紫外、深紫外非线性光学晶体的最新进展和应用前景

国家自然科学基金委员会 

数理学部实验物理讲习班 

Beijing Center for Crystal R&D, 

Technical Institute of Physics and Chemistry, 

Chinese Academy of Sciences 

Recent Advances and applications 

of NLO Crystals 

陈创天(Chuangtian Chen)



(一)非线性光学晶体的主要应用领域 

(1) 红外光谱区(900nm~10µm) 

目标:产生3~8µm连续可调光源 

方法:使用I.R. NLO 晶体,通过光参量(或差频) 

下转换。 

2.1 µm→2.7µm~8.0 µm 

2.93 µm→3.8 µm~12.4µm 

用途:测量分子的振动谱 

测量大气污染(CO, CO 2 , NO x ,C n H 2n+2 ……) 

军事



主要晶体: ZGP(ZnGeP 2 ) 

问题: 光损伤阈值过低 

60MW/cm 2 

New crystals: LiInS 2 , LiInSe 2 

0.4μm -12μm; 

d 15 =(7.94±20%) pm/v, d 24 =(5.73±20%) pm/v 

Thermal conductivity is 5 times larger 

than those of AGS and AGSe 

Damage threshold ~ 100mw/cm 2 

LiGaS2 , LiGaSe2 and LiGaTe2



(b)远红外光谱区(~100µm, THz) 

方法:使用I.R. NLO 晶体( GaSe, GaP ), 

通过差频下转换。 

用途: (1) Identification of chemicals and 

explosives 

(2) Detection of DNA and Cancer 

(3) Imaging of drugs 

…



(2) 可见光谱区(700nm~400nm) 

目标:产生瓦级(W) RGB光源 

100mW RGB光源 

方法:(1)Nd:YVO 4 的3条发射谱 

(1342nm, 1064nm, 946nm)的倍频 

671nm(R), 532nm(G), 473nm(B) 

(2) 532nm 泵光参量,再倍频 

630nm(R), 532nm(G), 460nm(B) 

LBO: 4×4 ×50 mm


数理学部实验物理讲习班



Bulk LBO



LBO OPO晶体器件



• 10瓦级全固态准连续红光红光激光器 

(DPL-SR01型)660nm 21.7W(4×4 ×50 mm 3 ) 

连续红光红光激光器660nm 11.3W(4×4 ×50 mm3 ) 

• 大功率端泵全固态准连续绿光绿光激光器 

(DPL-EG04型) 532nm 200.0W(4×4 ×50 mm 3 ) 

高光束质量 M 2 x=1.34、M 2 y=1.49 

• 大功率准连续蓝光激光器 

(DPL-SB01型) 440nm 7.6W( 4×4 ×50 mm 3 ) 

连续蓝光激光器 440nm 3.0W( 4×4 ×50 mm 3 )



晶体:瓦级:LBO (3×3 ×20 mm) 

100 mW: Nd:YAG + KTP 

用途:大型激光显示,激光影院(瓦级) 

小型激光显示,家庭影院(100mW)



红光激光器 

绿光激光器 

蓝光激光器 

实现60 实现 60 吋激光家庭影院原理演示 

激光家庭影院原理演示 

透镜 

透镜 

透镜 

国内首次 

屏



激光投影与显示已成为关键的核心技术。 

利用红、绿、蓝三色激光器做成的超小型集成显示, 

以及在此基础上开发出便携式投影与显示技术, 

将成为下一代高分辨率、高清晰度、可携带, 

甚至装在口袋里的数字显示设备。



(3) 近紫外光谱区(400nm~200nm) 

目标:获得30W ; 10W; (CW 或 QCW) 

355nm; 266nm ;212 nm光源 

方法:Nd: YAG (Nd:YVO 4 ) 激光(1064nm)3,4 ,5 

倍频 

晶体 3倍频 LBO-15W(可能 CBO-17W) 

4倍频 CLBO-4-6W(20W) 

5倍频 CLBO-(5.6W) 

用途:激光印刷、激光照片冲洗 

实现革命性变化:无需暗房,不需要冲洗….. 

光刻技术



CBO:65x44x49 mm 3



CBO Bulk Crystal



CBO device for THG(355 nm)



355nm Output Power (W) 

20 

18 

16 

14 

12 

10 

8 

6 

4 

2 

THG in CBO Crystal 

Crystal Length: 16.17mm 

0 

0 20 40 60 80 100 120 140 

Inout 1064&532nm Power (W) 

17.7w→



(4) 深紫外、真空紫外光谱区(λ





Development of Photolithography 

Recent Status: 

Optical source for lithography 

ArF excimer Laser : 193 nm 20W 

Optical source for Inspection : 193 nm 5mW 

Δλ~0.1 pm 

Ti:sapphire (772 nm)+LBO (2HG)+BBO (3HG) 

+BBO (4HG) → 193 nm 

Ti:sapphire+LBO (2HG) +KBBF (4HG) → 193 nm



Fs, 193 nm pulse –nanosurgery tool 

Power: 5-10 mw 

Pulse duration: 50-100 fs 

Focused laser beam diameter: ≈100 nm 

Efficiency absorbed by tissue and protein: 

The laser permits surgery within cells 

≈100% power of 193 nm



The photoemission spectrometer using VUV laser 

Photon energy: hν=6.994 ev 

High-energy resolution:





Linear and nonlinear optical properties of 

Crystal Ponit group 

KBBF and SBBO family 

Transparent 

Range (nm) 

dij 

(pm/V) 

Δn 

(1064-532nm) 

Shortest SHG 

Wavelength 

(nm) 

KBBF D3 155-3660 d 11 = 0.49 0.077 170.0 

SBBO D3h 175-3780 d 22 =? 

TBO D3h 200-3780 d 22 =? 

BABO D3 ≈180-3780 d 11 = 0.75 ≈ 0.05 

KABO D3 180-3780 d 11 = 0.48 0.074 225 

♣SBBO: Sr 2 Be 2 B 2 O 7 ; BABO: BaAl 2 B 2 O 7 …



Basic Data of KBBF (KBe 2BO 3F 2) Crystal 

Space group: R32 

Unit cell: a =b = 4.427(4) Å 

c = 18.744(9) Å 

z = 3 

Density: 2.41 g/cm3 Decomposition temperature: (820±3) °C 

Melt point: ≈ 1030 °C 

No other phase at from room temperature to 820 °C 

Chem-Physical Properties: No hygroscopicity 

layer habit 

Good mechanical property 

Hardness: ≈BBO 

Growth method: top seed with flux 

Size of KBBF crystal: Year 2004: 10×10×2.5 mm3 Year 2006: 10×10×3.5 mm3



KBBF has now two growth methods 

(1) Flux method: 10x10x3.5 mm 3 

(2) New method: 15x10x5.5 mm 3



KBBF structure





cm



cm





cm 

KBBF 

KBBF-Glass prism



n 

Sellmeier Equations of KBBF Crystal 

1.1713⋅ 

λ 

λ − 0.00733 

2 

2 

o = 1+ 2 

2 

−0.01022⋅λ refractive index 

1.65 

1.60 

1.55 

1.50 

1.45 

1.40 

n 

2 

2 

e = 1+ 2 

2 

−0.00169⋅λ KBBF crystal 

0.9316⋅ 

λ 

λ − 0.00675 

n o measured 

n e measured 

1.35 

0.0 0.4 0.8 1.2 1.6 2.0 

Wavelength (μm)



SHG PM Angle 

75 

70 

65 

60 

55 

KBBF Crystal 

experimental data 

old relation 

50 

330 340 350 360 370 380 390 400 410 420 

Fundamental Wavelength (nm)

SHG PM Angle 

70 

60 

50 

40 

30 

20 

KBBF Crystal 



expeimental data 

old relation 

200 400 600 800 1000 1200 1400 

Fundamental Wavelength (nm)



Phase-matching angles 

(from I.R. region to visible region) 

λ ω λ 2ω Exp.(°) Cal.(°) Error(°) 

1400 700 19.3 19.06 0.24 

1300 650 19.3 19.05 0.25 

1200 600 19.6 19.27 0.33 

1342 671 18.6 19.03 -0.43 

1064 532 20.2 20.11 0.09 

950 475 21 21.41 -0.41 

900 450 22 22.21 -0.21 

850 425 23.1 23.18 -0.08 

770 385 25.1 25.16 -0.06 

680 340 27.6 28.24 -0.64 

600 300 32.1 32.07 0.03 

589 294.5 32.5 32.71 -0.21 

550 275 34.9 35.25 -0.35

Phase-matching angles 

(from visible region to UV region) 



λ ω λ 2ω Exp.(°) Cal.(°) Error(°) 

532 266 36.2 36.6 -0.4 

500 250 39.6 39.34 0.26 

480 240 41.7 41.33 0.37 

460 230 44 43.57 0.43 

410 205 51.5 50.83 0.67 

388.4 194.2 55.1 55.08 0.02 

367.4 183.7 60.2 60.35 -0.15 

354.7 177.35 64.5 64.42 0.08 

352.4 176.2 65.3 65.27 0.03 

345 172.5 68.3 68.28 0.02 

340 170 70.4 70.66 -0.26



Problems: 

(1) The bulk crystal is still easy of cleaving. 

So, PCT technique of KBBF is needed 

for harmonic generation. 

(2) The bulk crystals grown by the new method 

have some of structural problems



θPM 

λω 

Prism-Coupling Technique 

λ 2ω 

λω 

C.T.Chen et al. Chin.Phys.Lett. 18(8), 1081 (2001)







1mm 

old crystal(1.2mm) 

Old crystal(0.7mm)



Conversion Efficiency (%) 

32 

28 

24 

20 

16 

12 

8 

4 

3mm KBBF 

1.8mm KBBF 

0 

0 1 2 3 4 5 6 7 8 9 10 11 12 

Peak-power Itensity (GW/cm 2 ) 

Fourth harmonic generation of Nd:YAG laser of 

KBBF crystals with flux method




32 

30 

28 

26 

24 

22 

20 

18 

16 

14 

12 

10 

8 

6 

4 

2 

1.8mm 

2.2mm 

0 

0 1 2 3 4 5 6 7 8 9 10 11 12 

Peak-power Intensity (GW/cm 2 ) 

Fourth harmonic generation of Nd:YAG laser 

of KBBF crystals with flux method



Conversion efficiency (%) 

4.0 

3.5 

3.0 

2.5 

2.0 

1.5 

1.0 

0.5 

crystal length: 1mm 

0.0 

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 

532nm Peak-power Density (GW/cm2 ) 

(New growth method) 

0 

0 1 2 3 4 5 6 7 8 9 10 11 12 

Fourth harmonic generation with KBBF crystal 


32 

28 

24 

20 

16 

12 

8 

4 

crystal length: 1.8mm 

532nm Peak-power Density (GW/cm2 ) 

(Flux method)



Conversion efficiency (%) 

0.14 

0.12 

0.10 

0.08 

0.06 

0.04 

0.02 

crystal length: 1.05mm 

0.00 

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 

532nm Peak-power Density (GW/cm 2 ) 

Fourth harmonic generation of Nd:YAG laser 

with KBBF crystal grown by the new method



The structural problems: 

d eff =d 11 × cosθ×cos3φ 

θ pm angle is fixed for the different position of the crystal 

φ pm angle can vary for the different position of the crystal 

As a result: 

η(shorter)>η(longer)



Laser excitation photoemission spectrometer 

Cryostat 

Electron analyzer 

Measurement chamber 

Laser 

KBBF crystal



The papers published at PRL: 

(1) “Photoemission spectroscopic evidence of gap anisotropy 

in an f-electron superconductor”, 

Phys.Rev. Lett. 94 , 057001 (2005) 

(2) “Bulk-And Surface-Sensitive High-Resolution 

Photoemission Study of Two Mott-Hubbard 

Systems:SrVO3 and CaVO3”, 

phys.Rev.Lett. 96 , 076402 (2006) 

(3) “Heavy-Fermion-Like State in A Transition Metal Oxide 

LiV2O4 Single Crystal: Indication of Kondo Resonance 

in The Photoemission Spectrum” 

Phys.Rev.Lett. 96 , 076402 (2006)



“Photoemission spectroscopic evidence of gap anisotropy in an f-electron 

superconductor”, Phys.Rev. Lett. 94, 57001,(2005)





Output power [mW] 

12 

10 

8 

6 

4 

2 

0 

0.69 original 

0.69 calculated 

4 

6 

400nm→200nm 

Power density [GW/cm2] 

8 

Pulse width : 180fs 

Repetition rate : 1kHz 

Beam diameter : 3mm 

10



Conversion efficiency [%] 

10 

8 

6 

4 

2 

0.69 original 


4 

400nm→200nm 

6 


8 




10




8 

6 

4 

2 

0.69mm_original 

0.69mm_calculated 

2 

3 

387nm→193.5nm 


4 

Pulse width : 180fs, 



5 

6



Conversion efficiency [%] 

12 

10 

8 

6 

4 

2 

0.69mm_original 

0.69mm_calculated 

2 

387nm →193.5nm 

3 


4 




5 

6




14 

12 

10 

8 

6 

4 

2 

0.69 original 


0.63 original 


5 

387nm→193.5nm 

10 





15 

20




1 

5 

4 

3 

2 

9 

0 

193 nm 

1 

2 

Time [hours] 

input power density 

9.2 GW/cm2 @0929 

4.3 GW/cm2 @0930 

3 

4




4 

3 

2 

1 

0 

0 

1 

2 

Time [hours] 

3 

Output power 

Fundamental 

4 

2.0 

2.1 

2.2 

2.3 

2.4 

Fundamental through LBO [W]



(=)The polymorphous problem of SBBO family 

Total 5 crystals of SBBO family have been 

discovered: 

SBBO (Sr 2 Be 2 B 2 O 7 ), TBO (Ba 2 Be 2 B 2 O 7 ) 

BABO(BaAl 2 B 2 O 7 ), 

KABO(K 2 Al 2 B 2 O 7 ), NABO (Na 2 Al 2 B 2 O 7 ) 

C. T. Chen, Y. B. Wang, B.C. Wu , K. C. Wu, W. L. Zeng, L. H. Yu, 

Nature .VOL 373 .26 January 1995 322-324.

(1) Only one space structure of KABO( P321 

) 



Al 

O 

K 

B 

Reason:The each layer [AlBO3] ∞ is bridged by the oxygen 

Al 

atom of the Al O 4 group to the next layer。 

K 

B 

O



B 

O 

O 

Al 

Each layer[AlBO 3 ] ∞ of KABO is bridged by the oxygen atom 

out-of the plane in the AlO 4 group to the next layer 

O 

O 

O 

B 

Al



Al 

O 

O 

B 

Network structure of each layer [AlBO 3 ] ∞ in a-b plane of KABO 

Al 

B



Structure Unit: 

Two structures 

coexist each other: 

(2)Structure of NABO 

[ ] 

2 

Al2B2O7 − 

∞ 

[ ] 

2 

Al2B2O7 − 

∞ 

P 31c 

P63 / m 

Double layers 

Na + ions located both within 

and between those double layers 

(No. 163) 

(No. 176) 

Space structure of BABO is similar with NABO



B 

O 

O 

Al 

Two double layer structures of NABO 

O



↑ 

tw isted 

↓ 

Na 

Al 

B O 

Na 

(N3) (N 6 ) 

↑ 

aligned 

↓ 

Al 

B O 

P31c P63/ m



E total (eV) 

-92.15 

-92.20 

-92.25 

-92.30 

-92.35 

-92.40 

-92.45 

N3 P-31c 

N6 P6 /m 3 

0.145 0.150 0.155 0.160 0.165 0.170 0.175 

Volume/mole (nm 3 ) 

↑ 

twisted 

↓ 

Na 

Al 

B O 

↑ 

aligned 

↓ 

Na 

(N3) (N6) 

Total energies of two structures calculated 

are near same with each other 

X.Y.Meng et al. J.Phys.Chem.Solids (2005) 

Al 

B O



6 months aged 

sample 

P63/m 

Freshly made P-31c 

structure 

P-31c

Structure Unit : 

(3)Space structure of SBBO 



[ ] 

4 

Be2B2O7 − 

∞ 

[ ] 

4 

Be2B2O7 − 

∞ 

Could be 5 structures coexisted。 

Double layers 

Sr 2+ ions located both within 

and between those double layers 

Structure of TBO is same with structure of SBBO。 

C. T. Chen, Y. B. Wang, B.C. Wu , K. C. Wu, W. L. Zeng, L. H. Yu, Nature .VOL 373 .26 January 1995 

322-324.



O 

B 

Be 

Two double layers structures of SBBO 

O



Type-I structure ( “Nature” 1995 )



twisted 

aligened 

Type-II structure



O 

B 

aligned 

aligned 

Be 

Type III structure 

Sr



Total energies of 3 structures of SBBO 

E SBBO-I = -96.23431 ev/mole 

E SBBO-II = -96.26539 ev/mole 

E SBBO-III 

= -96.25578 ev/mole



SBBO lattice could be to have the following 

domain structures: 

(1) (2) (3) (4) 

—— 

+ 

+ 

+ 

+ 

—— 

> > > 

—— 

—— 

+ + 

— — 

—— 

+ 

+ 

——



(三) New members of KBBF family 

(1) NBBF (NaBe 2 BO 3 F 2 ): Monoclinic, C121, C 2 

Mat.Res.Bull., 29 pp.81-87, 1994 

(2) CBBF (CsBe 2 BO 3 F 2 ): Trigonal, R32, D 3 

(3) RBBF(RbBe 2 BO 3 F 2 ): Trigonal, R32, D 3

Basic Data of RBBF (RbBe 2BO 3F 2) Crystal 




Unit cell: a =b = 4.43987(3) Å 

c = 19.769(2) Å 

z = 3 

Density: 2.966 g/cm3 Decomposition temperature: ≈ 1000°C 


No other phases from room temperature to 1000°C 


layer habit 


Hardness: Mohs 4-6 

Growth method: top seed with flux 

Size of RBBF crystal: Year 2005: Φ50×0.3 mm3



KBBF structure



RBBF Structure





d 11 =0.41pm/v 

d11 Maker fringes of RBBF 

d11 (RBBF) ≈ 1.06d36 (KDP) ≈ 0.41pm/v



In the future: 

(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 

200 nm-170.0 nm with 4th HG of tunable 

Ti:sapphire Laser



B 

K 

Be 

F 

O 

Space structure of 

KBBF



F 

B 

The (Be 2 BO 3 F 2 ) ∝ layer structure along a-b plane 

O 

Be





Bulk LBO



Basic Data of KBBF (KBe 2BO 3F 2) Crystal 


Unit cell: a =b = 4.427(4) Å 

c = 18.744(9) Å 

z = 3 

Density: 2.41 g/cm3 Decomposition temperature: (820±3) °C 


No other phase at from room temperature to 820 °C 


layer habit 


Hardness: ≈BBO 

Growth method: 

10×10×3.5 mm3 (Flux) 

15×10×5.5 mm3 ( New growth method )

紫外、深紫外非线性光学晶体的最新进展和应用前景

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