lithium niobateLiNbO3
PPLN Λ = 6.82 µm · 1064 → 532 nm · 2 px/µm
lithium niobate / 07 History / 7.2

7.2 Bell Labs grows a crystal

1960–1967

L1 Narrative

1960-1967 · 13 events

Between 1964 and 1966 a Bell Telephone Laboratories group measured how a voltage changes the speed of light in it [Peterson et al. 1964 rec], showed it could change laser color efficiently [Boyd et al. 1964 rec], pulled large single crystals from the melt [BALLMAN 1965 P], made the electric arrows in a whole crystal point the same way [Nassau et al. 1966b rec], and published the crystal's complete description as five consecutive papers in one journal issue [Nassau et al. 1966a rec; Abrahams et al. 1966c rec]. In June 1965 J. A. Giordmaine and R. C. Miller used it to build the first tunable optical parametric oscillator: green laser light in, two new infrared colors out, tuned by warming the crystal [Giordmaine & Miller 1965 rec; Harris 1969 P; Chinese translation of 1965 S]. In the same year a Soviet group reported pulling lithium niobate crystals too [Fedulov & al. 1965 P], and in 1967 Crystal Technology in Palo Alto began selling them [optics.org 2026 rec].

Pull a boule — A seed is drawn from a melt at a chosen rate and rotation; the boule grows as an illustration; sizes and rates are not data. OPO dial: The first OPO.
Czochralski pullillustration, no data
 5 / 10
Rotation
Seed
Display scale only: no growth rates or diameters are sourced in this chapter. Method: Czochralski 1918; LN growth 1965: BALLMAN 1965, Fedulov & al. 1965.
 5/10

An illustration with no data: growth rates and diameters are not sourced in this chapter. Method: Czochralski 1918; LN growth 1965: BALLMAN 1965, Fedulov & al. 1965.

Bell Telephone Laboratories, Murray Hill, 1942.
Bell Telephone Laboratories, Murray Hill, 1942. Gottscho-Schleisner Collection, Public domain, file page

The first OPO

OPO dial

L1

In 1965 Giordmaine and Miller pumped a lithium niobate crystal with green laser light inside a resonator and got two new beams whose colors moved when they warmed the crystal [Giordmaine & Miller 1965 rec; Chinese translation of 1965 S]. It was the first tunable optical parametric oscillator [Harris 1969 rec]. In 1995 Stanford built a PPLN OPO, temperature-tuned at a 31 µm period [Myers et al. 1995a rec]. In 2026 reviews describe PPLN OPOs on thin-film chips [Wang et al. 2026 rec].

OPO dial — An OPO dial: pump 0.529 µm (1965) or 1.064 µm (1995). The knob is the crystal angle in 1965 mode and the crystal temperature, plus a poling-period model extension, in 1995 mode; signal and idler follow from energy conservation and phase matching with the Zelmon 1997 (1965) and Jundt 1997 (1995) Sellmeier equations. The 1965 tuning band (0.97-1.15 µm, S) and 1995 bands (1.66-2.95 µm at 31 µm period; 1.4-4 µm overall) are drawn as reference bars with sources.
OPO: pump 1.064 µm, PPLN e+e→e, Λ = 31.0 µm
0.5123452050100150200250µmtemperature (°C)VVas reported
100 °C
31.0 µm
70.0 deg
Signal derived1.744 µm
Idler derived2.729 µm
Bars: Myers et al. 1995a V; Myers et al. 1995b V
Bar: Chinese translation of 1965 S
Jundt 1997 ne(λ, T) for congruent LN Jundt 1997 (coefficients via a secondary transcription), first-order QPM, thermal expansion of Λ neglected. Λ other than 31 µm: model extension; the 1995 experiment was temperature-tuned.
Zelmon 1997 congruent LN at 21 °C Zelmon et al. 1997. No temperature-dependent no model is held, so the knob is the angle; near degeneracy congruent LN at 21 °C has no solution even at 90°. The phase-matching temperature depends strongly on Li content (4 to 238 °C for 1064 nm SHG in fibers Luh et al. 1987); the 1965 crystal composition is not documented here.
oven 100 °Csignal 1.744 µmidler 2.729 µmpump 1.064 µm 0.40.50.711.52345
100 °C
31.0 µm
70.0 deg
Signal (derived)
1.744 µm
Idler (derived)
2.729 µm

Bands as reported: Myers et al. 1995a V; Myers et al. 1995b V. Phase matching e+e→e, first-order QPM; Jundt 1997 ne(λ, T) for congruent LN Jundt 1997 (coefficients via a secondary transcription); thermal expansion of Λ neglected. Periods other than 31 µm: model extension.

Band as reported: Chinese translation of 1965 S. Type I o+o→e; Zelmon 1997 congruent LN at 21 °C Zelmon et al. 1997. No temperature-dependent no model is held, so the knob is the angle; near degeneracy there is no solution even at 90°. The phase-matching temperature depends strongly on Li content (4 to 238 °C for 1064 nm SHG in fibers Luh et al. 1987); the 1965 crystal composition is not documented here.

0.5123452050100150200250µmtemperature (°C)VVas reported

L2

Energy: 1/λp = 1/λs + 1/λi. Momentum: kp - ks - ki = 0 (birefringent, 1965) or = 2 π / Λ (QPM, 1995). Myers et al. (OL, 1995): 1.064 µm pumped, temperature-tuned 1.66-2.95 µm, threshold about 0.1 mJ, crystal 0.5 mm thick and 5.2 mm long, Λ = 31 µm [Myers et al. 1995a rec]. JOSA B 1995: 1.4-4 µm, threshold as low as 0.012 mJ, cw doubly resonant OPO near 1.96 µm pumped by a 978 nm diode [Myers et al. 1995b rec]. Giordmaine and Miller (S, via the Bell Laboratories Record translation): 5290 A pump, output 9700-11500 A, about 12 C of temperature change shifting each beam by more than 6%, efficiency about 0.45% [Chinese translation of 1965 S].

L3

Operating details are from a secondary source (S); the 1965 PRL full text was not read. Pump laser type for 1965 not confirmed. Whether the 1965 crystal came from Ballman's Czochralski growth: the Record item credits Ballman with large-crystal growth (S).

L2 Numbers and mechanisms

Bell Labs grows a crystal

Phase matching. Boyd et al. (1964) established LiNbO3 as “an efficient phase matchable nonlinear optical material” [Boyd et al. 1964 rec]. In 1965 Miller, Boyd and Savage reached noncritical (90 degree) phase matching by temperature tuning, which removes walk-off between the fundamental and harmonic beams [Miller et al. 1965 rec].

Single-domain crystals. Nassau, Levinstein and Loiacono revealed domains by acid etching [Nassau et al. 1965 rec] and described growth, domain structure, dislocations, etching and the preparation of single-domain crystals in parts 1-2 of the 1966 series [Nassau et al. 1966a rec; Nassau et al. 1966b rec]. Abrahams and coworkers gave the X-ray and neutron structures at 24 C and the polycrystal X-ray study from 24 to 1200 C in parts 3-5 [Abrahams et al. 1966a rec; Abrahams et al. 1966b rec; Abrahams et al. 1966c rec]. Electro-optic coefficients of single-domain material followed [Lenzo et al. 1966 rec], and Kaminow and Turner reviewed electro-optic modulators the same year [Kaminow & Turner 1966 rec].

Growth. Ballman's paper covers Czochralski growth of several piezoelectric and ferroelectric materials, LN included [BALLMAN 1965 P]. Bell Labs had pulled large CaWO4 crystals for masers by 1960 [Nassau & Uitert 1960 P]. A Bell Laboratories Record item of 1965 credits Ballman with the large-crystal technique and Nassau and Levinstein with crystal quality for the OPO work [Chinese translation of 1965 S].

USSR. Fedulov et al., Kristallografiya 10, 268 (1965), is cited by four 1966 papers for Czochralski growth of LiNbO3, LiTaO3 and NaNbO3 [Fedulov & al. 1965 P]. Smolenskii et al. reported the Curie temperature of LiNbO3 in January 1966 [Smolenskii et al. 1966 rec]. Yu. S. Kuz'minov's monographs on LN appeared in Russian in 1975 and 1987 and in English in 1990 (with A. M. Prokhorov) and 1999 [Kuz'minov & Prokhorov 2026 S].

L3 Sources and status

28 sources cited on this page
ClaimSourceStatus
EO properties 1964; NLO 1964; noncritical PM 1965Peterson et al. 1964, Boyd et al. 1964, Miller et al. 1965rec
Ballman 1965 is LN Czochralski growthBALLMAN 1965 via Abrahams et al. 1966a, Uecker 2014P
First tunable OPO, 1965-06-14Giordmaine & Miller 1965 (metadata); “first tunable” per Harris 1969 (later secondary)P
OPO pump 0.529 µm, tuning 0.97-1.15 µm by temperatureChinese translation of 1965 (Chinese translation)S
Five-part series, JPCS 27, 983-1026 (1966)Crossref, five DOIsrec
Soviet Czochralski LN 1965Fedulov & al. 1965 via citing reference listsP
Crystal Technology from 1967company statementsV (company claim)

Dispute: who pulled LN first, Ballman (US, 1965-02) or Fedulov et al. (USSR, 1965)? See D3.

References

  1. G. E. Peterson et al., Applied Physics Letters 5 62-64 (1964). ELECTRO-OPTIC PROPERTIES OF LiNbO3. Issued 1964-08-01. doi:10.1063/1.1754053
  2. Boyd et al., Applied Physics Letters 5 234-236 (1964). LiNbO3: AN EFFICIENT PHASE MATCHABLE NONLINEAR OPTICAL MATERIAL. Issued 1964-12-01. doi:10.1063/1.1723604
  3. BALLMAN, Journal of the American Ceramic Society 48 112-113 (1965). Growth of Piezoelectric and Ferroelectric Materials by the CzochraIski Technique. Issued 1965-02. doi:10.1111/j.1151-2916.1965.tb11814.x
  4. K. Nassau et al., Journal of Physics and Chemistry of Solids 27 989-996 (1966). Ferroelectric lithium niobate. 2. Preparation of single domain crystals. Issued 1966-06. doi:10.1016/0022-3697(66)90071-0
  5. K. Nassau et al., Journal of Physics and Chemistry of Solids 27 983-988 (1966). Ferroelectric lithium niobate. 1. Growth, domain structure, dislocations and etching. Issued 1966-06. doi:10.1016/0022-3697(66)90070-9
  6. S.C. Abrahams et al., Journal of Physics and Chemistry of Solids 27 1019-1026 (1966). Ferroelectric lithium niobate. 5. Polycrystal X-ray diffraction study between 24° and 1200°C. Issued 1966-06. doi:10.1016/0022-3697(66)90074-6
  7. Giordmaine & Miller, Physical Review Letters 14 973-976 (1965). Tunable Coherent Parametric Oscillation in LiNb O 3 at Optical Frequencies. Issued 1965-06-14. doi:10.1103/physrevlett.14.973
  8. S. E. Harris, Proceedings of the IEEE 57 2096-2113 (1969). Tunable optical parametric oscillators. Issued 1969. doi:10.1109/PROC.1969.7495
  9. Chinese translation of a Bell Laboratories Record item on the tunable parametric oscillator, Bell Lab. Rec. 43(7), 310-311 (1965) (1965). Chinese translation of a Bell Laboratories Record item on the tunable parametric oscillator, Bell Lab. Rec. 43(7), 310-311 (1965). Issued 1965. www.researching.cn/ArticlePdf/m00002/1965/2/10/1965-10-0031.pdf
  10. S. A. Fedulov & et al., Kristallografiya 10 268 (1965). Czochralski growth of LiNbO3, LiTaO3 and NaNbO3 single crystals (title as cited; variants conflict). Issued 1965
  11. optics.org buyers guide: Crystal Technology, Inc. (2026). optics.org buyers guide: Crystal Technology, Inc.. Issued 2026. optics.org/buyers-guide/crystal-technology-inc
  12. Miller et al., Applied Physics Letters 6 77-79 (1965). NONLINEAR OPTICAL INTERACTIONS IN LiNbO3 WITHOUT DOUBLE REFRACTION. Issued 1965-02-15. doi:10.1063/1.1754174
  13. Nassau et al., Applied Physics Letters 6 228-229 (1965). THE DOMAIN STRUCTURE AND ETCHING OF FERROELECTRIC LITHIUM NIOBATE. Issued 1965-06-01. doi:10.1063/1.1754147
  14. Abrahams et al., Journal of Physics and Chemistry of Solids 27 997 (1966). Ferroelectric lithium niobate. 3. Single crystal X-ray diffraction study at 24 C. Issued 1966-06. doi:10.1016/0022-3697(66)90072-2
  15. S.C. Abrahams et al., Journal of Physics and Chemistry of Solids 27 1013-1018 (1966). Ferroelectric lithium niobate. 4. Single crystal neutron diffraction study at 24°C. Issued 1966-06. doi:10.1016/0022-3697(66)90073-4
  16. P. V. Lenzo et al., Journal of the Optical Society of America 56 633 (1966). Electro-Optic Coefficients in Single-Domain Ferroelectric Lithium Niobate. Issued 1966-05-01. doi:10.1364/josa.56.000633
  17. I.P. Kaminow & E.H. Turner, Proceedings of the IEEE 54 1374-1390 (1966). Electrooptic light modulators. Issued 1966. doi:10.1109/proc.1966.5124
  18. K. Nassau & L. G. Van Uitert, Journal of Applied Physics 31 1508-1508 (1960). Preparation of Large Calcium-Tungstate Crystals Containing Paramagnetic Ions for Maser Applications. Issued 1960-08-01. doi:10.1063/1.1735881
  19. G. A. Smolenskii et al., physica status solidi (b) 13 309-314 (1966). The Curie Temperature of LiNbO3. Issued 1966-01. doi:10.1002/pssb.19660130202
  20. Yu. S. Kuz'minov & A. M. Prokhorov (2026). Kuz'minov monographs: Niobat i tantalat litiya (Nauka 1975); Elektroopticheskii i nelineinoopticheskii kristall niobata litiya (Nauka 1987); Physics and Chemistry of Crystalline Lithium Niobate (Adam Hilger 1990, with Prokhorov); Lithium Niobate Crystals (Cambridge International Science Publishing 1999). Issued 2026
  21. Reinhard Uecker, Journal of Crystal Growth 401 7-24 (2014). The historical development of the Czochralski method. Issued 2014-09. doi:10.1016/j.jcrysgro.2013.11.095
  22. 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
  23. Zhenyu Wang et al., Applied Physics Reviews 13 031312 (2026). On-chip nonlinear photonics: Advances and challenges in integrated PPLN optical parametric oscillators. Issued 2026-09-01. doi:10.1063/5.0315274
  24. 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
  25. J. Czochralski, Zeitschrift für Physikalische Chemie 92U 219-221 (1918). Ein neues Verfahren zur Messung der Kristallisationsgeschwindigkeit der Metalle. Issued 1918-11-01. doi:10.1515/zpch-1918-9212
  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. 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
  28. 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

Events of 7.2

13 events; status per event
DateEventWhoRefSt
1960-08-01Bell Labs pulls large CaWO4 crystals by Czochralski for masersK. Nassau, L. G. Van UitertDOIP
1964-08-01Electro-optic properties of LiNbO3 measuredG. E. Peterson, A. A. Ballman +2DOIrec
1964-12-01LiNbO3: an efficient phase-matchable nonlinear optical materialG. D. Boyd, R. C. Miller +3DOIrec
1965Soviet Czochralski growth of LiNbO3, LiTaO3 and NaNbO3S. A. Fedulov-P
1965-02Ballman grows LiNbO3 and other piezoelectric and ferroelectric crystals by Czochralski pullingA. A. BallmanDOIP
1965-02-15Noncritical (90 degree) phase matching in LiNbO3R. C. Miller, G. D. Boyd +1DOIrec
1965-06-01Ferroelectric domain structure of LiNbO3 revealed by etchingK. Nassau, H. J. Levinstein +1DOIrec
1965-06-14First tunable optical parametric oscillator, in LiNbO3J. A. Giordmaine, R. C. MillerDOIrec
1966Electro-optic light modulators (review)I. P. Kaminow, E. H. TurnerDOIrec
1966-01Soviet measurement of the Curie temperature of LiNbO3G. A. Smolenskii, N. N. Krainik +3DOIrec
1966-05-01Electro-optic coefficients of single-domain LiNbO3P. V. Lenzo, E. G. Spencer +1DOIrec
1966-06'Ferroelectric lithium niobate' parts 1-5: growth, single-domain poling, X-ray and neutron structureK. Nassau, H. J. Levinstein +5DOIrec
1967Crystal Technology (Palo Alto) begins making oxide single crystals including LiNbO3URLrec