Beijing Center for Crystal R&D,T h i l I tit t f Ph i d Ch i t

陈 创 天(Chuangtian Chen)

Technical Institute of Physics and Chemistry,Chinese Academy of Sciences

陈 创 天(Chuangtian Chen)

Recent Advances for UV and DeepRecent Advances for UV and Deep--UV UV

Co-Workers:

NLO Crystals and ApplicationsNLO Crystals and ApplicationsCo-Workers:Watanabe’s group,Institute for Solid State Physics, University of TokyoZ Y X ’ GZu-Yan Xu’s GroupInstitute of Physics, Chinese Academy of SciencesJi-Yang Wang’group,State Key Laboratory of Crystal Materials,Shandong University

Nonlinear Optics and NLO CrystalsNonlinear Optics and NLO Crystals

Ruby 694 nm laser focused on quartz to produce 347 nm UV laser, q p

Very low efficiency.(P t F k t l 1961)(Peter Franken et al. 1961)

ω2ω

ω2)2(χχ ω

Birefringence Phse Matching (BPM)

ω ω2

ω)2(χ

λπβ ωω

nkkLcII •=⎟

⎠⎞

⎜⎝⎛ Δ=

2,2

sin 22

02 12 =−=Δ ωωω{λ⎠⎝ 2

12

02 12 =−=Δ kkk{ne(2ω) = no(ω)

P D Maker et al PRLP.D.Maker et al., PRL1962

Laser promotes NLO crystal researchNLO crystal stimulates laser application

Na0

e

νh Er

+-

E

ω2ω’ω

ω)2(χ To produce new

wavelength

KTIOPO CRYSTAL GROWTHKTIOPO4 CRYSTAL GROWTH

hHistory of KTP research

1890 Ouvrard First synthesise of KTP

1971 R Masse RTP TlTP crystal structure1971 R.Masse RTP TlTP crystal structure

1974 I.Tordjman KTP crystal structure

1976 F C Z J D Bi l i1976 F.C.Zumsteg, J.D.Bierlein

confirm KTP as NLO crystal

Flux growth of KTP crystalFlux growth of KTP crystal

TSSG GROWTH KTP CRYSTALTSSG GROWTH KTP CRYSTAL

TSSG GROWTH KTP CRYSTALTSSG GROWTH KTP CRYSTAL

Application of 193nm laser

193 nm Laser Source

Semiconductor industry・lithography・alignment

Spectroscopy

alignment・inspection

BiotechnologyMedical instruments

― 2 ―

Nikon Core Technology Center

Ablation on enucleated pig eyes

Condition & Results• Average power : 3mW at 10 kHz

I di t d 1 1 (PTK)• Irradiated area : 1mm x 1mm (PTK)• Exposure time : 9 minutes• Ablated depth : > 200 micron

SEM imageOptical microscope image

― 21 ―

Nikon Core Technology Center

Important applications

(1) Precision processing and micro-machining

(266 nm) and in the future (193 nm and 177.3 nm)

(2) Ph li h h 193 d 157 (?)(2) Photolithography: 193 nm and 157 nm (?)

(3) Fabrication of photonic devices (193 nm and(3) Fabrication of photonic devices (193 nm and

177.3 nm)

(4) Medical application( fs,193 nm in particular)

(5) L Ph t i i t t(5) Laser Photoemission spectrometer

Anion group theory

The structure for high NLO effects:

Anion group theory

e st uctu e o g O e ects

1. Basic structure for NLO crystal：Molecule and group;

2. For anion groups:

(1) Polyhedrons, large distortion;

(2) Lone electron pair;

(3) C j t d t l(3) Conjugated systems, planar.

3. Space effect: geological additive: NaSbF5, KB5

4. As much as possible in a unit volume.

Borate crystal chemistry1) A boron atom can link either three oxygen atoms to form atriangular BO3 group or four oxygen atoms to form atetrahedral BO4 group.

2) P l b t f d f th t i l d

BO3 BO4

2) Polyborate groups are formed from these triangles andtetrahedra by corner-sharing. In the groups containing threeor more boron atoms the basic structure is a six-membered-or more boron atoms, the basic structure is a six-membered-ring with alternate boron and oxygen atoms.

B3O6 B3O7 B3O8 B3O9

Crystals with B3O6 groupCrystals with B3O6 group

UV b ti d 189UV absorption edge: 189nm

NLO coeffs: d22=4.1×d36(KDP)

BBO crystal d31=0.07 d22

Damage threshold: 10GW/cm2

C.Chen et al.,Sci. Sin. B28, 235(1985)

Damage threshold: 10GW/cm

( )

BBO has been widely applied to harmonic generations in the visible and UV spectral region.p g

Because of the limitation of the bandgap, It can not be used in DUV rangeDUV range.

Basic properties of LBO crystalBasic properties of LBO crystalUV absorption: 160nmNLO: d = 2 5 d (KDP) d = 2 7 d (KDP)NLO: d31 2.5 d36(KDP) d32 2.7 d36(KDP)Damage threshold: 25 GW/cm2 (0.1 ns, 1064 nm)Birefringence : 0 04

Due to the very high damage threshold relatively

Birefringence : 0.04

Due to the very high damage threshold, relatively large NLO coefficients and wide transparent range, LBO is one of the mostly effective materials availableLBO is one of the mostly effective materials available at present for the UV and visible generation.

The birefringence of LBO is too small to produce harmonic generation in the deep UV.

Bulk LBO

Crystal with B3O7 group

CBO (CsB3O5 Crystal) YW l A l Ph L 62 2614Y.Wu et al., Appl. Phys. Lett. 62, 2614

(1993)UV absorption: 167nmNLO : d14 = 2.7 d36(KDP)Damage threshould: 26 GW/cm2(1.0 ns,1053 nm)

The boron-oxygen networks in CBO are ygvery similar to that in LBO

The structures of CBO and LBO.

LBO: point group mm2 CBO : point group 222.

Their effective NLO coefficient are different

CBO+LBO => CLBOCBO+LBO => CLBO Interacting wavelengths Crystal deff (d36(KDP))

SHG: 1064 + 1064→532 CBO 1.2LBO 2.4

THG: 1064+532→355 CBO 2.7LBO 1.9

CBO is more favorable for THG than LBO.

Li d li ti l ti fLinear and nonlinear optical properties of

KBBF and SBBO familyy

Crystal Ponit group Transparent dij Δn Shortest SHGWavelengthCrystal Ponit group Range (nm)

j(pm/V) (1064-532nm) Wavelength

(nm)

KBBF D3 155-3660 d11 = 0.49 0.077 170.0

SBBO D3h 175-3780 d22 =?

TBO D3h 200-3780 d22 =?

BABO D3 ≈180-3780 d11 = 0.75 ≈ 0.05

KABO D3 180-3780 d11 = 0.48 0.074 225KABO D3 180 3780 d11 0.48 0.074 225

♣SBBO: Sr2Be2B2O7; BABO: BaAl2B2O7…

KK

BeB

F

Space structure ofO

Space structure of KBBF

SPONTANEOUS GROWTH OF KBBF CRYSTALSPONTANEOUS GROWTH OF KBBF CRYSTAL

•KBBF:KF:B2O3

=1.5:5.0:0.8

•Temperature：

600～750oC

•-5oC/d

20 d•20 days

Apparatus:

1、耐火砖 2、炉管3、电阻丝 4、保温材料1、耐火砖 2、炉管3、电阻丝 4、保温材料

5、铂坩埚 6、氧化铝坩埚7、热电偶

KBBF Single CrystalKBBF Single Crystal

KBBF crystal morphologyKBBF crystal morphology

Atom distance: 0.48nm，

a=0.4427nm

Basic Data of KBBF (KBe2BO3F2) Crystal

Space group: R32Unit cell: a =b = 4 427(4) ÅUnit cell: a =b = 4.427(4) Å

c = 18.744(9) Åz = 3

Density: 2.41 g/cm3

Decomposition temperature: (820±3) °CMelt point: ≈ 1030 °CMelt point: ≈ 1030 °CNo other phase at from room temperature to 820 °CChem-Physical Properties: No hygroscopicityy p yg p y

layer habitGood mechanical property

H d BBOHardness: ≈BBOGrowth method: top seed with fluxSize of KBBF crystal: Year 2003: 10×10×2.0 mm3y

Year 2004: 10×10×2.5 mm3

Transmittance

80

incident angle：0°random polarization157.6nm

60

70

80

40

50

nsm

ittan

ce (%

)

10

20

30Tran

0

10

130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300

W l h（ ）Wavelength（nm）

C f KBBF t ittCurve of KBBF transmittance

d 0 49 /Vd11=0.49 pm/V

L=0.55 mm

M k f i f KBBF lMaker fringes of KBBF crystal

G.L.Wang et al. Chin.Phys.Lett. 20(2), 243-245 (2003)

O i ll d P i C l d KBBFOptically contacted Prism Coupled KBBF

Thickness is limited to 1.8 mmz-cut is impossible

Apex anglez-axis1.2 mm

Thickness

�

60.0 deg.

�+4�

5�CaF2

�

CaF2

KBBFOptical Contact

KBBF-Glass prismKBBF Glass prism

C.T.Chen et al.

KBBFChin.Phys.Lett. 18(8),

1081 (2001)Patent No.

Z101115313.X(China)

10/125,024(USA)

cmcm

FoHG from KBBF crystalFoHG from KBBF crystal

358.7nm → 179.4nm

Si th Harmonic Generation of Nd:YVO4 LaserSixth Harmonic Generation of Nd:YVO4 Laser

SHG by KBBF (177.3nm)

3.0

) [m

W]

f = 200 f = 300

2.0 (

177.

3 nm

) f = 300 f = 500

1.0

H-P

ower

(1

0.0SH-

3.53.02.52.01.51.00.50.0Fundamental Power (355 nm) [W]Fundamental Power (355 nm) [W]

SHG by KBBF from 355nm to 177.3nm

177 3 t t 3 5 W

T Togashi et al Opt Lett 28(4) 254-256 (2003)

177.3nm output power: 3.5mW

T.Togashi et al. Opt.Lett. 28(4), 254 256 (2003)

深紫外谐波光从KBBF晶体中放出

Ps SHG: 177.3nm,Ps SHG: 177.3nm, 12.95mW12.95mWPs SHG: 177.3nm,Ps SHG: 177.3nm, 12.95mW 12.95mW

14Power

10

12

r (m

W)

Power12.95mW12.95mW

4

6

8

nm P

ower 355 nm pump355 nm pump

PP：：4 W4 W

D ationD ation 10 ps10 ps

0

2

4

177n 10ps

80MHz160um

DurationDuration：：10 ps 10 ps

FrequencyFrequency：：80 MHz 80 MHz

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

355nm Power (W)

Ns SHG: 177.3nm, 34.7mWNs SHG: 177.3nm, 34.7mWNs SHG: 177.3nm, 34.7mW Ns SHG: 177.3nm, 34.7mW

40

34.7mW30r (

mW

)

355nm355nm pumppump

P: 4.2WP: 4.2W20

m p

owe

DurationDuration：：49ns 49ns

FrequencyFrequency：：

10

177.

3nm

FrequencyFrequency：：10kHz 10kHz

1 2 3 40

1

355nm power355nm power355nm power355nm power

ps 177.3nm output stability

Working timeWorking time more than200 min.

Long time work:Long time work:

More than 1000 h.

SHG by KBBF (197nm)y ( )

4.55

33.5

4

ty [m

W]

22.5

3

G In

tens

it

0 51

1.5

SHG

00.5

0 100 200 300 400 500 600 700 800 900Fundamental (394 nm) [mW]

SHG f KBBF (394 197 1kH 17 )SHG of KBBF (394 nm→197 nm , 1kHz, 17 ns)

ns Ti：S Tunable DUV Laser systemTunable DUV Laser systemns Ti：S Tunable DUV Laser systemTunable DUV Laser system

深紫外宽调谐激光产生的光路图

Tunable Ti：S FoHGu ab e ：S o G

2 4

1.6

2.0

2.4

193nm

wer

(mW

)

20 ns

0.8

1.22.3mW

KBBF-I

KBBF-II

4HG

pow

176 180 184 188 192 196 200 204 208 2120.0

0.4KBBF-I

W l th ( )Wavelength (nm)

175175～～210 nm 210 nm 2.2mW @193nm 8 kHz

Light sources for Photoemission Spectroscopy

Light source DUV DPL Synchrotron DUV light

Light sources for Photoemission Spectroscopy

g y g

Energy resolution（meV） ～0.26 1～5 ～1.2（meV）

Photon flow（Photon/s） 1014～1015 1010～1012 ～1012（Photon/s）

Photon flow density（Photon/s.cm2）

1019～1020 1012～1014 ＜1014（Photon/s.cm ）

Wavelenrth (nm) 175－210 1－210 58.5

Modes ns、ps、fs pulse ns、ps pulse cw

10 0 5 2 0 5Deepth（nm） ～10（Body effect）

0.5～2（Surface effect）

～0.5( Surface effect)

(a) (b)

) GoldElectron analyzer

ty (

arb.

units

) Goldhν = 6.994 eV

T = 2.9 K

data fit

Inte

nsit

y

ΔE = 360 μeV

Binding energy (m eV)1.5 1 0.5 EF

electronFused silicaview port

Optically-contacted prism-coupledKBBFCaF2 lens

Sample

CaF2view port

E

view port

Quasi-CWFrequency-tripledNd:YVO4 laserKBBF

view port4

Fig. 1

Ultrahigh resolution photoelectron spectrometerUltrahigh resolution photoelectron spectrometer(sub-mev)

AngleAngle--resolved Photoemssion resolved Photoemssion ggSpectroscopySpectroscopy

InstrumentationData processing

Materials

Scientific issuesScientific issues

AngleAngle-- Energy resolved Energy resolved PhotoemssionPhotoemssion SpectroscopySpectroscopy

样品传输系统 样品控制台

六倍频激光系统六倍频激光系统

样品制备室

样品测量室

应用于能量分辨角分辨光电子能谱应用于能量分辨角分辨光电子能谱仪光源获得成功

最尖锐的最尖锐的最尖锐的最尖锐的光电子能谱曲线光电子能谱曲线

rb. U

nit) Bi2212

Nodalhv=6 994

nten

sity

(Ar

15 meVhv=6.994T=18K

同步辐射对应宽度~30 meV

EDC

In

2 82 62 42 22 0 2. 82. 62. 42. 22. 0

Energy (eV)

非线性光学晶体KBBF

应用于能量分辨角分辨光电子能谱仪光源获得成功仪光源获得成功

首次对高温超导首次对高温超导体的测量体的测量

November 23, 2006

Bi2212 Tc=90K

T=18K

hv=6.994 eV

(0,0)—(p,p) direction( , ) (p,p)

Fermi Surface of Sr2RuO4

Fermi Surface from ARPES Band Structure Calculations

Γ M Γ MΓ M

M X M XM X M X• Luttinger volume obeyed to within experimental error (4.02 electrons in 3 bands

• Excellent quantitative agreement with both band structure and de Haas-van AlphenK M Shen A Damascelli et al (PRB ‘01)

I.I. Mazin & D.J. Singh (PRL ‘97)K.M. Shen, A. Damascelli, et al. (PRB 01)

A. Damascelli, D.H. Lu, K.M. Shen, et al. (PRL ‘00)

Photoemission spectroscopic evidence of gap anisotropy inPhotoemission spectroscopic evidence of gap anisotropy in an f-electron superconductor, Phys.Rev. Lett. (2004)

LBOQuartz Rotator780 nmω 1.7 W

B OBω+2ω

4.2 W

2 5 WB OB

ω

2.5 W

1.5 W

Quartz Rotator 3ω1 W

Quartz Rotator

B OBω

5

ω

156 nm4ω5ω

蛍光ガラスKBBF

Chamber

深紫外固态激光光源及新型科学仪器深紫外固态激光光源及新型科学仪器

深紫外全固态激光器深紫外全固态激光器

深紫外激光拉曼谱仪

深紫外光化学反应仪深紫外光化学反应仪

深紫外激光光发射电子显微镜

深紫外激光原位时间分辨隧道电子谱仪

深紫外致发光谱仪深紫外致发光谱仪

深紫外激光同时具有自旋分辨和角分辨

的光电子能谱仪的光电子能谱仪

光子能量可调谐深紫外激光光电子能谱仪

In the future:(1) 100 mw QCW 193 nm output power with 4th(1) 100 mw QCW 193 nm output power with 4th

HG of Ti:sapphire Laser

(2) 100 mw QCW 177.3 nm output power with 6th

HG of Nd:YAG Laser

(3) Wide tunable coherent light output from(3) Wide tunable coherent light output from

200 nm-170.0 nm with 4th HG of tunable

Ti:sapphire Laser

谢谢大家！谢谢大家！

Thank You!Thank You!