Layer compression and enhanced optical properties of few-layer graphene nanosheets

induced by ion irradiation

Yang Tan,,* Zhen Shang, Shavkat Akhmadaliev, Shengqiang Zhou, and Feng Chen,,**

School of Physics, State Key Laboratory of Crystal Materials, Shandong University,

Institute of Ion Beam and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf,

Graphene has been recognized as an attractive two-dimensional material for fundamental

research and wide applications in electronic and photonic devices owing to its unique properties.

The technologies to modulate the properties of graphene are of continuous interest to

researchers in multidisciplinary areas. Herein, we report on the first experimental observation

of the layer-to-layer compression and enhanced optical properties of few-layer graphene

nanosheets by applying the irradiation of energetic ion beams. After the irradiation, the space

between the graphene layers was reduced, resulting in a tighter contact between the few-layer

graphene nanosheet and the surface of the substrate. This processing also enhanced the

interaction between the graphene nanosheets and the evanescent-field wave near the surface,

thus reinforcing the polarization-dependent light absorption of the graphene layers (with 3-fold

polarization extinction ratio increment). Utilizing the ion-irradiated graphene nanosheets as

saturable absorbers, the passively Q-switched waveguide lasing with considerably improved

performances was achieved, owing to the enhanced interactions between the graphene

nanosheets and evanescent field of light. The obtained repetition rate of waveguide laser was

up to 2.3 MHz with a pulse duration of 101 ns.

KEYWORDS: Graphene, Ion irradiation, Q-switched waveguide laser, Layer-to-layer

1
Since the discovery in 2004, graphene has attracted great interest as a monolayer graphite sheet

for a broad spectrum of multidisciplinary applications in electronics, optics, biology, and

material sciences.1,2 Graphene has saturable absorption due to the Pauli blocking effect3 and hot

luminescence resulting from nonequilibrium carriers.4 The unique photonic and electronic

properties enable graphene as intriguing candidate for various electronic and optoelectronic

devices. For example, graphene has been demonstrated to have the potential to act as a biosensor

for DNA and glucose5 and can be used for the detection of individual gas molecules.6 In optics,

owing to the nonlinear absorption, graphene has been applied for ultrafast laser generation in

fibers and bulks as saturable absorbers (SAs) based on the energy-band structure.7,8 Moreover,

graphene nanosheets exhibit strong polarization-dependent absorption of the evanescent field

from photonic devices such as waveguides and fibers. This feature enables graphene-coated

optical fibers acting as broadband polarizers.9

The graphene technology offers large-area few-layer graphene nanosheets of high quality

synthesized on metal foils by the chemical vapor deposition (CVD) process.10,11 To fabricate

graphene-based devices, it is usually necessary to transfer the graphene nanosheets from the

surface of metals to the target substrates. To achieve a clean, easy transfer process for large-

area graphene nanosheets, the transfer technology is required for improvement in terms of speed,

uniformity, and close attachment with targets.12-14 The conventional methods for graphene

transfer include the exfoliation of several graphene layers from highly ordered pyrolytic

graphite by a mechanical 3M tape, or using electrostatic force and wet-transfer for CVD

graphene.15-17 These processes usually require long treatment cycles with the increment of

manufacturing costs, and much effort on the quality control of the transferred graphene.12

Recently, ion irradiation has been proved to be an efficient method to provide a perfect

lattice of graphene.18-21 During the ion-irradiation process, the energy of incident ions is

transferred onto graphene layers through nuclear collisions and electronic excitations, which

are characterized by so-called nuclear (Sn) and electronic (Se) stopping powers, respectively.
2
When Sn or Se is sufficiently high, controllable defects can be introduced into the few-layer

graphene nanosheets.22-27 Moreover, the ion irradiation of optical materials has been proved to

be an efficient method to develop optical waveguide structures by modifying the refractive

index of substrates. The successful examples include more than 100 materials of single crystals,

ceramics, and glasses.28-30 With the synergetic ion-irradiation-induced effects from both

graphene and optical materials, it is possible to develop novel graphene-on-chip devices for

diverse applications.

In this work, we demonstrate the irradiation of energetic ions (e.g., carbon or oxygen) as an

efficient method to modify the optical properties of transferred few-layer graphene nanosheets

with an area of 1 cm2. The ion irradiation not only reduces the space between the graphene

layers, remaining the number of layers unchanged, but enables an enhanced contact between

few-layer graphene nanosheets and substrate. Owing to this feature, the polarization-dependent

linear absorption of few-layer graphene nanosheets considerably increases. In addition, the ion

irradiation produces a planar optical waveguide below the graphene layer. With this one-step

irradiation processing, a platform with graphene coated planar waveguide structure has been

manufactured. In case of the substrate of laser crystals, such as the Nd:YAG crystal investigated

in the work, it is possible to achieve the graphene Q-switched waveguide lasing through the

interaction between the evanescent field of waveguide modes and ion-modified few-layer

graphene as SA. Excellent performances such as a stable emission, shortened pulse duration,

and increased repetition rate are obtained in the passively Q-switched waveguide laser systems.

This work also offers a new solution to modify the optical properties of transferred few-layer

graphene nanosheets in optical devices by ion irradiation.

The few-layer graphene nanosheets used in this work were fabricated by the CVD method

followed by multiple transfers. First, a bilayer graphene was fabricated by the CVD method on

copper and nickel disks. Then, the bilayer graphene was transferred four times to prepare few-

layer (eight layers) graphene nanosheets. The dimension of the graphene nanosheet was 1 cm2.
3
Two few-layer (eight layers) graphene nanosheets were irradiated by carbon (Sample 1) and

oxygen (Sample 2) ions. The oxyegn (O5+)-ion irradiation was carried out at an energy of 15

MeV and a fluence of 21014 ions/cm2 using a 3 MV Tandetron accelerator at Helmholtz-

Zentrum Dresden-Rossendorf, Germany. The carbon (C3+)-ion irradiation was carried out at an

energy of 6 MeV and a fluence of 11015 ions/cm2 using a 21.7 MV tandem accelerator at

Peking University, China.

Figures 1a and 1b show the microscopic images of few-layer graphene nanosheets

(transferred on a Nd:YAG crystal wafer) obtained by an atomic force microscope (AFM) before

and after carbon-ion irradiation (Sample 1), exhibiting an area of 2500 m2 and a vertical extent

of a few nanometers. As shown in Figure 1c, the maximum and minimum values of the surface

roughness of the graphene nanosheets before the irradiation were 37 and 7 nm, respectively.

The height variation (RMS 6.67 nm) was induced by bubble-like structures, which were formed

during the fabrication of few-layer graphene nanosheets through the multiple transfer of the

bilayer graphene. A perfect contact between each bilayer graphene is difficult to be achieved

over the large-area graphene nanosheets, forming extra space between the adjacent graphene

layers. After the carbon ion irradiation, the bubble-like structures inside the few-layer graphene

nanosheets disappeared, as shown in Figure 1b, and the height variation of graphene nanosheets

(RMS 3.00 nm) was shown as meandering wrinkles. As indicated in Figure 1c, the height of

the flat area of the nanosheet was varied from 17 to 5 nm. Extensive analysis of the AFM data

shown in Figures 1a and 1b revealed the two variations of graphene nanosheets induced by ion

irradiation: (i) the morphology of the graphene nanosheets changed from bubble-like structures

to meandering wrinkles (the surface of the graphene nanosheets became smooth); and (ii) the

average thickness of the graphene nanosheets decreased from 12.55 nm to 7.66 nm. The few-

layer graphene nanosheets possessed an enhanced contact with the Nd:YAG substrate. Two

possible reasons may be responsible for this phenomenon. One was that the graphene

nanosheets were directly sputtered by energetic ion beams, and the average thickness was
4
reduced due to the decrease in the number of graphene layers. The other was that the number

of layers was the same, whilst their appearance was changed by the ion irradiation process.

To confirm the origin of the ion induced effect, we utilized the Raman spectroscopy to

investigate the structural and electronic characteristics of the graphene nanosheets with and

without ion irradiation. Figure 2a shows the three intense bands in the spectra: (1) the major

Raman band of graphene (G band), (2) D band, and (3) 2D band. The Raman spectrum shown

in Figure 2a was normalized with the maximum intensity of the G band (red line). The intensity

of the D band clearly increased after the ion irradiation. The intensity ratio of the D and G bands

(ID/IG) in Raman spectroscopy was used to calculate the zero-dimensional point-like defects in

the graphene nanosheets after the ion-beam bombardment. The density of defects was usually

determined by the average distance of defects (LD). In the low-defect-density regime, LD can be

calculated as follows[31]:

I D 1
L2D(nm 2 ) 1.8 109 L4 ( ) (1)
IG

In this work, the ID/IG value was increased from 0.26 to 0.65 corresponding to the variation of

LD from 23.5 to 14.9 nm. Clearly, the defect density of graphene nanosheets was increased by

the carbon-ion-beam bombardment.

The energy deposition process of the ion bombardment was calculated by the well-known

computer programStopping and Range of Ions in Matter (SRIM 2013), [32] on the interaction

between carbon ions and few-layer graphene/Nd:YAG system. As shown in Figure 2b, the

percentage of displaced atoms induced by the ion irradiation was less than 0.01%, which was

too low to create significant damage of the graphene layer. This also suggests the maintained

number of graphene layers after the ion irradiation.

Further evidence was also obtained by the Raman spectroscopy. The 2D and G bands (shape

and intensity) can be used to determine the number of graphene layers.[33] Furthermore, the
5
intensity of the G band exhibited almost a linear relationship with the graphene thickness.

Compared to the spectra shown in Figure 2a, the relative intensity ratio of the 2D and G bands

was similar for the sample with and without ion irradiation. Thus, it can be concluded that the

number of graphene layers did not change after ion irradiation. To conclude, the layer number

of the few-layer graphene was not affected by the carbon ion irradiation in this work.

The smooth and compaction of graphene nanosheets can be attributed to the atomic

rearrangements during the ion irradiation. During the irradiation, most of the slowing down of

the ions occurs due to the loss in electronic energy (Se), particularly in the graphene layer in

this case. A large number of near-surface atoms in the graphene layer are set into motion by

this electronic excitation. The mobility results in atomic rearrangements including the

sputtering and re-deposition of carbon ions, consequently leading to the smoothing and

compaction.[34,35] In case of oxygen ion irradiation (Sample 2), the thickness of the graphene

nanosheets decreased to 5.17 nm, even less than the carbon ion irradiated sample (i.e., 7.66 nm

for Sample 1). Clearly, the space between the graphene layers can be adjusted to a certain value

by selecting an appropriate energy of incident ions.

The nonlinear absorption coefficient of the graphene nanosheets was measured by the single-

beam Z-scan technology. A 532-nm laser with 4-ns pulse duration and an energy of 1 J was

focused using a lens (a focal distance of 400 mm), resulting in 24.5-m beam waist. A large-

aperture lens was used for collecting the transmitted laser light. By moving the graphene

nanosheets around the focal point, the power of the transmitted light was measured as a function

of the distance from the focal point. The nonlinear absorption coefficient was calculated using

the eq 2, where z is the distance of the graphene nanosheet from the focal point, I is the intensity

of the focused laser, and 0 is the linear absorption coefficient.

dI
( 0 I ) I (1)
dz

6
 Figures 3a, 3b and 3c show the open-aperture Z-scan curves of Sample 1 (carbon-ion-

irradiated graphene nanosheets), Sample 2 (oxygen-ion-irradiated graphene nanosheets), and

the original sample (non-irradiated), respectively. The nonlinear absorption coefficients () of

the graphene nanosheets were -2.8 104 and -3.2 104 m/W for Samples 1 and 2, respectively.

Compared with the original sample (-3.0 104 m/W), the value slightly changed after the

irradiation. This indicates that the nonlinear absorption of the graphene nanosheets did not

change significantly after ion irradiation.

Graphene nanosheets were prepared by two methods for the linear absorption measurements:

1) Graphene nanosheets were coated on a neodymium-doped yttrium aluminum garnet

(Nd:YAG) crystal with dimensions of 10 10 1.5 mm3. Inside the graphene nanosheets, the

Nd:YAG crystal was irradiated by oxygen ions at an energy of 15 MeV and a fluence of 2

1014 ions/cm2 (Sample 2). The waveguide structure was fabricated on the surface of the

Nd:YAG crystal after ion irradiation. 2) The Nd:YAG crystal with same dimensions was

irradiated by oxygen ions at an energy of 15 MeV and a fluence of 2 1014 ions/cm2, and the

waveguide structure was fabricated. Then, the graphene nanosheet was coated onto the surface

of the Nd:YAG waveguide. The experimental setup is shown in Figure 4a. Linearly polarized

light at a wavelength of 1064 nm was coupled to the waveguide using a convex lens. By

changing the polarization angle of the input light by the waveplate, the power of the output light

was collected using a microscope objective and measured by varying the angle.

The maximum output occurred at 0or 180, and the minimum appeared at 90or 270. As

shown in Figures 3d and 3e, the graphene nanosheets resulted in an extinction of light with

different polarization angles. For the graphene without ion irradiation, the absorption of the

light at 1064 nm was 1.26 dB (0) and 0.16 dB (90), respectively. The extinction ratio of the

light with two polarizations was 1.1 dB (0 90). Moreover, the extinction ratio of the light

with ion irradiation increased to 3 dB. This indicates that the polarization-dependent absorption

7
was enhanced to a certain exntent. Because the graphene nanosheets were contacted tightly onto

the surface of the waveguide, a better overlap of the evanescence field and graphene nanosheets

occurred.

With the enhanced linear absorption and unchanged nonlinear absorption of the graphene

nanosheets, it is possible to apply it for the improvement of the performance in the Q-switched

waveguide laser system. The few-layer graphene nanosheets (eight layers) were first transferred

onto the surface of a Nd:YAG crystal, and the graphene-coated Nd:YAG crystal was irradiated

by oxygen ions at energy of 15 MeV and fluence of 2 1014 ions/cm2. In this work, the Nd:YAG

waveguide structure served as a laser resonator, and the graphene nanosheets were coated as SA.

Two specially designed mirrors were adhered to the end-facets of the planar waveguide to

construct a FabryPerot oscillator. A high reflectivity (HR) at 1064 nm (reflectivity, R >99.9%)

was observed with a high transmission (HT) at 810 nm (transmission, T >99.9%) for the input

mirror (M1). However, the out-coupling mirror (M2) had a T of 5% at 1064 nm. A laser with

a wavelength of 810 nm, obtained from a Ti:Sapphire CW laser (Coherent MBR PE), was

coupled into the waveguide as the pumping laser. The output light was collected using a long-

working-distance microscope objective.

The laser emission from the waveguide structure was obtained at a wavelength of 1064 nm

as shown in the inset of Figure 5a. The output power of 1064-nm laser as a function of the

pumping power is also shown in Figure 5a. The lasing threshold corresponding to the slope

efficiency of 2.6% was 75 mW. The maximum output power was 4.9 mW. Typical Q-switched

pulse trains were observed with the pumping power over the threshold as shown in Figure 5b.

The variations of the pulse duration and repetition rate with the pumping power are shown in

Figure 5a. Clearly, the pulse duration was stable at 101 ns with much higher pumping power

than the lasing threshold, a typical phenomenon for a passively Q-switched laser.36 The

8
repetition rate of the pulsed laser exhibited a linear variation with the pumping power, and the

maximum pulse repetition rate was up to 2.3 MHz.

An experiment for lasing was also conducted for a non-irradiated graphene SA as a

comparison. The waveguide structure was first produced on the surface of the Nd:YAG crystal

(without graphene layer covered) under the same ion-irradiation conditions. Then, the few-layer

graphene nanosheets (eight layers) were coated onto the surface of the waveguide. Under the

same pumping condition, the laser emission at a wavelength of 1064 nm was also obtained. The

output power as a function of the pumping power is shown in Figure 5b. However, no regular

pulse train was observed in this experiment. This can be explained by the previous discussion

on the linear absorption of graphene as shown in Figures 3d and 3e. Without the ion irradiation

of graphene, the contact between the graphene nanosheets and waveguide was not adequate

tight. Consequently, the absorption induced by the graphene nanosheets was too low to achieve

Q-switching for pulsed lasing. Moreover, a similar design was performed in Ref. [37], in which

an index-matching fluid was added onto the surface of the waveguide to increase the absorption

of the graphene. However, the absorption of the graphene nanosheets through the evanescent

field was still in a low level, generating the pulse duration larger than 10 s and the repetition

rate less than 29 kHz. In this work, with the enhancement of properties of graphene by ion

irradiation, the pulse duration was decreased from 10 s to 100 ns, and the repetition rate

was 2.3 MHz. This comparison shows advantages of ion-irradiation as an efficient technique to

improve the graphene-based Q-switching features.

In conclusion, the ion-irradiation was demonstrated as a novel method to enhance the

performance of graphene-based optical devices. For transferred graphene nanosheets on

Nd:YAG laser crystal, ion irradiation has shown the capability to improve the smoothness of

graphene and to enhance the contact between graphene and Nd:YAG crystal, resulting in

enhanced the linear optical absorption of the graphene. By utilizing this technique for passive

Q-switching, the pulsed lasing based on the graphene-coated waveguide system was
9
considerably improved, with stable pulses of 101ns duration and 2.3 MHz repetition rate. This

work also paves a way to improve performances of graphene-on-chip devices for various

applications.

AUTHOR INFORMATION
Corresponding Author

*E-mail: tanyang@sdu.edu.cn

**E-mail: drfchen@sdu.edu.cn

Notes

The authors declare no competing financial interest.

ACKNOWLEDGEMENTS
This work is carried out with the financial support by the National Natural Science Foundation

of China (No. U1332121). S. Z. acknowledges the financial support from the Helmholtz-

Association (VH-NG-713).

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Figure 1. Morphology of the few-layer graphene nanosheets before (a) and after (b) ion
irradiation captured by AFM. (c) Thickness of the few-layer graphene nanosheets along the
lines in (a) and (b).

Figure 2. (a) Raman spectra of the few-layer graphene nanosheets before and after ion
irradiation. (b) Relative atom displacement of the graphene lattice induced by ion irradiation.

15
Figure 3. Open-aperture Z-scan curves of the original sample (a), Sample 1 (b), and Sample 2
(c). Light extinction of the original sample (d) and Sample 3 (e) in different polarization angles.

Figure 4. (a) Experiment setup for the linear absorption measurements of few-layer graphene
nanosheets. (b) Experimental scheme for Q-switched waveguide laser operation.

16
Figure 5. (a) Power of the output pulsed laser as a function of the incident pumping power
modulated by the few-layer graphene nanosheets without (blue square) and with (red circle) ion
irradiation; the inset picture shows the spectrum of the output laser. (b) Pulse train of pulsed
waveguide laser with a pumping power of 158 mW. (c) Variation of the pulse duration and the
repetition rate of the graphene Q-switched pulsed waveguide laser as a function of the input
pump power.

17
Supporting Information

18