By Maker Fringe (MF) method, all of the nonlinear optical (NLO) coefficients including d11, d12, d13, d31, d32 and d33 of TmCa4O(BO3)3 (TmCOB) crystals were measured to be 0.19, 0.26, −0.61, −0.30, 1.66 and −1.25 pm/V, respectively. Based on which, the second-harmonic-generation (SHG) phase-matching (PM) characteristics of TmCOB crystals in two-dimensional principal planes and three-dimensional non-principal planes (space) were theoretically calculated, such as PM tuning curves, distribution of effective NLO coefficient (deff), beam walk-off angle, and angular acceptance bandwidth. At the fundamental waves of 1064 nm, the type-II optimal PM angles with largest deff for principal planes and space were decided to be (52.8°, 90.0°) (deff = 0.24 pm/V) and (118.0°, 77.2°) (deff = 0.35 pm/V), respectively. The type-II SHG of TmCOB crystals was found to present large acceptance angle bandwidth (~2–12 times of type-I values) and small beam walk-off angle (~0.2–0.4 times of type-I values). At a high input energy of 6.89 mJ (35 ps, 10 Hz, 1064 nm), the SHG transformation efficiency for an uncoated TmCOB crystal sample cut along type-II optimal angle (118.0°, 77.2°) with 12 mm in length was measured to be 55.9%, which achieved the same conversion efficiency grade as type-I optimal PM.
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