of producing interchanged structures. For typical substrates, the ASN 

process uses precision Ni electroforming to create a family of nanoimprinting tools that are used to 

replicate the photonic pattern (see Fig. 6). 

Although outside the scope of this program, the process is designed for ultimate use in R2R 

manufacturing. Here, the Ni tool is formed into a cylinder, similar to that used in the graphic arts 

flexographic printing process and allows high-precision imprinting of radiation cured layers on 

flexible plastic and metal foil substrates. In this process, the rotary imprinting tool itself is

transparent and uses a new, solid-state radiation source to crosslink a liquid patterning polymer. 

This transparent rotary tool is used to continuously form the photo-plasmonic layer in a single 

unwind-to-rewind pass, which is followed by a subsequent pass in a R2R vacuum coater in which 

the conductive/reflective layers are deposited. This material will serve as the foundation substrate 

for the next steps, deposition of the tandem PV layers. The key R2R nanopatterning step is 

illustrated in the schematic in Fig. 7a, which shows an unwind station for feeding the carrier 

substrate into the pattern forming station, an in-line laser-based diffraction measurement station, 

and a rewind station for the patterned substrate. A photograph of an ASN pilot process machine is 

given in Fig. 7b. Fig. 8 shows the schematic of a R2R machine for sputtering the metal and ZnO 

layers, and Fig. 9 shows various photographs of the R2R type imprinter. 

These pilot processors have already been used to produce many thousands of feet of various 

nanopatterned substrates at a production rate of many square feet per minute, a process which 

would otherwise take many hours per square inch if direct write (e-beam, etc.) were required to 

form each pattern. 
6 

QuickTimeTM and a

 decompressor

are needed to see this picture.

substrate

unwind 

substrate 

rewind

ASN

station 

Q-measurement

station cleaning Station

HEPA module

 

Fig 7 (a, b). Schematic of ASN process for replicating photonic array (l), consisting of a substrate 

unwind station, film pre-cleaner, nanoimprint station, Q-measurement station, and rewind. 

Photograph on right shows the imprint station of a pilot R 2R imprint machine designed for 

processing 150mm wide substrates.

Fig 6. Process steps for forming durable manufacturing tooling and for imprinting photonic 

array on flexible substrate. Ni tool is electroformed from master pattern (left) and used to 

replicate pattern on flexible substrate (right) 
7 

Fig 8. R2R sputter coater used to deposit conductive and/or reflective layers on patterned substrate. 

Rolls of material made in the imprinter (Figs 2, 4) are unwound from left station so that the patterned 

surface faces down when traversing the deposition zones (i.e., no face-side contact to damage the 

nanopattern), then rewound onto right spool. Reflectivity can be measured after deposition zone(s) 

to control layer uniformity.

 

Fig 9. External views of MOD3 ASN processor/HEPA module (l, center); vacuum roll coater (r) with 

four in-line sputter cathodes (RF & DC magnetron) for depositing metallic and dielectric layers.

vacuum

chamber 

sputter sources

embossed

substrate 

unwind 

coated

substrate

rewind

embossed

surface

reflectance

measurement
8 

Ag

ZnO

Ag Ag Ag

ITO

nc-Si

 

Fig 10. Photo-plasmonic structure for enhancing light absorption. The structure is imprinted into a 

polymer that is coated on top of a steel substrate.

2.1.3 Fabrication of solar cell devices

The nano-imprinted substrates received from Lightwave Power have the photonic plasmon structure 

on them. They are cleaned in methanol and dried and then Ag is evaporated on them to a thickness 

of 200 nm in a thermal evaporator. Then, a 100 nm layer of Al doped ZnO is sputtered on the Ag 

coated photonic plasmon using a RF sputtering system and Ar as the sputter gas. The target is ZnO 

doped 1% with Al. Before depositing on the substrate, the target is cleaned for 2 minutes in an Ar 

plasma and then the shutter which isolates the substrate from the target is opened and ZnO:Al 

sputtered on Ag coated photonic plasmon. During the sputtering process, the pressure is maintained 

at 5 mTorr, the substrate temperature at 200 C, and the RF power at 75 W. 

Fabrication procedure for a-Si devices on photonic plasmon substrates

After sputtering of ZnO, the substrate is loaded into a VHF PECVD reactor for depositing the p-i-n 

a-Si:H cell. The VHF frequency is ~45 MHz. First, a n+ a(Si,C):H layer is deposited on the sample 

from mixtures of silane, methane, hydrogen and phosphine. The objective behind using a-(Si,C):H 

is to minimize absorption losses in the n+ layer, and allow reflected photons to traverse this layer 

with minimum absorption. Typical deposition conditions are to use T=250 C for the substrate and 

pressure of 50-100 mT. After depositing the n+ layer, the gases are evacuated and the chamber is 

purged 10 times with nitrogen to exhaust any residual phosphine. Then the chamber is purged with 

silane and hydrogen many times, and finally, a 15 minute plasma cleaning procedure is used to 

overcoat any n+ layers on the chamber walls[15]. During this procedure, the sample is covered with 

a shutter so as to prevent any deposition on it. After such a cleaning, the active I layer is deposited, 

followed by a very thin a-(Si,C) graded gap buffer layer [16] so as to prevent recombination of 

electron-hole pairs at the p-i interface. Finally, the top p+ layer is deposited using mixtures of 

silane, hydrogen, methane and diborane. The substrate temperature during the growth of the p layer 

is lower, about 200 C. The p layer is followed by the sputtering of 75 nm of ITO at a temperature 

of 150C. During this sputtering, the Ar gas is mixed with small amounts of oxygen so as to achieve 

the correct stoichiometry for ITO. Fig. 11 shows the typical optical absorption characteristics of the 

ITO layer. A thicker ITO layer is used for this measurement as compared to the thin ITO layer used 
9 

for devices. The thickness of the ITO layer for devices is based on achieving an optimum antireflection effect. A photograph of the reactor used for depositing a-Si is shown in Fig. 12. 

40

50

60

70

80

90

100

350 450 550 650 750 850 950 1050

% Transmission

Wavelength

Transmission on ITO

Fig 11. Transmission data for a thick ITO film

Fig 12. Plasma reactor used for depositing a-Si top cell

The tandem junction a-Si/nano Si solar cells are fabricated on photonic plasmon structures nanoimprinted into Kapton substrates. The substrates are coated with 200nm of Ag and 100 nm of ZnO 

as described above. After the deposition of ZnO, the substrates are moved to the reactor for 

depositing nano Si. It is a diode coupled VHF PECVD reactor capable of having layers deposited at 

frequencies ranging from a few MHz to 50 MHz. An Agilent signal generator is coupled into an 

Fabrication procedure for tandem junction a-Si/nano Si solar cells on photonic plasmon 

substr ates 
10 

ENI power amplifier that provides the power to the reactor. Typical frequencies that we use are ~45 

MHz. The typical growth temperatures for growing nano Si cells on the photonic plasmon 

substrates are ~225 C and pressure is 100mT. The i layer of the p-i-n cell cells was grown using a 

graded hydrogen:silane dilution ratio which varied during growth, decreasing from 3);1 at the 

initiation of the crystalline layer to about 15:1 at the end[17]. After the i layer deposition, a p+ nano 

Si layer was deposited from mixtures of silane, hydrogen and diborane, using VHF PECVD, again 

at 45 MHz frequency. 

Next, the top p-i-n a-Si cell was deposited, starting with the n+ layer. Next, an appropriate thickness 

of the amorphous Si i layer was deposited as described in paragraph 1 above. The thickness was 

calculated using optical constants of a-Si and nano Si so that the currents in the top and bottom cells 

could be matched. The I layer was followed by the buffer layer and the p+ a-Si layer as described 

above. Finally, a 75 nm ITO layer was deposited to make the ohmic contact, as described in 

paragraph 1 above. 

In Fig. 13, we show the I-V curve of a small area cell, ~0.105cm2, deposited on Kapton, with an 

efficiency of ~9.5% (not verified by NREL). Note the excellent fill factor, signifying very good 

properties for the p+/n+ tunnel junction, which connects the two cells. In Fig. 14, we show the 

corresponding quantum efficiency curves for each of the component cells showing the excellent 

agreement between currents produced in the top and the bottom cells. 

-0.5 0.0 0.5 1.0 1.5

-10

-5

0

5

10

Current Density (mA/cm2

)

Voltage (V)

Tandem on Kapton

Fig 13. I-V curve of small area a-Si/nano Si tandem junction solar cell on Kapton substrate. 
11 

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

400 600 800 1000

QE (Normalized)

Wavelength (nm)

Red Blue

Jred = 10.29 

Fig 14. QE curves for top and bottom cells measured using red light bias (top cell) and blue light 

bias (bottom cell).

Several papers have been published on device fabrication and results [18-20], and the interested 

reader is referred to these papers.

3 OBJECTIVES

The primary Technical Improvement Opportunities

1. To significantly improve light absorption in nano Si and thereby increase efficiency 

(TIO) for this project were:

2. Use a low cost plastic substrate and production-type photonic technology to reduce LCOE

The primary program objectives were:

1. To design and fabricate optimized nano-imprinted photonic bandgap light enhancement

structures and study their optical properties with thin film of nano Si deposited on them. 

2. To fabricate working solar cells on PEN substrates with the photonic structure with reasonable 

efficiencies in this first phase. For comparison, photonic bandgap PEN coated with Ag/ZnO will be 

evaluated against plain PEN coated with Ag/ZnO (control cell). A study of the quantum efficiency 

(QE) of the two cells will reveal how additional light absorption is achieved by our experimental 

cell. By achieving these objectives in this incubator phase, we can proceed to make efficient and 

stable tandem junction thin film Si based cells and modules in future projects. 

3.1 Tasks and Results 

The program began with a photonic band gap structure being generated by computer model. Using 

the model structure as input, the design was converted into a direct write tool path in a 
12 

semiconductor fab and reproduced in etched silicon (sketch of the mastering and replication process 

was previously shown in Fig. 6, and SEM of actual patterns are shown in Figs 15-16). Multiplebeam laser interferometry was also used to make master patterns, but the higher uniformity 

produced by the direct write process combined with its shorter ‘learning curve’ resulted in its 

selection as the preferred method for tooling generation within the constrains of the present 

program. We feel, however, that further development of the laser approach will ultimately provide 

a better approach for making very large-area nanopatterns. 

The silicon master formed by the direct write process was used to produce several sets of soft and 

hard tools (described previously, Sec 2.1.2) that in turn were used to produce the nanopatterned 

flexible substrates upon which the a-Si cells were built. It should be noted that only a single--

although very expensive--master silicon pattern was required for the entire program, and all of the 

subsequent soft and hard tool generations required for this program came from this single master. 

Since the master pattern was used only to form the working tools, this approach eliminated the 

concern of damaging or otherwise contaminating the Si master by using it for direct imprinting. The 

imprint tools used to produce the polymer replicas, on the other hand, were very inexpensive and 

could be replaced readily. Generation 1 and Generation 2 tools (“negatives” and “positives”) were 

both formed (in sequence) from the original master pattern, thus both bumps and holes could be 

formed through our process. With the peak-to-valley wavelength phase shift being essentially 

equivalent for both structures, both were evaluated during the program. The bump geometry was 

ultimately preferred over the hole geometry due to the former’s gentler sloping topography at the 

base of the structure that helped to eliminate the sharp angles that contributed to electrical layer 

shorting. 

The Gen-1 and Gen-2 tooling was used to form the PBG structure in various types of flexible 

polymer and foil films, including PET, Kapton, stainless steel and the preferred substrate, PEN. 

Numerous samples were produced with PBG-patterned areas of up to 3.5 x 3.5-in. Samples of these 

materials were analyzed using SEM and diffraction measurements to confirm the structure. SEMs 

of the master pattern in etched silicon are shown in Figs. 15 and 16, and polymer replicas made 

from tooling from this master pattern are given in Fig. 17. The completed design served as 

Deliverable #1 (Baseline Deliverable) for the program, which was completed on schedule. 

 

Fig 15. SEM of master pattern (etched silicon wafer) at various magnifications.
13 

 

 

Fig 16. SEMs of etched silicon master pattern (cups). Top three images are normal incidence view of 

surface of wafer after etching at various magnifications (holes are 750 nm dia). Bottom row shows 

cross-section of same holes at 2 magnifications.

Fig 17. Normal incidence SEMs of PBG polymer bump structures
14 

After PBG pattern was imprinted into polymer layer on flexible substrate, the film was placed into a 

vacuum chamber and outgassed prior to Si deposition in order to stabilize the polymer to resist the 

PE-CVD temperature (see Fig 18). The outgassing procedure that was developed was as follows:

 

Fig 18. SEMs of imprint polymer after outgassing tests (hole pattern shown). Outgassing was 

carried out prior to vacuum heating to improve temperature resistance of imprint polymer.

1. Samples were loaded individually through a load lock into a vacuum chamber preheated to 

300°C and pumped down to better than 6x10-7 Torr.

2. Transferring a sample into the main vacuum chamber caused the temperature to drop by 

about 100°C, which was then recovered within less than 2 min. 

3. Each sample was annealed for 2 hours in the vacuum better than 4x10-7 Torr.

4. Vacuum changes happening during this time were recorded. 

5. After the test, each sample was inspected by SEM. A control sample (obtained from the 

same sheet, i.e. prepared simultaneously with the test sample), which was not annealed, was 

inspected as well. 
15 

Fig 19. Evaluation of nanoimprinted polymer materials after vacuum annealing at elevated 

temperatures (stainless steel reference substrate used to eliminate substrate thermal effects) 

Figs. 18 & 19, showing the imprinted polymer layer before and after vacuum annealing (225C for 

30 min) indicate that the pattern is not deformed by high temperature annealing. Fig. 20 shows 

photographs of the imprinted polymer substrates illuminated so as to show diffractive separation of 

light at different angles of incidence due to the periodicity of the nanopattern. 
16 

Fig 20. Transparent polymeric substrate with nano-imprinted PBG layer (left: 5 mil thick PEN) and 

after metallization (right).

Multiple single junction cells were made during Q2 and sent to Dr. H. Ullal (late April 2010) and 

verified in May by NREL as having efficiency >4.5 %. These met the requirements of Deliverable 

#2, and the NREL test results are reproduced in Appendix A at the end of this report. 

Fabrication of Solar Cells

Program Tasks also included efforts to “improve PBG-patterned substrate with...improved 

temperature resistance.” Given the thermal limitations of the cost-effective substrates (PET & 

PEN), other substrates are being investigated to meet this requirement. By modifying our process 

for forming PBG patterns, we have been successful in incorporating them onto polyimide plastic 

films as well as inexpensive grade stainless steel foil (in gauges from ~12μm to 1.25mm). Such 

substrates will allow much higher CVD deposition temperatures and improved device performance. 

A photo of the PBG pattern on a 150mm x 150mm foil substrate is given in Fig. 21. 

By Q3, the nanoimprinting of the photonic substrate had been improved to the point that the desired 

pattern can routinely and accurately be reproduced on flexible polymeric (PEN or polyimide) 

substrates. The work then focused on improving throughput to enable sufficient substrates to be 

made to support the development of the tandem cells, and this was successfully accomplished 

during Q3. The resulting efficiency was higher than the target (7.5%), albeit on an area that is 

smaller. But it demonstrates that we can indeed achieve high efficiencies by using the photonic 

reflector concept on a flexible substrate. 
17 

4 REVIEW OF MILESTONES & DELIVERABLES 

The Milestones & Deliverables as set out in the SOW for Q1 were as follows:

Milestone 1 – Completion of PBG Structure Design* Month 1 2/28/10

Milestone 2 – Completion of NIL Tooling Month 2 3/28/10

Milestone 3 – PGB Pattern on Polymer Substrates Month 2 3/28/10

 Milestone 4 – Optical Measurement PBG Pattern Month 2 3/28/10

1st Quarterly Progress Report Month 3 4/28/10 

*Baseline Deliverable

All Milestones for Q1 were achieved on schedule (or slightly early).

The SOW Milestones & Deliverables for Q2 were as follows:

Milestone 5 - Demonstrate Solar Cell with Single 

Junction 4.5% Conversion Efficiency with a total area of 0.25 cm2 Month 6 +6 mo

2nd Quarterly Progress Report Month 6 +6 mo

All Milestones for Q2 were completed on time, and Task #5 was accomplished early.

The Milestones & Deliverables as set out in the SOW for Q3 are as follows:

3rd Quarterly Progress Report Month 9 +9 mo

Milestone 6 - Improved PBG Substrate Month 9 10/28/10

The Milestone for Q3 (#6) was completed during this reporting period. 

The Milestone & Deliverable for Q4 was as follows:

Milestone 7 - Demonstrate Tandem Solar Cells with 

7.5% Conversion Efficiency with a total are of 0.25cm2 Month 12 1/28/11 

The Final Milestone (#7) and Final Deliverable was completed on time during the final reporting 

period. Results from NREL testing are given in Appendix B. 
18 

5 SUMMARY OF RESULTS

In summary, subcontractor has delivered on all the Goals, Milestones & Deliverables of the 

research project. As described above, LWP/ISU has fabricated novel photonic structures on plastic 

substrates, fabricated tandem junction a-Si/nano Si solar cells on these flexible substrates, and has 

demonstrated that the use of such plastic substrates increases the short-circuit current generated in 

the solar cells significantly. Total-area, conversion efficiency of 4.62% for single junction a-Si solar 

cell has been demonstrated, and for the tandem junction a-Si/nano-Si solar cell total-area 

conversion efficiency achieved was 7.6% on plastic substrates. Two scientific papers were 

published as a result of this research effort. 
19 

APPENDIX A

Statement of Completion of Delivery #2

Subcontract No. NEU-0-99010-05 

Prime Contract No. DE-AC36-08GO28308 

NREL Report Summary:
20 
21 
22 
23 
24 

APPENDIX B

I-V and QE Curves

Fig. 1 I-V curve with J~9.8 mA/cm2, Voc~1.40 V and FF ~0.62, for an efficiency of ~8.5% on an area of 

0.12cm2

. 

-1.5

-1

-0.5

0

0.5

1

1.5

1.5 -1 -0.5 0 0.5 1 1.5 2
25 

Fig. 2 QE of the components of tandem cell measured using blue and red bias.

Norm QE Blue

Norm QE Red
26 

APPENDIX C

Statement of Completion of Final Deliverable

Subcontract No. NEU-0-99010-05 

Prime Contract No. DE-AC36-08GO28308 
27 
28 
29 
30 
31 
32 
33 
34 
35 
36 

REFERENCES

1. See www.solarbuzz.com

2. http://solarbuzz.com/facts-and-figures/retail-price-environment/solar-electricity-prices

3. http://www.uni-solar.com/

4. Y. Nakata, Proceedings of 2011 IEEE Technology Management Conference (ITMC) (2011)

5. http://www.solarpanelbuzz.com/solarpanels.kaneka.html

6. B. Yan Baojie; G. Yue, L. Sivec, J. yang and S. Guha, Appl. Phys. Lett. 99,

7. A. V. Shah, J. Meier, E. Vallat-Sauvain, N. Wyrsch, U. Kroll, C. Droz and U. Graf, Solar 

Energy Materials and Solar cells, 

Article Number: 

113512 (2011)

78

8. J. Müller, O. Kluth, S. Wieder, H. Siekmann, G. Schöpe, W. Reetz, O. Vetterl, D. 

Lundszien, A. Lambertz, F. Finger, B. Rech and H. Wagner, 

Solar Energy Materials and Solar Cells, 

, 469 (2003)

66

9. B. Yan, G. Yue, L. Sivec, J. yang, S. Guha, Proc. Of Conference: SPIE Conference On Thin 

Film Solar Technology II Location: San Diego, CA (2010)

, 275(2001)

10. Rana Biswas, Dayu Zhou, Proc. Of MRS, 989- A03-02 (2007)

11. D. Y. Zhou and R. Biswas, J. Appl. Phys. 103

12. B. Curtin,R. Biswas, V. L. Dalal et al, Appl. Phys. Lett.,

, May 2008. 

95

13. Biswas Rana; Xu Chun; Optics Express,

, 2009. 

19, 

14. J. J. Cowan, Aztec surface-relief volume diffractive structure, OSA A, Vol. 7, Issue 8, pp. 

1529-1544 (1990)

A664-A672 (2011) 

15. A. Vaseashta, V. L. Dalal, A. Greenwald and W. Halverson, Proc. of 18th. IEEE Photovolt. 

Spec. Conf., 847(1985)

16. V. L. Dalal, M. Leonard, J. F. Booker and A. Vaseashta, Proc. of 18th. IEEE Photovolt. Spec. 

Conf., 847(1985)

17. B. J. Yan, G. Z. Yue, Yang J and S. Guha, Appl. Phys. Lett. 85

18. S. Pattnaik, N. Chakravarty, D. Slafer, R. Biswas and V. L. Dalal, Paper presented at 2011 

MRS Conference in San Francisco, Symp. A (2011)-under print. 

,1955 (2004)

19. S. Pattnaik, V. Dalal, D. Slafer and Jin Ji, Proc. of IEEE PVSC (2010)

20. Bhattacharya Joydeep; Chakravarty Nayan; Pattnaik Sambit; Biswas, R; Dalal V.L.

Source: Appl. Phys. Lett. 99, Article # 131114 (2011)