lithium niobateLiNbO3
PPLN Λ = 6.82 µm · 1064 → 532 nm · 2 px/µm
lithium niobate / 07 History / 7.6

7.6 Taming the crystal

1962–2021

L1 Narrative

1962-2021 · 25 events

Two problems limited lithium niobate as a nonlinear crystal: high-power light induced index changes (optical damage), and second-harmonic phase matching held only at one angle and temperature. The responses changed the crystal itself: dopants and composition for the first, domain patterns for the second.

The damage: in 1980 a Chinese group reported that about 4.6 mol% magnesium raises the damage resistance of LiNbO3 at least a hundredfold [Eleventh International Quantum 1980 P; Zheng et al. 2016 P]; a US team confirmed it in 1984 (their abstract opens “We have confirmed”) and traced it to a hundredfold rise in photoconductivity [Bryan et al. 1984 rec]. Zinc (1990) and indium (1992) followed from Moscow [Volk et al. 1990 rec; Volk & Rubinina 1992 rec]. Growing crystals with the full share of lithium also helped: by vapor treatment of fibers at Stanford (1987) [Luh et al. 1987 rec] and by a double crucible (Kitamura et al., 1992) [Kitamura et al. 1992 rec].

The colors: in 1962 Armstrong, Bloembergen, Ducuing and Pershan proposed flipping the crystal's nonlinearity every coherence length so that converted light keeps adding up [Armstrong et al. 1962 rec]. Electric-field poling of LN came 31 years later [Yamada et al. 1993 rec]. Story: The stripes.

A lithium niobate crystal in a NIST quantum-optics experiment, 2012.
A lithium niobate crystal in a NIST quantum-optics experiment, 2012. National Institute of Standards and Technology, Public domain (NIST, US Government work), file page

The stripes

Flip the stripes

L1

Light at one color and its double travel at different speeds in a crystal, so the converted light builds up and then cancels every few micrometers. In 1962 Armstrong, Bloembergen, Ducuing and Pershan proposed reversing the crystal's nonlinearity at each of those points [Armstrong et al. 1962 rec]. In 1980 Feng Duan's group at Nanjing grew lithium niobate with such stripes built in [Feng et al. 1980 rec]. In 1989-1990 Stanford put stripes into waveguides and fibers [Lim et al. 1989a rec; Magel et al. 1990 rec]. In 1993 Sony engineers wrote them by applying an external field at room temperature [Yamada et al. 1993 rec]. In 1995 Stanford built PPLN OPOs tunable from 1.4 to 4 µm [Myers et al. 1995a rec; Myers et al. 1995b rec], and in 2018 the stripes moved onto chips [Wang et al. 2018c rec].

Flip the stripes — A year scrubber from 1962 to 2019 over the rows of the table below. The domain strip changes from the 1962 schematic to growth stripes (1980), pedestal-grown fiber domains (1990) and an electrode-poled grating (1993); the phasor sum of SH contributions per coherence length is drawn live, and SH power grows as N2 with flipped stripes and stays bounded without. The period readout is the first-order period for the chosen wavelength (Zelmon 1997 Sellmeier equation, derived).
Domains, 1993: Field poling at room temperature
1993
++++|----|++++|----|++++|----|++++|----|++++|----|++++|----|++++|----|++++|----
Re AIm A
0.010.11101001000length / l_c024
12 lc
Stripes
First-order period Λ = 2 lc derived6.818 µm
SH power after N lc / after 1 lc   144
RowArmstrong et al. 1962 VFeng et al. 1980 VYING-HUA et al. 1983 VLim et al. 1989a VMagel et al. 1990 VFejer et al. 1992 VYamada et al. 1993 VMyers et al. 1995a VZhu et al. 1997 VNishida et al. 2003 VWang et al. 2018c VLu et al. 2019 V
 QPM for d33 approximately realizedSH power proportional to N2, N up to 2005%/W cm2, CW, room temperature407 nm, > 230 domains effective 20.7 mW blue; 600%/W cm2Λ = 31 µm 44%/WΛ = 4 µm, 2600%/W cm2250,000%/W
Undepleted pump, ideal 50% duty cycle; stage drawings are schematic. Λ: Zelmon 1997 congruent LN, 21 °C Zelmon et al. 1997.
1993

Periodic reversal proposed

  Armstrong et al. 1962

Czochralski-grown periodic laminar domains, half-period near lc

QPM for d33 approximately realized Feng et al. 1980

Order-of-magnitude enhancement

SH power proportional to N2, N up to 200 YING-HUA et al. 1983

Planar periodically poled waveguide, 532 nm

5%/W cm2, CW, room temperature Lim et al. 1989a

Laser-heated pedestal growth, 1 µm domains

407 nm, > 230 domains effective Magel et al. 1990

Tuning and tolerances

  Fejer et al. 1992

Field poling at room temperature

20.7 mW blue; 600%/W cm2 Yamada et al. 1993

Bulk PPLN OPO

Λ = 31 µm Myers et al. 1995a

Quasi-periodic superlattice THG (LiTaO3)

  Zhu et al. 1997

Direct-bonded QPM ridge

44%/W Nishida et al. 2003

Nanophotonic PPLN

Λ = 4 µm, 2600%/W cm2 Wang et al. 2018c

PP-TFLN microring

250,000%/W Lu et al. 2019

Re AIm A
Second-harmonic field, summed per coherence length
0.010.11101001000length / l_c024
Power versus length: N2 flipped, bounded uniform
12 lc
Period Λ (derived)
6.818 µm
SH power / 1 lc
   144

Undepleted pump, ideal 50% duty cycle; stage drawings are schematic. Period: Zelmon 1997 congruent LN, 21 °C Zelmon et al. 1997.

L2

YearStepNumbersSource
1962Periodic reversal proposed-[Armstrong et al. 1962 rec]
1980Czochralski-grown periodic laminar domains, half-period near lc; QPM for d33 approximately realized[Feng et al. 1980 rec]
1983Order-of-magnitude enhancement; SH power proportional to N2, N up to 200[YING-HUA et al. 1983 rec]
1989Planar PP waveguide, 532 nm, 5%/W cm2, CW, room temperature[Lim et al. 1989a rec]
1990Laser-heated pedestal growth, 1 µm domains, 407 nm, > 230 domains effective[Magel et al. 1990 rec]
1992Tuning and tolerances[Fejer et al. 1992 rec]
1993Field poling at room temperature; 20.7 mW blue; 600%/W cm2[Yamada et al. 1993 rec]
1995Bulk PPLN OPO, Λ = 31 µm[Myers et al. 1995a rec]
1997Quasi-periodic superlattice THG (LiTaO3)[Zhu et al. 1997 rec]
2003Direct-bonded QPM ridge, 44%/W[Nishida et al. 2003 rec]
2018Nanophotonic PPLN, Λ = 4 µm, 2600%/W cm2[Wang et al. 2018c rec]
2019PP-TFLN microring, 250,000%/W[Lu et al. 2019 rec]

Normalized efficiencies have different units (%/W cm2 for waveguides, %/W for resonators) and are not comparable across rows.

L3

The 1980 abstract says only “Czochralski method”; the striation mechanism (rotation off the thermal axis) is the usual secondary account and is not stated in the abstract (P). The 1990 Stanford bulk work used growth, not electric poling; “periodically poled” in its title means periodic domains, however made.

L2 Numbers and mechanisms

Taming the crystal

MgO. The 1980 IQEC abstract (Zhong, Jin, Wu) is cited by Nankai authors for a doping threshold of 4.6 mol% Mg giving at least two orders of magnitude higher damage resistance than congruent LN [Zheng et al. 2016 P]. Zhong's 1983 paper (Southwest Institute of Technical Physics, Chengdu) reports growth of heavily Mg-doped crystals and up to 2 W average second-harmonic power in an intracavity Q-switched Nd:YAG laser [Ji-guo et al. 1983 rec]. Bryan, Gerson and Tomaschke: greatly improved resistance at 4.5 at.% MgO or more, from a hundredfold increase in photoconductivity; OH absorption shifts from 2.87 to 2.83 µm [Bryan et al. 1984 rec]. In the band-transport picture (7.3), a larger photoconductivity shortens the dielectric relaxation time and lowers the saturated space-charge field.

Zn, In. About 50% SHG conversion of 1.06 µm without damage in LiNbO3:Zn, threshold about 4-6 mol% Zn in the melt [Volk et al. 1990 rec]; In in 1992 [Volk & Rubinina 1992 rec]; review 1994 [Volk et al. 1994 rec]; monograph [Volk & Wöhlecke 2009 rec].

Stoichiometry. Lerner, Legras and Dumas showed commercial LiNbO3 is Li-deficient [Lerner et al. 1968 rec]; the congruent composition is 48.6 mol% Li2O [Carruthers et al. 1971 rec]. Vapor transport equilibration with Li-rich powder raised the 1064 nm SHG phase-matching temperature of crystal fibers from 4 to 238 C, above the photorefractive annealing temperature [Luh et al. 1987 rec]. Double-crucible Czochralski growth with automatic powder supply gave stoichiometric boules [Kitamura et al. 1992 rec]. Oxide Corporation was founded in 2000-10 by Y. Furukawa, who left NIMS in 2003 [Oxide Corporation 2026 rec]; Furukawa and Kitamura co-authored the 2000 study of photorefraction versus [Li]/[Nb] and MgO [Furukawa et al. 2000 rec].

QPM. Wave-vector mismatch for SHG: Δ k = k(2 ω) - 2 k(ω). Coherence length lc = π / Δ k. First-order QPM period Λ = 2 lc = λ / (2 (n(2 ω) - n(ω))), with λ the fundamental wavelength. The effective coefficient is deff = (2/π) d33 for a 50% duty cycle (standard result; Fejer et al. 1992 [Fejer et al. 1992 rec]), and the harmonic power grows as N2 with N coherent domains [YING-HUA et al. 1983 rec]. Derived from the Zelmon et al. congruent-LN Sellmeier coefficients at 21 C [Zelmon et al. 1997 rec]: Λ about 6.8 µm for 1064 to 532 nm and 18.99 µm for 1550 to 775 nm.

Steps to PPLN (detail in The stripes): Feng et al. 1980, domains grown in [Feng et al. 1980 rec]; Lim, Fejer, Byer 1989, waveguides [Lim et al. 1989a rec; Lim et al. 1989b rec]; Magel 1990, laser-heated pedestal growth, domains as thin as 1 µm, SHG down to 407 nm [Magel et al. 1990 rec]; Yamada et al. 1993, field poling at room temperature [Yamada et al. 1993 rec]; Myers et al. 1995, PPLN OPOs [Myers et al. 1995a rec; Myers et al. 1995b rec]; Jundt 1997, the temperature-dependent ne Sellmeier equation used for PPLN design [Jundt 1997 rec]; NTT 2003, direct-bonded QPM-LN ridge waveguides, 44%/W SHG over 13 mm with high photorefractive resistance at room temperature [Nishida et al. 2003 rec]; NTT 2021, a PPLN waveguide OPA module giving 6.3 dB of squeezed light from DC to 6 THz [Kashiwazaki et al. 2021 rec].

Sibling crystal. Zhu, Zhu and Ming (Nanjing, 1997) used a quasi-periodic domain superlattice in LiTaO3 to couple SHG and sum-frequency generation and generate the third harmonic directly [Zhu et al. 1997 rec].

L3 Sources and status

31 sources cited on this page
ClaimSourceStatus
MgO 1980 abstract exists in JOSA 70(6) IQEC blockEleventh International Quantum 1980 (no authors in record)P
4.6 mol% threshold, > 100xZheng et al. 2016 citing the 1980 abstractP
Zhong at SWITP Chengdu (1983)Ji-guo et al. 1983 journal metadatarec
MgO >= 4.5 at.%, photoconductivity x100Bryan et al. 1984 abstractrec
Bryan, Gerson, Tomaschke affiliationsbylines (journal page)rec
Zn 1990, In 1992Volk et al. 1990, Volk & Rubinina 1992rec
Double-crucible SLN 1992Kitamura et al. 1992; NIRIM affiliation seen on Furukawa et al. 2000rec / P
Field poling, Sony 1993Yamada et al. 1993 Crossref bylinerec

The 1980 MgO work is not shown to be from Nankai University; the first author's next paper lists the Southwest Institute of Technical Physics, Chengdu (D4). The 1997 Nanjing quasi-periodic superlattice is LiTaO3.

References

  1. Journal of the Optical Society of America 70 577 (1980). Eleventh International Quantum Electronics Conference. Issued 1980-06-01. doi:10.1364/josa.70.000577
  2. Dahuai Zheng et al., Scientific Reports 6 20308 (2016). The simultaneous enhancement of photorefraction and optical damage resistance in MgO and Bi2O3 co-doped LiNbO3 crystals. Issued 2016-02-03. doi:10.1038/srep20308
  3. Bryan et al., Applied Physics Letters 44 847 (1984). Increased optical damage resistance in lithium niobate. Issued 1984-05-01. doi:10.1063/1.94946
  4. T. R. Volk et al., Optics Letters 15 996 (1990). Optical-damage-resistant LiNbO_3:Zn crystal. Issued 1990-09-15. doi:10.1364/ol.15.000996
  5. T. R. Volk & N. M. Rubinina, Ferroelectrics Letters Section 14 37-43 (1992). A new optical damage resistant impurity in lithium niobate crystals: Indium. Issued 1992-05. doi:10.1080/07315179208203341
  6. Y.S. Luh et al., Journal of Crystal Growth 85 264-269 (1987). Stoichiometric LiNbO3 single-crystal fibers for nonlinear optical applications. Issued 1987-11. doi:10.1016/0022-0248(87)90233-8
  7. Kitamura et al., Journal of Crystal Growth 116 327-332 (1992). Stoichiometric LiNbO3 single crystal growth by double crucible Czochralski method using automatic powder supply system. Issued 1992-02. doi:10.1016/0022-0248(92)90640-5
  8. Armstrong et al., Physical Review 127 1918-1939 (1962). Interactions between Light Waves in a Nonlinear Dielectric. Issued 1962-09-15. doi:10.1103/physrev.127.1918
  9. Yamada et al., Applied Physics Letters 62 435-436 (1993). First-order quasi-phase matched LiNbO3 waveguide periodically poled by applying an external field for efficient blue second-harmonic generation. Issued 1993-02-01. doi:10.1063/1.108925
  10. Zhong Ji-guo et al., Acta Physica Sinica 32 795 (1983). THE GROWTH AND THE FREQUENCY DOUBLING CHARACTERS OF HEAVILY DOPED Mg:LiNbO3 CRYSTALS. Issued 1983. doi:10.7498/aps.32.795
  11. T. Volk et al., Journal of the Optical Society of America B 11 1681 (1994). Optical-damage-resistant impurities in lithium niobate. Issued 1994-09-01. doi:10.1364/josab.11.001681
  12. Volk & Wöhlecke, Springer Series in Materials Science 115 (2009). Lithium Niobate: Defects, Photorefraction and Ferroelectric Switching. Issued 2009. doi:10.1007/978-3-540-70766-0
  13. Lerner et al., Journal of Crystal Growth 3-4 231-235 (1968). Stoechiométrie des monocristaux de métaniobate de lithium. Issued 1968-01. doi:10.1016/0022-0248(68)90139-5
  14. Carruthers et al., Journal of Applied Physics 42 1846-1851 (1971). Nonstoichiometry and Crystal Growth of Lithium Niobate. Issued 1971-04-01. doi:10.1063/1.1660455
  15. Oxide Corporation company history (2026). Oxide Corporation company history. Issued 2026. www.opt-oxide.com/company/history/
  16. Y. Furukawa et al., Applied Physics Letters 77 2494-2496 (2000). Photorefraction in LiNbO3 as a function of [Li]/[Nb] and MgO concentrations. Issued 2000-10-16. doi:10.1063/1.1318721
  17. Fejer et al., IEEE Journal of Quantum Electronics 28 2631-2654 (1992). Quasi-phase-matched second harmonic generation: tuning and tolerances. Issued 1992. doi:10.1109/3.161322
  18. XUE YING-HUA et al., Acta Physica Sinica 32 1515 (1983). THE SECOND HARMONIC GENERATION IN LiNbO3 CRYSTALS WITH PERIODIC LAMINAR FERROELECTRIC DOMAINS. Issued 1983. doi:10.7498/aps.32.1515
  19. Zelmon et al., Journal of the Optical Society of America B 14 3319 (1997). Infrared corrected Sellmeier coefficients for congruently grown lithium niobate and 5 mol% magnesium oxide-doped lithium niobate. Issued 1997-12-01. doi:10.1364/JOSAB.14.003319
  20. Feng et al., Applied Physics Letters 37 607-609 (1980). Enhancement of second-harmonic generation in LiNbO3 crystals with periodic laminar ferroelectric domains. Issued 1980-10-01. doi:10.1063/1.92035
  21. E.J. Lim et al., Electronics Letters 25 174-174 (1989). Second-harmonic generation of green light in periodically poled planar lithium niobate waveguide. Issued 1989-02-02. doi:10.1049/el:19890127
  22. E.J. Lim et al., Electronics Letters 25 731-732 (1989). Blue light generation by frequency doubling in periodically poled lithium niobate channel waveguide. Issued 1989-05-25. doi:10.1049/el:19890495
  23. G. A. Magel et al., Applied Physics Letters 56 108-110 (1990). Quasi-phase-matched second-harmonic generation of blue light in periodically poled LiNbO3. Issued 1990-01-08. doi:10.1063/1.103276
  24. L. E. Myers et al., Optics Letters 20 52 (1995). Quasi-phase-matched 1064-μm-pumped optical parametric oscillator in bulk periodically poled LiNbO_3. Issued 1995-01-01. doi:10.1364/ol.20.000052
  25. Myers et al., Journal of the Optical Society of America B 12 2102 (1995). Quasi-phase-matched optical parametric oscillators in bulk periodically poled LiNbO_3. Issued 1995-11-01. doi:10.1364/josab.12.002102
  26. Jundt, Optics Letters 22 1553 (1997). Temperature-dependent Sellmeier equation for the index of refraction, n_e, in congruent lithium niobate. Issued 1997-10-15. doi:10.1364/OL.22.001553
  27. Y. Nishida et al., Electronics Letters 39 609-611 (2003). Direct-bonded QPM-LN ridge waveguide with high damage resistance at room temperature. Issued 2003-04-03. doi:10.1049/el:20030402
  28. Takahiro Kashiwazaki et al., Applied Physics Letters 119 251104 (2021). Fabrication of low-loss quasi-single-mode PPLN waveguide and its application to a modularized broadband high-level squeezer. Issued 2021-12-20. doi:10.1063/5.0063118
  29. Shi-ning Zhu et al., Science 278 843-846 (1997). Quasi-Phase-Matched Third-Harmonic Generation in a Quasi-Periodic Optical Superlattice. Issued 1997-10-31. doi:10.1126/science.278.5339.843
  30. Cheng Wang et al., Optica 5 1438 (2018). Ultrahigh-efficiency wavelength conversion in nanophotonic periodically poled lithium niobate waveguides. Issued 2018-11-20. doi:10.1364/optica.5.001438
  31. Juanjuan Lu et al., Optica 6 1455 (2019). Periodically poled thin-film lithium niobate microring resonators with a second-harmonic generation efficiency of 250,000%/W. Issued 2019-12-20. doi:10.1364/optica.6.001455

Events of 7.6

25 events; status per event
DateEventWhoRefSt
1962-09-15Theory of light-wave interactions in nonlinear dielectrics, including periodic reversal (quasi-phase matching)J. A. Armstrong, N. Bloembergen +2DOIrec
1968-01Commercial LiNbO3 crystals are lithium-deficientP. Lerner, C. Legras +1DOIrec
1971-04-01Congruent melting composition located at 48.6 mol% Li2OJ. R. Carruthers, G. E. Peterson +2DOIrec
1980-06MgO doping raises the optical-damage resistance of LiNbO3 (conference abstract)Zhong Ji-guo, Jin J. +1DOIP
1980-10-01SHG enhanced in LiNbO3 crystals grown with periodic laminar ferroelectric domains (first QPM experiment in LN, standard attribution)Duan Feng, Nai-Ben Ming +5DOIrec
1983Heavily Mg-doped LiNbO3: growth and 2 W average second-harmonic powerZhong Ji-guo, Xu Guan-feng +2DOIrec
1984-05-01Increased optical damage resistance in MgO-doped lithium niobateD. A. Bryan, R. Gerson +1DOIrec
1985-08"Lithium niobate: summary of physical properties and crystal structure"R. S. Weis, T. K. GaylordDOIrec
1987-11Stoichiometric LiNbO3 single-crystal fibers by vapor transport equilibrationY. S. Luh, M. M. Fejer +2DOIrec
1989-02-02Green SHG in a periodically poled planar LiNbO3 waveguideE. J. Lim, M. M. Fejer +1DOIrec
1989-05-25Blue SHG in a periodically poled LiNbO3 channel waveguideE. J. Lim, M. M. Fejer +2DOIrec
1990-01-08Blue QPM SHG in LiNbO3 with periodic domains grown by laser-heated pedestal growthG. A. Magel, M. M. Fejer +1DOIrec
1990-09-15Zinc as an optical-damage-resistant dopant in LiNbO3T. R. Volk, V. I. Pryalkin +1DOIrec
1992QPM second-harmonic generation: tuning and tolerancesM. M. Fejer, G. A. Magel +2DOIrec
1992-02Stoichiometric LiNbO3 grown by double-crucible Czochralski with automatic powder supplyK. Kitamura, J. K. Yamamoto +3DOIrec
1993-02-01Electric-field periodic poling of LiNbO3 at room temperature for first-order QPM blue SHGM. Yamada, N. Nada +2DOIrec
1994-09-01Optical-damage-resistant impurities in lithium niobate (review)T. Volk, N. Rubinina +1DOIrec
1995-01-01Quasi-phase-matched 1.064 µm pumped OPO in bulk periodically poled LiNbO3L. E. Myers, W. R. Bosenberg +4DOIrec
1995-11-01Quasi-phase-matched OPOs in bulk PPLN (full paper)L. E. Myers, R. C. Eckardt +4DOIrec
1997-10-15Temperature-dependent Sellmeier equation for n_e of congruent LiNbO3Dieter H. JundtDOIrec
1997-10-31Quasi-phase-matched third-harmonic generation in a quasi-periodic optical superlattice (LiTaO3)Shi-ning Zhu, Yong-yuan Zhu +1DOIrec
2000-10Oxide Corporation founded (Yamanashi) to commercialize 'Super LN/LT' crystalsYasunori FurukawaURLrec
2003-04-03Direct-bonded QPM-LN ridge waveguide with high damage resistance at room temperatureY. Nishida, H. Miyazawa +3DOIrec
2009-09-17MgO:PPLN chips for 1060 to 530 nm green in pico-projectors-S
2021-12-20Low-loss PPLN waveguide OPA module gives 6.3 dB squeezed light up to 6 THzTakahiro Kashiwazaki, Taichi Yamashima +3DOIrec