Single-shot femtosecond laser ablation experiments with linearly and circularly polarized light were conducted in order to investigate the morphological characteristics of surface nanostructures in lithium borate crystals and glasses, a strontium borate crystal, lanthanide containing borate crystals, and aluminate silicate crystals: Li2B4O7 (LTB) and LiB3O5 (LBO) crystals and Li2O⋅2B2O3 (LTB) and Li2O⋅3B2O3 (LBO) glasses; SrB4O7 (SBO) crystal; Li6Gd(BO3)3 (LGB) and LaSc3(BO3)4 (LSB) crystals; and Ca2Al2SiO7 (CAS) and CaSrAl2SiO7 (CSAS) crystals. In the present study, the material and laser polarization dependance of the morphology of nanoholes was examined in these crystals and glasses. A single nanohole or two holes (a primary hole and a secondary hole) were observed in the borate and aluminate silicate crystals. The size of the nanohole is not restricted by the diffraction limit but instead is dependent on the laser fluence and the materials. It is suggested that the formation of these secondary nanoholes in the studied crystals is attributed to a spontaneous reshaping of the incoming Gaussian pulse into a Gaussian–Bessel pulse. In the LTB and LBO crystals, nanoholes (both primary and secondary holes) with subwavelength sides exhibit a quadrilateral (approximately square or rectangular) morphology, regardless of linear or circular polarization. The sides of the quadrilateral nanoholes lie approximately in the {h h 0} planes on the LTB crystal and in the ({h 0 0} and {0 0 l}) planes on the LBO crystal. We found that the nanohole morphology did not reflect the spatial distribution of the laser intensity. These phenomena were the first observations on the anisotropic morphology of nanoholes. These morphologies do not correspond to the circular symmetric pattern of the Gaussian intensity distribution of the incoming laser beam. This is contrary to the expectations based on the generally accepted laser ablation mechanism. The quadrilateral nanoholes could be an inherent morphology in the LTB and LBO crystals. The morphology of the quadrilateral holes in the LTB and LBO crystals is considered to reflect the continuous BO33− and/or BO45− network structure in their respective tetragonal or orthorhombic unit cells, in which self-tapped excitons are formed in an initial process under multiphoton excitation. In contrast, the SBO, LGB, LSB, CAS, and CSAS crystals and the LTB and LBO glasses exhibit circular nanoholes with subwavelength diameters independent of the laser polarization, the structure, or the composition. The isotropic morphology of nanoholes in these samples reflects the circular pattern of the Gaussian intensity profile of the focused laser beam.

1.
E.
Miyai
,
K.
Sakai
,
T.
Okano
,
W.
Kunishi
,
D.
Ohnishi
, and
S.
Noda
, “
Lasers producing tailored beams
,”
Nature
441
,
946
947
(
2006
).
2.
Y.
Shimotsuma
,
P. G.
Kazansky
,
J.
Qiu
, and
K.
Hirao
, “
Self-organized nanogratings in glass irradiated by ultrashort light pulses
,”
Phys. Rev. Lett.
91
,
247405
(
2003
).
3.
N.
Koadama
,
K.
Saito
,
T.
Nakaya
,
T.
Takahashi
,
D.
Shibata
, and
H.
Takeda
, “
Formation of periodicsurface nanostructures on Ti3+:Al2O3 crystals using femtosecond laser pulses
,”
Appl. Surf. Sci.
257
,
686
690
(
2002
).
4.
K.
Kawamura
,
M.
Hirano
,
K.
Kamiya
, and
H.
Hosono
, “
Holographic writing of volume-type microgratings in silica glass by a single chirped laser pulse
,”
Appl. Phys. Lett.
81
,
1137
1139
(
2002
).
5.
Y.
Han
and
S.
Qu
, “
Two-dimensional ‘hat-scratch’ periodic structures induced by a single femtosecond laser pulse on silica glass
,”
Appl. Surf. Sci.
255
,
7524
7528
(
2009
).
6.
R. R.
Gattass
and
E.
Mazur
, “
Femtosecond laser micromachining in transparent materials
,”
Nat. Photonics
2
,
219
225
(
2008
).
7.
W.
Yang
,
P. G.
Kazansky
, and
Y. P.
Svirko
, “
Non-reciprocal ultrafast laser writing
,”
Nat. Photonics
2
,
99
104
(
2008
).
8.
M.
Lenzner
,
J.
Kruger
,
S.
Sartania
,
Z.
Cheng
,
C.
Spielmann
,
G.
Marron
,
W.
Kautek
, and
F.
Krausz
, “
Femtosecond optical breakdown in dielectrics
,”
Phys. Rev. Lett.
80
,
4076
4079
(
1998
).
9.
A. P.
Joglekar
,
H.
Liu
,
G. J.
Spooner
,
E.
Meyhofer
,
G.
Mourou
, and
A. J.
Hunt
, “
A study of the deterministic character of optical damage by femtosecond laser pulses and applications to nanomachining
,”
Appl. Phys. B.
77
,
4076
4079
(
2003
).
10.
P. P.
Pronko
,
S. K.
Dutta
,
J.
Squier
,
J. V.
Rudd
,
D.
Du
, and
G.
Mourou
, “
Machining of sub-micron holes using a femtosecond laser at 800 nm
,”
Opt. Commun.
144
,
106
110
(
1995
).
11.
M.
Hashida
,
A.
Semerok
,
G.
Gobert
,
G.
Petit
,
Y.
Izawa
, and
J. F.-
Wagner
, “
Ablation threshold dependence on pulse duration for copper
,”
Appl. Surf. Sci.
197–198
,
862
867
(
2002
).
12.
Y.
Yasumaru
,
K.
Miyazaki
, and
J.
Kiuchi
, “
Femtosecond-laser-induced nanostructure formed on hard thin films of TiN and DLC
,”
Appl. Phys. A
76
,
983
985
(
2003
).
13.
T. O.
Jia
,
Z. Z.
Xu
,
R. X.
Li
,
D. H.
Feng
,
X. X.
Li
,
C. F.
Cheng
 et al., “
Mechanisms in fs-laser ablation in fused silica
,”
J. Appl. Phys.
95
,
5166
5171
(
2004
).
14.
S.
Guizard
,
A.
Semerok
,
J.
Gaudin
,
A.
Hashida
,
P.
Martin
, and
F.
Quere
, “
Femtosecond laser ablation of transparent dielectrics: measurement and modelisation of crater profiles
,”
Appl. Surf. Sci.
186
,
364
368
(
2002
).
15.
S.
Nolte
,
C.
Monma
,
G.
Kamlage
,
A.
Ostendortf
,
C.
Fallnich
,
F. V.
Alvensleben
, and
H.
Welling
, “
Polarization effects in ultrashort-pulse laser drilling
,”
Appl. Phys. A. Mat. Sci. Process
68
,
563
567
(
1999
).
16.
C. S.
Nielsen
and
P.
Balling
, “
Deep drilling of metals with ultrashort laser pulses: A two-stage process
,”
J. Appl. Phys.
99
,
093101
(
2006
).
17.
D. J.
Little
,
M.
Ams
,
P.
Dekker
,
G. D.
Marshall
, and
J. N.
Dawes
, “
Withford, femtosecond laser modification of fused silica: The effect of writing polarization on Si-O ring structure
,”
Opt. Express
16
,
20029
20037
(
2008
).
18.
P. G.
Kazansky
,
W.
Yang
,
E.
Bricchi
,
J.
Bovatsek
,
A.
Arai
,
Y.
Shimotsuma
,
K.
Miura
, and
K.
Hirao
, “
‘Quill’ writing with ultrashort light pulses in transparent materials
,”
Appl. Phys. Lett.
90
,
151120
(
2007
).
19.
N.
Kodama
,
H.
Kubota
,
M.
Kudo
, and
T.
Takahashi
, “
Radiative decay of intrinsic luminescence from self-trapped excitons in orthoborates with plural nonequivalent BO33- groups upon VUV excitation
,”
UVSOR Act. Rep.
44
,
59
(
2017
).
20.
S.
Natalia
,
B.
Rimma
,
S.
Jurii
,
F.
Stanislav
, and
Y.
Olga
, “
Li2B4O7 crystal structure in anharmonic approximation at 20, 200, 400 and 500 °C
,”
J. Alloys. Compd.
428
,
290
296
(
2007
).
21.
Y. F.
Shepelev
,
R. S.
Bubnova
,
S. K.
Filatov
,
N. A.
Sennova
, and
N. A.
Pilneva
, “
LiB3O5 crystal structure at 20, 227 and 377 °C
,”
J. Solid State Chem.
178
,
2987
2997
(
2005
).
22.
S.
Block
,
A.
Perloff
, and
C. E.
Weir
, “
The crystallography of some M2+ borates
,”
Acta Cryst.
17
,
314
315
(
1964
).
23.
A. N.
Shekhovtsov
,
A. V.
Tolmachev
,
M. F.
Dubovik
,
E. F.
Dolzhenkova
,
T. I.
Korshikova
,
B. V.
Grinyov
,
V. N.
Baumer
, and
O. V.
Zelenskaya
, “
Structure and growth of pure and Ce3+-doped Li6Gd(BO3)3 single crystals
,”
J. Cryst. Growth
242
,
167
171
(
2002
).
24.
G. M.
Kuz’micheva
,
V. B.
Rybakov
,
S. A.
Kutovoi
,
O. V.
Kuz’min
, and
V. L.
Panyutin
, “
Morphotropic series of LnSc3(BO3)4 compounds
,”
Crystallogr. Rep.
45
,
910
915
(
2000
).
25.
M.
Kimata
, “
The structural properties of synthetic Sr-gehlenite Sr2Al2SiO7
,”
Z. Kristallogr.
167
,
103
116
(
1984
).
26.
R.
Kelly
and
A.
Miotello
, “
Comments on explosive mechanisms of laser sputtering
,”
Appl. Surf. Sci.
96–98
,
205
215
(
1996
).
27.
S. S.
Mao
,
F.
Quere
,
S.
Guizard
,
X.
Mao
,
R. E.
Russo
,
G.
Petite
, and
P.
Martin
, “
Dynamics of femtosecond laser interactions with dielectrics
,”
Appl. Phys. A
79
,
1695
1709
(
2004
).
28.
P. L.
Kelley
, “
Self-focusing of optical beams
,”
Phys. Rev. Lett.
15
,
1005
1008
(
1965
).
29.
A.
Dubietis
,
E.
Gaizauska
,
G.
Tamosauska
, and
P.
Trapani
, “
Light filaments without self-channeling
,”
Phys. Rev. Lett.
92
,
253903
(
2004
).
30.
P.
Polesana
,
M.
Franco
,
A.
Couairon
,
D.
Faccio
, and
P. Di.
Tirapani
, “
Filamentation in Kerr media from pulsed Bessel beams
,”
Phys. Rev. A
77
,
043814
(
2008
).
31.
B.
Delobelle
,
R.
Salut
,
F.
Courvoisier
, and
P.
Delbelle
, “
A detailed study through the focal region of near-threshold single-shot femtosecond laser ablation nano-holes in borosilicate glass
,”
Opt. Commun.
284
,
5746
5757
(
2011
).
32.
T.
Sugawara
,
R.
Komatsu
, and
S.
Ueda
, “
Linear and nonlinear optical properties of lithium tetraborate
,”
Solid State Commun.
107
,
233
237
(
1998
).
33.
M.
Sheik-Bahae
and
M.
Ebrahimzadeh
, “
Measurements of nonlinear refraction in the second-order χ(2) materials KTiOPO4, KNbO3, β-BaB2O4, and LiB3O5
,”
Opt. Commun.
142
,
294
298
(
1997
).
34.
E. E. B.
Campbell
,
D.
Ashkenski
, and
A.
Rosenfeld
, “
Ultra-short-pulse laser irradiation and ablation of dielectrics
,”
Mater. Sci. Forum
301
,
123
144
(
1999
).
35.
J.
Li
,
G. G.
Duan
,
Z. Q.
Gu
, and
D. S.
Wang
, “
First-principles calculations of the electronic structure and optical properties of LiB3O5, CsB3O5, and BaB2O4 crystals
,”
Phys. Rev. B
57
,
6925
6932
(
1998
).
36.
A. J.
Fisher
,
W.
Hayes
, and
A. M.
Stoneham
, “
Structure of the self-trapped exciton in quartz
,”
Phys. Rev. Lett.
64
,
2667
2670
(
1999
).
37.
X. A.
Shen
,
S. C.
Jones
, and
P.
Braunlich
, “
Laser heating of free electrons in wide-gap optical materials at 1064 nm
,”
Phys. Rev. Lett.
62
,
2711
2713
(
1989
).
38.
X. A.
Shen
,
S. C.
Jones
,
X. A.
Shen
,
P. F.
Braunlich
,
P.
Kelly
, and
A. S.
Epifanov
, “
Mechanism of prebreakdown nonlinear energy deposition from intense photon fields at 532 nm in NaCl
,”
Phys. Rev. B
35
,
894
897
(
1987
).
39.
F.
Agullo-Lopez
and
P. D.
Townsend
, “
Interstitial motion during radiation damage and sputtering processes
,”
Phys. State Solidi B
97
,
575
580
(
1980
).
40.
B.
Delobelle
,
F.
Courvoisier
, and
P.
Delobelle
, “
Morphology study of femtosecond laser nano-structured borosilicate glass using atomic force microscopy and scanning electron microscopy
,”
Opt. Lasers Eng.
48
,
616
625
(
2010
).
41.
K. C.
Mishra
,
B. G.
DeBoer
,
P. C.
Schmidt
,
I.
Osterloh
,
M.
Stephan
,
V.
Eyert
, and
K. H.
Johnson
, “
Electronic structures and nature of host excitation in borates
,”
Ber. Bunsenges. Phys. Chem.
102
,
1772
1782
(
1998
).
42.
M.
Yamaga
,
Y.
Tanii
,
N.
Kodama
,
T.
Takahashi
, and
M.
Honda
, “
Mechanism of long-lasting phosphorescence process of Ce3+-doped Ca2Al2SiO7 melilite crystals
,”
Phys. Rev. B
65
,
235108
(
2002
).
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