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Energy transfer in a rare earth doped activator-activator system

Evan P. Chicklis, Charles S. Naiman

Published Oct 1, 1977• 1 citation
OpenAlex

Abstract

This report summarizes research carried out to investigate energy transfer in an activator-activator system; that is a system for which energy transfer is reversible between certain metastable levels and for which stimulated emission from each of these levels can be generated. The specific system investigated is Er-Ho:YLF. Laser operation from two different ions in the same solid state host has been demonstrated. The 750nm (5S(2) - 5I(7):Ho) and 850nm (4S(3/2) - 4I(13/2:Er) transitions were observed simultaneously and separately at 77K. Cross transfer between the S levels was also observed and the cross transfer rates measured in crystals of five different compositions. Cross transfer between the S levels is mitigated by other cross relaxation transfer schemes which quench the S level storage time of each ion. Only about 25% of the initial population of one ion is transferred to the other in the optimum concentration, 2%Ho-2%Er, at room temperature. The cross transfer rate is only weakly temperature and concentration dependent; at low temperatures cross transfer is somewhat more effective as the decay rates of each ion are longer.

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We have investigated the energy transfers in the 1.54- μ m region of (Er,Sc) 2 O 3 epitaxial thin films grown on Si(111). The interplay of the energy transfers between Er ions in the different and the same symmetry sites makes the dynamics complicated. To suppress the energy transfer upconversion, low power and resonant excitation of the third crystal-field level ( 4 I 13 / 2 : Y 3 ′ ) of the Er 3 + site with C 3 i symmetry was employed. The time-resolved photoluminescence measurements of the Y 1 ′ - Z 1 ′ transition indicate the existence of two decay components having fast (10–100 μ s) and slow (0.1–1 ms) relaxation times in the range of 4–60 K. The model calculation including the inter-site energy transfers, the temperature-sensitive and -insensitive non-radiative relaxations fits the experimental results well. Moreover, the long averaged inter-Er 3 + distance obtained by decreasing Er concentration was found to reduce two kinds of non-radiative relaxation rates and the energy transfer rates between Er ions very effectively.

Applied Sciences•May 25, 2018•3 citations
This report summarizes research carried out to investigate energy transfer in an activator-activator system; that is a system for which energy transfer is reversible between certain metastable levels and for which stimulated emission from each of these levels can be generated. The specific system investigated is Er-Ho:YLF. Laser operation from two different ions in the same solid state host has been demonstrated. The 750nm (5S(2) - 5I(7):Ho) and 850nm (4S(3/2) - 4I(13/2:Er) transitions were observed simultaneously and separately at 77K. Cross transfer between the S levels was also observed and the cross transfer rates measured in crystals of five different compositions. Cross transfer between the S levels is mitigated by other cross relaxation transfer schemes which quench the S level storage time of each ion. Only about 25% of the initial population of one ion is transferred to the other in the optimum concentration, 2%Ho-2%Er, at room temperature. The cross transfer rate is only weakly temperature and concentration dependent; at low temperatures cross transfer is somewhat more effective as the decay rates of each ion are longer.
Yttrium Aluminum Garnet (YAG, Y_3 〖Al〗_5 O_12) crystals doped with Erbium have posed an interesting position in the field of rare earth solid state lasers as they possess the property of self-saturation, in which the upper energy level in a laser has a much shorter lifetime than that of the lower level. This is the case of the 2.94μm transition in Er:YAG. That property at first seems to make this material unfit for use as a laser gain medium, however further research into these classes of rare earth materials revealed interesting non-liner energy transfer mechanisms that allow it to be a useful mid wave infra-red (MWIR) coherent source in the continuous wave (CW) and pulsed regimes. This came to fruition due to decades of modeling and spectroscopic research investigating the non-linear energy transfer mechanisms of excited state absorption (ESA), energy transfer up-conversion (ETU), and cross relaxation (XR). These effects show up in the rise and fall times of the levels observed through fluorescence. Resulting in the non-exponential rise and fall characteristics and having a squared or even cubed relation to the population. The population evolution for each of the lasing levels is now affected by ions recycling energy and in turn cause the lifetimes of the levels to “effectively” change to a point where simple linear models do not adequately describe the system and its performance. The non-linear energy transfer dynamics of Er:YAG are modeled under high resonant pump conditions. By pumping with selective resonant pumps, the interaction dynamics of the (_ ^4)I_(11/2) and the (_ ^4)I_(13/2) levels in the Erbium ion reveal the contributions from generally ignored non-linear energy transfer mechanisms. Specifically, the multi-photon effect known as excited state absorption (ESA) is modeled by measuring and characterizing the cross section in single crystal Er:YAG samples utilizing a pump and probe technique coupled with transient fluorescence measurements. The measured ESA cross section is then included in the rate equation modeling.
Yttrium Aluminum Garnet (YAG) crystals doped with Erbium have posed an interesting position in the field of rare earth solid state lasers as they possess the property of self-saturation, in which the upper energy level in a laser has a much shorter lifetime than that of the lower level.The non-linear energy transfer dynamics of Er:YAG are modeled under high resonant pump conditions. Specifically the multi-photon effect known as excited state absorption (ESA) is modeled by measuring the cross section in a single crystal Er:YAG sample utilizing a pump and probe technique. The measured ESA cross section is then included in the rate equation modeling that has typically been ignored such an effect when modeling the non-linear ion to ion interactions. By pumping with selective resonant pumps, the interaction dynamics of the upper and the lower laser levels in the Erbium ion reveal the contributions of the non-linear energy transfer mechanisms towards the populations of the levels respectively. This thesis work shows the added accuracy of the rate equation modeling by its inclusion of the measured ESA cross-section and its effect on the population evolution in the Er:YAG system. The model will be tested with measurements made with select Er:YAG crystals being pumped by combinations of resonant infra-red lasers with a chopper spinning at a rate on the order of magnitude of the lower lasing level lifetime.
To overcome the ETU-induced heating and realize efficient and enhanced laser cooling in Ho3+-doped solids, in Section 4.3, we will provide a modified excitation scheme based on ground-state absorption (GSA) of 5I8 Æ 5I7 at around 2.07 μm and ESA of 5I5 Æ 5F5 at around 2.28 μm. Compared with the conventional pumping scheme, the co-pumping scheme ameliorates the cooling performance significantly through alleviating the upconversion-quenching-induced heat [12], that is, the heat-producing 5I5 Ho3+ions are pumped to the 5F5 state by the laser at 2.28 μm. Fortunately, the 5F5 Ho3+ ions barely transit to the lower nearby state and tend to decay radiatively. Therefore, major heat produced in the conventional laser cooling of Ho3+-doped solids is avoided, and both cooling efficiency and cooling power density can be improved. In Section 4.4, we broaden the research domain of optical refrigeration to rare earth ion co-doped systems. Specifically, when Ho3+–Tm3+ co-doped YLiF4 crystals are pumped at around 2.07 μm, Ho3+ ions will populate at the 5I7 manifold. Meanwhile, Tm3+ ions will also be sensitized by absorbing energy transferred from 5I7 Ho3+ ions. Since the average energy of fluorescence photons generated by Tm3+3F4 Æ 3H6 radiative transitions is higher than that generated by Ho3+5I7 Æ 5I8 radiative transitions, energy transfer (ET) from Ho3+ to Tm3+ ions will induce annihilation of host phonons, and bring enhancement in both the cooling efficiency and the cooling power. Therefore, this cooling mechanism is referred next as energy transfer-enhanced laser cooling (ETLC) of solids [11]. 4.2 Conventional Laser Cooling of Holmium- The main upconversion process and the anti-Stokes fluorescence cooling (ASFC) processes of Ho3+-doped fluoride crystals are illustrated in Fig. 4.1. The ground-state (5I8) Ho3+ ions are pumped to the first excited state (5I7) with laser excitations of energy hν (solid red arrow on the left) and then relax thermally among the Stark levels in a timescale of picoseconds with host phonon absorption. Part of the Ho3+5I7 ions de-excite by emitting fluorescence photons of mean energy hν10 (solid blue arrow, ν10 > ν), which accounts for the ASFC process. The rest of the 5I7 Ho3+ ions de-excited and transfer their energy to the neighboring 5I7 Ho3+ ions, causing population accumulation at the third excited state (5I5) with host phonon absorption (solid green arrows). Comparison between the energy mismatch and the host phonon energy (for YLiF4 crystal host, ħω ≈ 450 cm-1) indicates that about two host phonons are annihilated for each ETU process (see Table 4.1).
Participation of shallow states in the energy transfer processes between the rare-earth ions and a host semiconductor matrix is discussed. It is argued that shallow levels link the atomic-like states of the inner core of the rare-earth ion with the band structure of the host crystal. For the two most investigated systems InP:Yb and Si:Er the important role of these states at various stages of excitation and de-excitation mechanisms is shown. Models of the energy transfer process with a formation of a shallow intermediate state are discussed. It is shown that the formation of such a state is essential for the RE ion core activation. Experimental results supporting the involvement of shallow states are reviewed. Temperature dependencies of the photoluminescence activation and decay time constants are presented; these show an important role of shallow doping in the activation of Auger processes relevant to the mechanism of rare-earth ion photoluminescence. For the Si:Er system direct evidence for the two-stage excitation mechanism is discussed.
Estimations are made of the critical concentration of energy-acceptor ions for which the average efficiency of the excitation transfer from energy-donor ions is 1/2. This gives a measure of the activator concentration at which Inokuti and Hirayama's theory is no longer applicable. Study is also made of the dominant multipole interaction responsible for the energy transfer between rare earth ions in inorganic solids. Finally, importance of the J -selection rule in the determination of the dominant interaction term in the resonance transfer and cooperative processes is emphasized.
We have investigated the energy transfers in the 1.54- μ m region of (Er,Sc) 2 O 3 epitaxial thin films grown on Si(111). The interplay of the energy transfers between Er ions in the different and the same symmetry sites makes the dynamics complicated. To suppress the energy transfer upconversion, low power and resonant excitation of the third crystal-field level ( 4 I 13 / 2 : Y 3 ′ ) of the Er 3 + site with C 3 i symmetry was employed. The time-resolved photoluminescence measurements of the Y 1 ′ - Z 1 ′ transition indicate the existence of two decay components having fast (10–100 μ s) and slow (0.1–1 ms) relaxation times in the range of 4–60 K. The model calculation including the inter-site energy transfers, the temperature-sensitive and -insensitive non-radiative relaxations fits the experimental results well. Moreover, the long averaged inter-Er 3 + distance obtained by decreasing Er concentration was found to reduce two kinds of non-radiative relaxation rates and the energy transfer rates between Er ions very effectively.