S-1

Supporting Information

Enhanced environmental stability coupled with a 12.5% power conversion

efficiency in an aluminum oxide encapsulated n-graphene/p-Silicon solar cell

Serdar Yavuz1, Erick M. Loran2, Nirjhar Sarkar1, David P. Fenning2, *, Prabhakar R. Bandaru1,2, *

1
Material Science and Engineering, Department of Mechanical Engineering

2
Department of Nanoengineering

University of California, San Diego, La Jolla, CA, 92093, USA

*Corresponding authors: dfenning@eng.ucsd.edu, pbandaru@ucsd.edu

S1. Device Fabrication

(a) Substrate preparation, (b) Graphene placement, (c) HF treatment,

(d) Atomic layer deposition (ALD) of AlOx, (e) Graphene field effect transistor (Gr-FET)

S2. Device Characterization

(a) Dark J-V analysis, (b) Raman Spectroscopy, (c) Electrical and Optoelectronic characterization

(d) External quantum efficiency, (e) Reflectance Measurements

S3. Structural Characterization

(a) XPS (x-ray photoelectron spectroscopy) analyses, (b) Atomic Force Microscopy (AFM)

(c) Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) mapping

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S1. Device Fabrication

(a) Substrate preparation: P-Silicon wafer with a resistivity of 1-10Ωcm covered with 200nm

PECVD SiO and patterned via photolithography followed by Au/Ti front and Al back contact
2

sputtering. Prior to the placement of the Gr on the front side, a buffered oxide etch (BOE:

constituted from NH F and HF in a 6:1 ratio) was used to remove the patterned SiO on the front
4 2

side. Subsequently, chemical vapor deposited (CVD) based single-layer graphene (SLG, obtained

from Grolltex) was placed on the front side using a wet transfer method dried overnight in ambient
1

air. All samples were annealed at 400°C for an hour under forming gas (H /N ), to remove any
2 2

polymer residue from the Gr and improve the contact between the Gr and Si substrate.

(b) Graphene placement: Single layer graphene synthesized through Chemical Vapor Deposition

(CVD) on Cu foil was obtained from Grolltex. PMMA was spin coated on Gr/Cu foil for a

mechanical support for the transfer of Gr. Cu foil was etched in 0.1M ammonium persulfate for 6

hours and free floating PMMA/Gr was transferred in DI water onto the samples2. After Gr transfer,

samples were left in ambient air overnight to dry, followed by removing PMMA through treatment

with acetone for 30 minutes and isopropyl alcohol for 1 min. Subsequently, samples were annealed

1 hour at 400°C under H2/N2 gas flow (10sccm) to improve the Gr/Si junction contact3

(c) HF treatment: After annealing graphene/p-silicon solar cells, from Set A, were exposed to HF

vapor at room temperature for 10 second. Similar treatment was applied to the Gr on glass for

Raman spectroscopy characterization. A schematic of process is shown in Figure S1.

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(a) (b)

Figure S1. (a) Schematic of HF treatment of graphene on glass prepared for Raman analysis.

Similar procedure applied for the HF treatment of solar cells. (b) Optical images of single layer Gr

on glass and SiO2 substrates.

AlOx/HF/Gr/p-Si solar cells (Set B) prepared with the above mentioned method. Following HF

treatment, an 80nm AlOx deposited directly on those set of wafers. In parallel to those samples,

AlOx/Gr/p-Si solar cells (Figure 3d) prepared by avoiding the HF treatment.

(d) Atomic layer deposition of AlOx: Atomic Layer Deposition (with the Beneq TFS200) used for

AlOx deposition. Trimethylaluminium (TMA) and water (H O) used as precursor with N gas flow
2 2

and deposition temperature set to 200°C. Deposition rate is found to be 1.01A per cycle by using

different number of cycles ranging from 50 to 1000 on polished (100) silicon substrate.

Ellipsometry (Rudolph Auto EL-III) was used to measure the thickness of the deposited AlOx.

(e) Graphene field effect transistor (Gr-FET): Around 300 nm PECVD SiO deposited on p-type
2

Silicon wafer (~1-10Ωcm ). Au/Ti electrical contacts were sputtered following the lithography
-1

process. CVD growth single layer graphene was suspended on contacts using the PMMA assisted

transfer process. After removing PMMA, a 4nm ALD-AlO deposited on top of graphene. The use
x

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of thin film of AlO was to minimize the contact resistance related issues since ALD is conformal.
x

Gate voltage applied through the back side of p-Silicon. This four pads contact pattern is also used

to measure the sheet resistance of Gr which is found to be ~400Ω/□.

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S2. Device Characterization

(a) Dark J-V analysis:

To extract related Schottky junction parameters (ɸb, Rs, and n) J-V analysis carried out in

a dark room at the absent of illumination (so called dark J-V measurements).

Figure S2. Dark ln(J)-V curves of bare Gr/p-Si and HF treated Gr/p-Si presented in Figure 1c.

Higher ɸb upon HF treatment indicates the possibility of n-doping brought by HF.

(b) Raman Spectroscopy: A Renishaw inVia (150W) Raman spectrometer with a laser excitation

of 514 nm was used to obtain the Raman spectra, which were calibrated using the Si 520 cm line. -1

Typically, Raman analysis of Gr is carried out on SiO /Si substrate. Since HF etches the SiO a
2 2

possible contamination/doping might be induced if SiO base substrate is used. To avoid such a
2

possibility, we carried out Raman analysis of HF treated Gr on glass. A glass slide clean in organic

solvents and dried with nitrogen before to Gr transfer. A PMMA assisted wet transfer process used

to transfer Gr onto glass and dried in ambient air over-night similar to solar cell fabrication process.

PMMA removed in acetone and isopropanol and before Raman characterization. Figure 3S shows

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a typical Raman analysis of Gr on glass. For the Raman analysis of ALD-AlO , the standard SiO /Si
x 2

substrate used with the above mentioned transfer process. A 4nm AlO deposited on Gr which
x

forms an AlO /Gr/SiO /Si while Gr/SiO /Si sample used as a control sample for this set up.
x 2 2

Figure S3. Raman spectrum of a typical bare Gr on glass (green), HF treated Gr on glass, (red

line). Glass substrate is used to avoid any etching related contamination to Gr from underlying

material. Orange line shows the Raman spectrum of bare Gr on SiO as a control sample. Blue line
2

shows the Raman spectrum of AlO coated Gr/SiO sample. Corresponding Raman parameters, by
x 2

using the bare samples as references, are summarized in the tables.

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(c) Electrical and Optoelectronic characterization:

Electrical current density (J)-voltage (V) characteristic of the Gr/Si based PV devices were

tested by a source meter (Keithley 2420) and a solar simulator (Newport 66905, 50-500Watt,

Xenon Lamp) under an illumination intensity of 100 mW/cm (AM1.5 G standard). The fill factor
2

(FF) and the maximum power point (MPP) of the solar cells was estimated from the J-V curves.

The device power conversion efficiency (PCE), was estimated from:

𝑉'( 𝐽+(
𝑃𝐶𝐸 = 𝐹𝐹 (S1)
𝑃,-

V is the open circuit voltage, J is short current density, and P is the input illumination power.
oc sc in

Figure S4 reports the J-V curve evolution of HF treated Gr/p-Si (Set A) solar cell.

Figure S4. (a) J-V curves of HF treated Gr/p-Si (HF/Gr/p-Si) solar cell over the period of 7 days.

Around 65% degradation of PCE indicates a possible counteracting by ambient exposure. (b) The

cross-section of device belongs to Set A samples is shown

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Table S1. Solar cell output parameters.

The number of tested samples per set is indicated in brackets

Jsc(mA/cm2) Voc (V) FF (%) PCE (%)

Gr/p-Si (15) 6.0 (±0.1) 0.195 (±0.021) 10.0 (±0.4) 0.1 (±0.0)

HF/Gr/p-Si (12) 26.5 (±0.2) 0.395 (±0.015) 58.2 (±1.1) 6.0 (±0.1)

AlOx/HF/Gr/p-Si/ (6) 34.5 (±0.2) 0.510 (±0.016) 71.1 (±1.0) 12.5 (±0.2)

AlOx/Gr/p-Si (5) 26.1 (±0.2) 0.412 (±0.021) 24.2 (±1.3) 2.6 (±0.3)

(d) External quantum efficiency:

A monochromator (Newport, CS260), equipped with a solar simulator, was used for

external quantum efficiency (EQE) measurements, as a function of wavelength (l). The response

was calibrated by a silicon photodiode (Thorlabs, S120VC). EQE, as defined through the ratio of

the number of collected electrical carriers (as measured by the electrical current) to the incident

photon intensity (measured through a photodiode) on the solar cell. The Jsc values were obtained

through the obtained EQE measurements of samples as follows:

1
𝐽+( = 3 𝐸𝑄𝐸( 𝜆)𝑥𝐸(𝜆)𝑥𝜆𝑥 𝑑𝜆 (𝑆2)
1240

Where, E(λ) is the standard solar spectrum and λ is the wavelength.

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(e) Reflectance Measurements:

We aimed to specifically enhance the EQE at the peak intensity of solar spectrum (~ 550nm

- 600nm). Considering that an ARC can provide minimum reflectance for a thickness: d =λ/4n, 0
4

we used a 80nm thick AlO (with refractive index of 1.75) to corresponds to a reflectance minimum
x

at λ~ 550 nm. Indeed, from Figure 2(b), the highest EQE of ~ 95% was obtained at such a

wavelength. For further confirmation, we carried out diffuse reflectance measurements with an

integrating sphere comparing a flat bare silicon and AlO /Si: Figure S5, below. A minimum
x

reflection (of ~3%) was obtained at λ~ 550 nm, which corresponds to an EQE of ~ 95%, as

reported. Of course, the increased reflection at other wavelengths reduces the EQE, as indicated in

Figure 2b. EQE of our AlO /HF/Gr/p-Si and reflectance spectrum of AlO /p-Si curves as function
x x

of wavelength is presented in Figure S6.

Figure S5. (a) Reflectance measurement is comparing a bare Si wafer to an 80nm AlO deposited
x

Si sample. (b) Optical images of samples used for reflectance measurements. It can be seen from

images that upon AlO deposition a darker color indicates reduced reflectance from silicon surface.
x

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Figure S6. EQE of AlO /Gr/p-Si/ sample and corresponding reflectance for AlO deposited Si
x x

(AlO /Si). The highest EQE is in accord with the lowest reflectance brought by ARC.
x

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S3. Structural Characterization

(a) XPS (x-ray photoelectron spectroscopy) analyses:

The HF vapor treatment reduces the interfacial oxide between the graphene and the underlying p-

Si substrate. We have performed XPS analysis of Gr/Si samples with and without HF treatment

and have seen that the underlying oxide is significantly removed – see Figure R1 below. The

graphene (synthesized through chemical vapor deposition) may have defects, such as holes5, and

may not be completely impervious to the HF.

(a) (b)

Figure S7. XPS spectra of Gr/Si sample (a) with and (b) without HF treatment. The relative area

of the Si 2p component corresponding to oxide is reduced by more than four times on the HF

treated sample compared to the untreated sample.

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The basis of HF doping Gr is based on an analogy with the effect of CsF - which has been

reported in literature[3], as responsible for electron transfer to the Gr and hence n-doping. We also

note that there is a tendency for forming fluorinated carbons/graphenes (see Figure R9 below). It

has been previously reported[4] that “strong donor doping (>1013 /cm2)” may occur, on F exposure,

and forms yet another basis for our assertion of n-doping.

Figure S8. The HF treatment results in fluorinated carbon, which may contribute to doping of the

graphene and/or the Si. It has been previously indicated[4] that fluorinated graphene (exposed to

atomic F formed by decomposition of xenon difluoride (XeF2) for less than 1 hour @ 700 C)

manifests donor-type/n-type doping.

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(b) Atomic Force Microscopy (AFM)

(a) (b)

Figure S9. AFM images of the (a) height, and (b) phase of AlOx coated Gr/Si samples.

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(c) Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS)

SiO2/Si

Figure S10. A scanning electron microscopy (SEM) image of a cross-section of the n-Gr/p-Si device
indicates ~ 80 nm of AlOx deposited through atomic layer deposition.

Figure S11. A top view of the device, indicating the AlOx layer, as well as the adjacent underlying Ti/Au.

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EDS: Elemental analysis of the deposited Aluminum oxide indicated a stoichiometry of AlO1.7.

Figure S12. Energy dispersive

spectroscopy (EDS) of the aluminum
oxide coating layer indicates a
stoichiometry corresponding to an
O:Al ratio of ~ 1.7.

Figure S13. The elemental mapping of the AlO1.7 coating layer placed on top of the solar cell.

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References

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R. S. Transfer of Large-Area Graphene Films for High-Performance Transparent

Conductive Electrodes. Nano Lett. 2009, 9 (12), 4359–4363.

(2) Yavuz, S.; Kuru, C.; Choi, D.; Kargar, A.; Jin, S.; Bandaru, P. R. Graphene Oxide as a P-

Dopant and an Anti-Reflection Coating Layer, in Graphene/Silicon Solar Cells. Nanoscale

2016, 8 (12).

(3) Shi, E.; Li, H.; Yang, L.; Zhang, L.; Li, Z.; Li, P.; Shang, Y.; Wu, S.; Li, X.; Wei, J.; et al.

Colloidal Antireflection Coating Improves Graphene-Silicon Solar Cells. Nano Lett. 2013,

13 (4), 1776–1781.

(4) Raut, H. K.; Ganesh, V. A.; Nair, A. S.; Ramakrishna, S. Anti-Reflective Coatings: A

Critical, in-Depth Review. Energy Environ. Sci. 2011, 4 (10), 3779.

(5) Narayanan, R.; Yamada, H.; Karakaya, M.; Podila, R.; Rao, A. M.; Bandaru, P. R.

Modulation of the Electrostatic and Quantum Capacitances of Few Layered Graphenes

through Plasma Processing. Nano Lett. 2015, 15 (5).

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