ZnGeP2 Crystals Research Articles

Narrowband mid-infrared optical parametric generator based on a type-II BaGa4Se7 crystal.

In this Letter, we first reported on a mid-infrared double-pass optical parametric generator (OPG) based on a single type-II phase-matching BaGa4Se7 (BGSe) crystal, pumped at 2.1 µm. The OPG achieved a maximum pulse energy of 55 µJ for generating narrowband mid-infrared laser pulses. The signal and idler lights exhibited center wavelengths of 4.04 and 4.33 µm, respectively, with bandwidths of 18.6 nm (11.4 cm-1) and 20.4 nm (10.9 cm-1). To improve the output performance, we utilized a cascaded scheme of type-I ZnGeP2 (ZGP) and type-II BGSe crystals. The spectral bandwidths of the signal and idler lights, nearing 4 µm, were narrower than 170 nm (90 cm-1), representing a significant improvement over the ZGP OPG. The cascaded OPG achieved a remarkable total optical-to-optical conversion efficiency (OOCE) of 14.9% and a maximum pulse energy of 0.329 mJ.

Tunable optical parametric oscillator based on ZnGeP2 crystal for greenhouse gas remote sensing systems

This work is devoted to the development of a compact source of coherent radiation with frequency-energy characteristics and a spectral generation range that allows remote determination of background concentrations of greenhouse gases in the atmosphere. The aim of this work was to create a frequency parametric converter based on ZGP, pumped by Ho:YAG laser radiation. For use as a source in a mobile lidar for remote determination of the concentration of greenhouse gases in the atmosphere. In the course of the research, a layout of an Optical parametric oscillator OPO based on a ZGP crystal with Ho:YAG laser radiation pumping was developed. The system’s continuous failure-free operation time was 1.5 h at a pulse repetition rate of 10 kHz and a pulse energy of the generated radiation of 0.08 mJ. The tuning range of the OPO was from 3.3 to 5 μm when using a Lyot filter. The losses from the average generation power when the Lyot filter was introduced into the resonator were 30%. At the same time, it was possible to achieve a linewidth of the generated radiation of 0.7 nm. The divergence of the generated radiation did not exceed 1.5 mrad.The absorption spectrum of gases CO2, CH4, N2O, CO in a gas cell was simulated for the entire generation range of the ZnGeP2-based OPO. As a result of the simulation, the most intense absorption lines of gases CO2, CH4, N2O, CO in the OPO tuning range were revealed, the central wavelengths of the absorption lines and their spectral width were determined.

Broadband sum-frequency conversion of multiline Q-switched CO laser emission under its double-pass through AR-coated ZnGeP2 crystal

Broadband sum-frequency conversion of multiline Q-switched CO laser emission under its double-pass through AR-coated ZnGeP2 crystal

Enhanced near-infrared optical transmission in zinc germanium phosphide crystals via precise magnesium doping.

A zinc germanium phosphorus (ZnGeP2) crystal with a chalcopyrite structure is an efficient frequency converter in the mid-infrared region. However, point defect-induced optical absorption at the pumping wavelength (near infrared region) blocked the further application of ZnGeP2. To alleviate the absorption losses caused by point defects, in situ magnesium doping compensation was presented during the ZnGeP2 bulk crystal growth process via the vertical Bridgman method. Combined with theoretical calculations, the structural distortion of the magnesium-doped ZnGeP2 crystals in different orientations was illustrated. The thermodynamic and kinetic stability of the magnesium-doped ZnGeP2 structure were demonstrated. The transmission results indicated the improvement of transmittance within a wavelength range of 1.8-2.4 μm when doped with magnesium, which revealed the powerful ability of the appropriate dopant in optimizing near-infrared optical properties. Thus, the introduction of magnesium is a practical approach to improve the transmittance performance and extend the pumping source wavelengths of ZnGeP2 crystals.

Broadband Sum-Frequency Generation of a CO Laser in Antireflection-Coated and Uncoated ZnGeP2 Crystals

Broadband Sum-Frequency Generation of a CO Laser in Antireflection-Coated and Uncoated ZnGeP2 Crystals

High power widely tunable mid-IR (5–7.2 μm) ZnGeP2 optical parametric oscillator pumped by a 2.09 μm laser

A high-power widely tunable nanosecond (ns) mid-infrared (mid-IR) optical parametric oscillator (OPO) in a ZnGeP2 crystal has been demonstrated. The OPO is pumped by a Q-switched 2.09 μm Ho: YAG laser with 10 kHz repetition frequency. Based on optimizing the parameters of ZGP-OPO system, a maximum idler power as high as 5.47 W is achieved at 5.05 μm with photon conversion efficiency of up to 46.4 %. By rotating the angle of the ZGP crystal, the idler tuning region across from 5 to 7.2 μm is realized, with >1 W of idler power over almost the entire tuning region. The idler operation displays high pulse stability with peak to peak amplitude fluctuation less than ±2.8 % in near-Gaussian spatial mode.

Effect of UV and IR Radiation on the Electrical Characteristics of Ga2O3/ZnGeP2 Hetero-Structures

The data on electrical and photoelectric characteristics of Ga2O3/ZnGeP2 hetero-structures formed by RF magnetron sputtering Ga2O3 target with a purity of (99.99%) were obtained. The samples are sensitive to UV radiation with a wavelength of λ = 254 nm and are able to work offline as detectors of short-wave radiation. Structures with Ga2O3 film that was not annealed at 400 °C show weak sensitivity to long-wavelength radiation, including white light and near-IR (λ = 808 and 1064 nm). After annealing in an air environment (400 °C, 30 min), ZnGeP2 crystals in contact with Ga2O3 show n-type conductivity semiconductor properties, the sensitivity of Ga2O3/ZnGeP2 hetero-structures increases in the UV and IR ranges; the photovoltaic effect is preserved. Under λ = 254 nm illumination, the open-circuit voltage is fixed at positive potentials on the electrode to Ga2O3, the short-circuit current increases by three orders of magnitude, and the responsivity increases by an order of magnitude. The structures detect the photovoltaic effect in the near-IR range and are able to work offline (remotely) as detectors of long-wavelength radiation.

Electrical Relaxation and Transport Properties of ZnGeP2 and 4H-SiC Crystals Measured with Terahertz Spectroscopy

Terahertz photoconductivity and charge carrier recombination dynamics at two-photon (ZnGeP2) and three-photon (4H-SiC) excitation were studied. Thermally annealed, high-energy electron-irradiated and Sc-doped ZnGeP2 crystals were tested. The terahertz charge carrier mobilities were extracted from both the differential terahertz transmission at a specified photoexcitation condition and the Drude–Smith fitting of the photoconductivity spectra. The determined terahertz charge carrier mobility values are ~453 cm2/V·s for 4H-SiC and ~37 cm2/V·s for ZnGeP2 crystals. The charge carrier lifetimes and the contributions from various recombination mechanisms were determined at different injection levels using the model, which takes into account the influence of bulk and surface Shockley–Read–Hall (SRH) recombination, interband radiative transitions and interband and trap-assisted Auger recombination. It was found that ZnGeP2 possesses short charge carrier lifetimes (a~0.01 ps−1, b~6 × 10−19 cm3·ps−1 and c~7 × 10−40 cm6·ps−1) compared with 4H-SiC (a~0.001 ps−1, b~3 × 10−18 cm3·ps−1 and c~2 × 10−36 cm6·ps−1), i.e., τ~100 ps and τ~1 ns at the limit of relatively low injection, when the contribution from Auger and interband radiative recombination is small. The thermal annealing of as-grown ZnGeP2 crystals and the electron irradiation reduced the charge carrier lifetime, while their doping with 0.01 mass % of Sc increased the charger carrier lifetime and reduced mobility. It was found that the dark terahertz complex conductivity of the measured crystals is not fitted by the Drude–Smith model with reasonable parameters, while their terahertz photoconductivity can be fitted with acceptable accuracy.

MgSiP2: An Infrared Nonlinear Optical Crystal with a Large Non‐Resonant Phase‐Matchable Second Harmonic Coefficient and High Laser Damage Threshold

AbstractSuperior infrared nonlinear optical (NLO) crystals are in urgent demand in the development of lasers and optical technologies for communications and computing. The critical challenge is to find a crystal with large non‐resonant phase‐matchable NLO coefficients and high laser damage threshold (LDTs) simultaneously, which however scale inversely. This work reports such a material, MgSiP2, that exhibits a large second harmonic generation (SHG) coefficient of d14≈d36 = 89 ± 5 pm V−1 at 1550 nm fundamental wavelength, surpassing the commercial NLO crystals AgGaS2, AgGaSe2, and ZnGeP2. First principles theory reveals the polarizability and geometric arrangement of the [SiP4] tetrahedral units as the origin of this large nonlinear response. Remarkably, it also exhibits a high LDT value of 684 GW cm−2, which is six times larger than ZnGeP2 and three times larger than CdSiP2. It has a wide transparency window of 0.53–10.35 µm, allowing broadband tunability. Further, it is Type I and Type II phase‐matchable with large effective SHG coefficients of deff,I ≈80.2 pm V−1 and deff,II ≈73.4 pm V−1. The outstanding properties of MgSiP2 make it a highly attractive candidate for optical frequency conversion in the infrared.

Broadband sum-frequency conversion of multiline Q-switched CO laser emission under its double-pass through uncoated ZnGeP2 crystal

Broadband sum-frequency conversion of multiline Q-switched CO laser emission in a single uncoated ZnGeP2 crystal was experimentally studied by application of single-pass and double-pass optical schemes. The laser emitted sub-microsecond pulses of 4 kW peak power at 100 Hz pulse repetition rate on ∼60 spectral lines within ∼5–6 μm wavelength interval. The sum-frequency emission spectrum consisted of at least ∼100 spectral lines covering the wavelength interval of ∼2.5–2.9 μm. The double-pass scheme provided about 30% higher efficiency as compared to a traditional single-pass one, while the spectral bandwidth of frequency converted radiation was the same. Moreover, a feasibility of slight spectral bandwidth extension by a variation of a reverse beam direction was demonstrated for the double-pass scheme.

Intra-pulse difference frequency generation in ZnGeP2 for high-frequency terahertz radiation generation

The highly-nonlinear chalcopyrite crystal family has experienced remarkable success as source crystals in the mid-infrared spectral range, such that these crystals are primary candidates for producing high terahertz frequency (i.e., gtrsim 10 THz) electric fields. A phase-resolved terahertz electric field pulse is produced via intra-pulse difference frequency generation in a chalcopyrite (110) ZnGeP2 crystal, with phase-matching being satisfied by the excitation electric field pulse having polarizations along both the ordinary and extraordinary crystal axes. While maximum spectral power is observed at the frequency of 24.5 THz (in agreement with intra-pulse phase-matching calculations), generation nonetheless occurs across the wide spectral range of 23–30 THz. To our knowledge, this is the first time a chalcopyrite ZnGeP2 crystal has been used for the generation of phase-resolved high-frequency terahertz electric fields.

Influences of process parameters on chemical mechanical polishing effect of ZnGeP2 crystal

To obtain the ultra-smooth surface of ZnGeP2 crystal (ZGP), the workpiece-abrasive-polishing pad contact model during polishing was established to calculate the load Fw and the cutting depth hw of a single abrasive. The influences of polishing methods, abrasive hardness, abrasive size, polishing pressure, polishing time and other factors on the polishing effect were studied, and the mechanism underpinning the formation of surface morphology after polishing was revealed, and the mathematical model between material removal rate (MRR) and surface roughness (Ra) was established. The results show that the critical cutting depth hc of ZnGeP2 crystal is 95.21 nm, when the polishing load is 5 N, the material removal under mechanical polishing and chemical mechanical polishing entails plastic removal. Compared with mechanical polishing, the MRR of chemical mechanical polishing is increased by 23.4% and Ra is decreased by 26.5%. The increases of abrasive hardness, abrasive size and polishing load will increase the cutting depth hw of the abrasive, resulting in the increases of MRR and Ra, but the influence forms of various factors are different. After optimizing the process parameters, the minimum Ra of ZnGeP2 crystal is 0.76 nm. MRR and Ra will decrease significantly with the increase of polishing time, and there is a significant correlation between them.

Long-wave-infrared pulse production at 11 µm via difference-frequency generation driven by femtosecond mid-infrared all-fluoride fiber laser.

We present an ultrafast long-wave infrared (LWIR) source driven by a mid-infrared fluoride fiber laser. It is based on a mode-locked Er:ZBLAN fiber oscillator and a nonlinear amplifier operating at 48 MHz. The amplified soliton pulses at ∼2.9 µm are shifted to ∼4 µm via the soliton self-frequency shifting process in an InF3 fiber. LWIR pulses with an average power of 1.25-mW centered at 11 µm with a spectral bandwidth of ∼1.3 µm are produced through difference-frequency generation (DFG) of the amplified soliton and its frequency-shifted replica in a ZnGeP2 crystal. Soliton-effect fluoride fiber sources operating in the mid-infrared for driving DFG conversion to LWIR enable higher pulse energies than with near-infrared sources, while maintaining relative simplicity and compactness, relevant for spectroscopy and other applications in LWIR.

Nanosecond pulsed narrow-linewidth all-fiber source for ZGP-OPO pumping

We demonstrate a pulsed three-stage master oscillator power amplifier (MOPA) at a wavelength of 2047 nm and its application for mid-IR generation via pumping a ZnGeP2 (ZGP) optical parametric oscillator (OPO). A maximum MOPA output power of 19.8 W is reached while achieving a diffraction limited beam quality M2 <1.1. By applying the MOPA setup to pump a ZGP crystal in a linear OPO cavity, a combined signal and idler mid-IR output power of 8.1 W is reached. For the highest mid-IR output power, a mid-IR conversion efficiency of 44 % and beam quality factors M2 of 2.2 and 2.0 are determined for signal and idler, respectively.

Atomic structures and carrier dynamics of defects in a ZnGeP2 crystal

ZnGeP2 (ZGP) crystals have attracted tremendous attention for their applications as frequency conversion devices. Nevertheless, the existence of native point defects, including at the surface and in the bulk, lowers their laser-induced damage threshold by increasing their absorption and forming starting points of the damage, limiting their applications. Here, native point defects in a ZGP crystal are fully studied by the combination of high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and optical measurements. The atomic structures of the native point defects of the Zn vacancy, P vacancy, and Ge-Zn antisite were directly obtained through an HAADF-STEM, and proved by photoluminescence (PL) spectra at 77 K. The carrier dynamics of these defects are further studied by ultrafast pump-probe spectroscopy, and the decay lifetimes of 180.49, 346.73, and 322.82 ps are attributed to the donor Vp+ → valence band maximum (VBM) recombination, donor GeZn+ → VBM recombination, and donor–acceptor pair recombination of Vp+ → VZn-, respectively, which further confirms the assignment of the electron transitions. The diagrams for the energy bands and excited electron dynamics are established based on these ultrahigh spatial and temporal results. Our work is helpful for understanding the interaction mechanism between a ZGP crystal and ultrafast laser, doing good to the ZGP crystal growth and device fabrication.

Trade-Off for Better Balanced Nonlinear Optical Performance with Disordered Si in ZnGeP2

ZnGeP2 (ZGP) possesses prominent mid-far infrared nonlinear optical (NLO) performance but suffers from a narrow bandgap. A comparative analysis revealed that the bandgap could be enhanced by substituting Si for Ge in ZGP, successfully synthesizing a series of ZnSixGe1–xP2 crystals with enlarged bandgaps compared with that of ZGP. Interestingly, when the x varies from 0 to 0.5, in addition to obtaining improved bandgaps, the second-harmonic generation (SHG) responses are enhanced simultaneously, which is abnormal because they are usually inversely proportional. Theoretical calculations with special quasirandom structures show that the NLO coefficient decreases gradually with increasing Si content, but the decrease is tiny in the 0–50% range and acute in the 50–100% range of Si. The transmission experiment of the ZnSi0.25Ge0.75P2 wafer indicates that the introduction of silicon effectively improves the transmittance in the 1–2 μm range. The enhanced transmittance and maintained NLO coefficients result in a better macroscopic SHG response. Combined with an increased laser-induced damage threshold, the introduction of Si becomes a practical approach to improve performance and extend the application of ZGP crystals.

Terahertz Generation by Optical Rectification of 780 nm Laser Pulses in Pure and Sc-Doped ZnGeP2 Crystals

Terahertz wave generation through the optical rectification of 780 nm femtosecond laser pulses in ZnGeP2 crystals has been studied. All of the possible interactions of types I and II were analyzed by modeling and experimentally. We demonstrate the possibility of broadband “low-frequency” terahertz generation by an ee–e interaction (with two pumping waves and a generated terahertz wave; all of these had extraordinary polarization in the crystal) and “high-frequency” terahertz generation by an oe–e interaction. The arising possibility of achieving the narrowing of the terahertz generation bandwidth at the oe–e interaction using thicker ZnGeP2 crystals is experimentally confirmed. It has been found that the thermal annealing of as-grown ZnGeP2 crystals and their doping with a 0.01 mass % of Sc reduces the absorption in the “anomalous absorption” region (λ = 0.62–3 μm). The terahertz generation by the oo–e interaction in (110) ZnGeP2:Sc and the as-grown ZnGeP2 crystals of equal thicknesses was compared. It has been found that ZnGeP2:Sc is more efficient for 780 nm femtosecond laser pulses optical rectification.

Efficient generation of femtosecond millijoule pulses at 3.1 µm.

3.2-mJ, 92-fs pulses centered at 3.1 µm are generated at a 1-kHz repetition rate through a tabletop optical parametric chirped pulse amplification (OPCPA) system based on ZnGeP2 crystals. Pumped by a 2-µm chirped pulse amplifier with a flat-top beam profile, the amplifier achieves a 16.5% overall efficiency, which, to the best of our knowledge, is the highest efficiency achieved by OPCPA at this wavelength. Harmonics up to the seventh order are observed after focusing the output in the air.

Compact Radio Frequency Discharge-Pumped Slab CO Laser System with a Zinc Germanium Phosphide (ZnGeP2) Sum-Frequency Generator for Remote Sensing of the Atmosphere.

Based on our experimental study of spectral characteristics of an improved compact CO laser system, the prospects of using such a laser system for solving urgent problems of atmospheric sounding were demonstrated. An increase in the number of laser lines due to intracavity generation of the second harmonic and sum-frequencies in a nonlinear zinc germanium phosphide (ZnGeP2) crystal enriches capabilities of the laser. It was shown that such a CO laser system with frequency conversion in ZnGeP2 crystal can be used for detection and measuring concentration of at least 14 minor natural and pollution gases components of the atmosphere. The advantages and disadvantages of various laser operation modes, and the prospects for using its radiation for atmospheric remote sensing in various spectral ranges are discussed.

Multispectral Anti-Reflection Coatings Based on YbF3/ZnS Materials on ZnGeP2 Substrate by the IBS Method for Mid-IR Laser Applications

A multispectral anti-reflective coating of high radiation strength for laser applications in the IR spectrum for nonlinear ZnGeP2 crystals has been developed for the first time. The coating was constructed using YbF3/ZnS. The developed coating was obtained by a novel approach using ion-beam deposition of these materials on a ZnGeP2 substrate. It has a high LIDT of more than 2 J/cm2. Optimal layer deposition regimes were found for high film density and low absorption, and good adhesion of the coating to the substrate was achieved. At the same time, there was no dissociation of the double compound under high-energy ions.