Dy(2+):CaF(2) saturable-absorber Q switch for the ruby laser

Passive Q switching of a flash-lamp-pumped ruby laser has been demonstrated with a Dy(2+):CaF(2) saturable absorber at room temperature. Typically a single Q-switched pulse of 4.5 mJ and 94 ns was observed. At 694 nm, the ground-state absorption cross section and the excited-state absorption cross section of the Dy(2+):CaF(2) absorber were found to be 1.2 × 10(-18) cm(2) and 0.9 × 10(-18) cm(2) respectively, with a four-level slow-relaxing saturable-absorber model.     

Low-temperature approach to high-yield and reproducible syntheses of high-quality small-sized PbSe colloidal nanocrystals for photovoltaic applications

Small-sized PbSe nanocrystals (NCs) were synthesized at low temperature such as 50-80 °C with high reaction yield (up to 100%), high quality, and high synthetic reproducibility, via a noninjection-based one-pot approach. These small-sized PbSe NCs with their first excitonic absorption in wavelength shorter than 1200 nm (corresponding to size < ～3.7 nm) were developed for photovoltaic applications requiring a large quantity of materials. These colloidal PbSe NCs, also called quantum dots, are high-quality, in terms of narrow size distribution with a typical standard deviation of ～7-9%, excellent optical properties with high quantum yield of ～50-90% and small full width at half-maximum of ～130-150 nm of their band-gap photoemission peaks, and high storage stability. Our synthetic design aimed at promotion of the formation of PbSe monomers for fast and sizable nucleation with the presence of a large number of nuclei at low temperature. For formation of the PbSe monomer, our low-temperature approach suggests the existence of two pathways of Pb-Se (route a) and Pb-P (route b) complexes. Either pathway may dominate, depending on the method used and its experimental conditions. Experimentally, a reducing/nucleation agent, diphenylphosphine, was added to enhance route b. The present study addresses two challenging issues in the NC community, the monomer formation mechanism and the reproducible syntheses of small-sized NCs with high yield and high quality and large-scale capability, bringing insight to the fundamental understanding of optimization of the NC yield and quality via control of the precursor complex reactivity and thus nucleation/growth. Such advances in colloidal science should, in turn, promote the development of next-generation low-cost and high-efficiency solar cells. Schottky-type solar cells using our PbSe NCs as the active material have achieved the highest power conversion efficiency of 2.82%, in comparison with the same type of solar cells using other PbSe NCs, under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm(2).     

Multiple exciton generation in films of electronically coupled PbSe quantum dots

We study multiple exciton generation (MEG) in electronically coupled films of PbSe quantum dots (QDs) employing ultrafast time-resolved transient absorption spectroscopy. We demonstrate that the MEG efficiency in PbSe does not decrease when the QDs are treated with hydrazine, which has been shown to greatly enhance carrier transport in PbSe QD films by decreasing the interdot distance. The quantum yield is measured and compared to previously reported values for electronically isolated QDs suspended in organic solvents at approximately 4 and 4.5 times the effective band gap. A slightly modified analysis is applied to extract the MEG efficiency and the absorption cross section of each sample at the pump wavelength. We compare the absorption cross sections of our samples to that of bulk PbSe. We find that both the biexciton lifetime and the absorption cross section increase in films relative to isolated QDs in solution.     

Continuous-wave power transmission and thermal lensing of a saturable absorber subject to excited-state absorption

Rate-equation analysis has been used in an investigation of the role of saturation and excited-state absorption in the power transmission characteristics and thermal lensing of an absorber. Use of an iterative approach gives explicit analytical results for power transmission and thermal focal length in the presence of excited-state absorption. Sample calculations indicate that pump absorption can increase or decrease with increasing incident pump power, depending on the relative strength of the excited-state absorption cross section with respect to the ground-state absorption cross section. In the case of thermal lensing, results further indicate that saturation and excited-state absorption act as two competing effects, the former reducing the strength of the thermal lens and the latter causing the opposite effect. The analytical formulas derived in this analysis should prove useful to experimentalists in determination of ground-state and excited-state absorption cross sections from experimental power transmission and lensing data.     

Quasi-Resonant Nonlinear Absorption for Optical Power Limiting: solgel-Processed Er(3+)-Doped Multicomponent Silica Glass

We demonstrate optical power limiting by what we believe to be a new mechanism of nonlinear absorption, which involves a quasi-resonant ground-state absorption that is either phonon assisted or assisted by the presence of defect sites (tail absorption). Such a mechanism provides high transmittance at low intensity yet optical limiting under cw conditions. The sample used was a novel solgel-processed Er(3+)-doped multicomponent silica glass. In this system the nonlinear absorption process is achieved because the resonant excited-state ((4)I(13/2) ? (4)S(3/2)) absorption cross section is larger than the quasi-resonant ground-state ((4)I(15/2) ? (4)I(9/2)) absorption cross section.     

Cobalt-doped transparent glass ceramic as a saturable absorber q switch for erbium:glass lasers

A new saturable absorber Q switch for 1.54-mum Er:glass lasers is presented. The saturable absorber is a transparent glass ceramic that contains magnesium-aluminum spinel nanocrystallites doped with tetrahedrally coordinated Co(2+) ions. We obtained Q-switched pulses of up to 5.5 mJ in energy and 80 ns in duration at 1.54 mum. The relaxation time of (4)A(2) ?(4)T(1)((4)F) transition bleaching was measured to be (450 ? 150) ns. Ground-state and excited-state absorption cross sections at 1.54-mum wavelength were estimated to be (3.2 ? 0.4) x 10(-19) cm(2) and (5.0 ? 0.6) x 10(-20) cm(2), respectively.     

Two-fold emission from the S-shell of PbSe/CdSe core/shell quantum dots

The optical properties of PbSe/CdSe core/shell quantum dots with core sizes smaller than 4 nm in the 5-300 K range are reported. The photoluminescence spectra show two peaks, which become increasingly separated in energy as the core diameter is reduced below 4 nm. It is shown that these peaks are due to intrinsic exciton transitions in each quantum dot, rather than emission from different quantum dot sub-ensembles. Most likely, the energy separation between the peaks is due to inter-valley coupling between the L-points of PbSe. The temperature dependence of the relative intensities of the peaks implies that the two emitting states are not in thermal equilibrium and that dark exciton states must play an important role.     

金属团簇化合物W2Ag4S8(dppf)2激发态非线性光学性质

用Z扫描方法测量了金属团簇化合物W2Ag4S8(dppf)2的非线性光学响应,发现团簇W2Ag4S8(dppf)2具有显著的反饱和吸收和自聚焦等非线性光学性质.应用激发态理论分析了团簇W2Ag4S8(dppf)2的非线性吸收和非线性折射,结果与实验数据一致.通过数值模拟获得激发态和基态吸收截面比值Ka及非线性折射度比值Kr,阐述了Ka和Kr的物理意义.确定了团簇W2Ag4S8(dppf)2的三阶极化率x(3).团簇化合物W2Ag4S8(dppf)2对脉宽为纳秒的激发脉冲限幅效果比较好.     

Studies of third-order optical nonlinearities and optical limiting of 2, 3-butanedione dihydrazone

2, 3-butanedione dihydrazone (BDDH) synthesized via chemical route and nonlinear optical parameters, such as nonlinear refractive index (n2), nonlinear absorption coefficient (β), third-order nonlinear optical susceptibility (χ(3)), second hyperpolarizability (γ), and optical-limiting behavior were investigated by single beam z-scan technique for different concentrations. Synthesized sample were irradiated by a Q-switched, frequency doubled Nd:YAG laser and found that n2 and β increases linearly with increasing concentration and hence γ decreases linearly. The excited-state absorption cross sections of BDDH were found to be larger than ground-state absorption cross sections, and it leads to reverse saturable absorption (RSA). The experimental results are well in agreement with the theory and also establish BDDH as one of the potential candidate materials for optical limiting at 532 nm.     

Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe?.?S?.? NCs as their active materials reached a high power conversion efficiency (PCE) of 3.44%, with an open circuit voltage (V(oc)) of 0.49 V, short circuit photocurrent (J(sc)) of 13.09 mA/cm2, and fill factor (FF) of 0.54 under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm2. The syntheses of the small-sized colloidal PbSe(x)S(1-x) NCs were carried out at low temperature (60 °C) with long growth periods (such as 45 min) via a one-pot noninjection-based approach in 1-octadecene (ODE), featuring high reaction yield, high product quality, and high synthetic reproducibility. This low-temperature approach employed Pb(oleate)? as a Pb precursor and air-stable low-cost thioacetamide (TAA) as a S source instead of air-sensitive high-cost bis(trimethylsilyl)sulfide ((TMS)?S), with n-tributylphosphine selenide (TBPSe) as a Se precursor instead of n-trioctylphosphine selenide (TOPSe). The reactivity difference of TOPSe made from commercial TOP 90% and TBPSe made from commercial TBP 97% and TBP 99% was addressed with in situ observation of the temporal evolution of NC absorption and with 31P nuclear magnetic resonance (NMR). Furthermore, the addition of a strong reducing/nucleation agent diphenylphosphine (DPP) promoted the reactivity of the Pb precursor through the formation of a Pb-P complex, which is much more reactive than Pb(oleate)?. Thus, the reactivity of TBPSe was increased more than that of TAA. The larger the DPP-to-Pb feed molar ratio, the more the Pb-P complex, the higher the Se amount in the resulting homogeneously alloyed PbSe(x)S(1-x) NCs. Therefore, the use of DPP allowed reactivity match of the Se and S precursors and led to sizable nucleation at low temperature so that long growth periods became feasible. The present study brings insight into the formation mechanism of monomers, nucleation/growth of colloidal composition-tunable NCs, and materials design and synthesis for next-generation low-cost and high-efficiency solar cells.     

Structural,optical and electrical properties of PbS and PbSe quantum dot thin films

PbS and PbSe were prepared by hot injection method. The powders were used for preparing the corresponding films by using thermal evaporation technique. The structural, optical and electrical properties of PbS and PbSe thin films were investigated. The structural properties of PbS and PbSe were investigated by X-ray diffraction, transmission electron microscopy and energy dispersive X-ray techniques (EDX). PbS and PbSe films were found to have cubic rock salt structure. The particles size ranged from 1.32 to 2.26 nm for PbS and 1.28–2.48 nm for PbSe. EDX results showed that PbS films have rich sulphur content, while PbSe films have rich lead content. The optical constants (absorption coefficient and the refractive index) of the films were determined in the wavelength range 200–2500 nm. The optical energy band gap of PbS and PbSe films was determined as 3.25 and 2.20 eV, respectively. The refractive index, the optical dielectric constant and the ratio of charge carriers concentration to its effective mass were determined. The electrical resistivity, charge carriers concentration and carriers mobility of PbS at room temperature were determined as 0.55 Ω cm, 1.7 × 10¹⁶ cm^?3 and 656 cm² V^?1 s^?1, respectively, and for PbSe films they were determined as 0.4 Ω cm, 9 × 10¹⁵ cm^?3 and 1735 cm² V^?1 s^?1, respectively. These electrical parameters were investigated as a function of temperature.     

Solution-processed,flexible and broadband photodetector based on CsPbBr_3/PbSe quantum dot heterostructures

Due to their promising applications in foldable displays,optical communication equipment and environmental monitoring systems,flexible and broadband optoelectronic devices have gained extensive attention in recent years.Here,a flexible and broadband photodetector based on CsPbBr₃/PbSe quantum dot(QD) heterostructures is firstly presented.The integrated QD heterostructures possess consecutive detection range from ultraviolet(UV) to long-wave length infrared(LW-IR) regions with efficient light absorption and chemical stability,in comparison with the pristine PbSe QDs.Systematic material characterizations reveal the improved exciton dissociation,carrier transport and carrier lifetime of the QD heterostructures.Flexible photodetector Ag/CsPbBr₃/PbSe/Ag demonstrate a high responsivity of 7.17 A/W with a specific detectivity of 8.97 × 10¹² Jones under 25 μW/cm² 365 nm illumination at 5 V.Furthermore,it could maintain 91.2 %(or 94.9 %) of its initial performance even after bending for thousands of times(or exposing in ambient air for 4 weeks).More importantly,its re s ponse time is shortened more than three orders of magnitude as that of pristine PbSe QDs-based photodetectors.Therefore,it provides a feasible and promising method for the next-generation high-performance broadband photodetectors via constructing heterostructures of various QDs.     

In-situ observation of nucleation and growth of PbSe magic-sized nanoclusters and regular nanocrystals

In-situ observation of the temporal evolution of the absorption of PbSe nanocrystals (NCs) via a low-temperature noninjection approach is presented. Based on a model reaction of lead oleate (Pb(OA)(2) ) and n-trioctylphosphine selenide (TOPSe) in 1-octadecene at 35-80 °C, the use of commercially available TOP (90 or 97%) in affecting the formation of the NCs is explored. TOPSe solutions made from TOP 90% exhibited higher reactivity than those made from TOP 97%. (31)P NMR spectroscopy detected no dioctylphosphine selenide (DOPSe) but some DOP in ≈1.0 M TOPSe/TOP solution (made from TOP 90%), as well as no diphenylphosphine selenide (DPPSe) when DPP was added to the ≈1.0 M solution. Hence, it is proposed that, for the formation of PbSe monomers, an indirect pathway dominates with the formation of a Pb-P complex/intermediate, which results from the activation of Pb(OA)(2) by a phosphine compound (such as DPP, DOP, or TOP) and in turn reacts with TOPSe. With the use of TOP 90% and the addition of secondary phosphine DPP, the formation of PbSe magic-sized nanoclusters (MSNCs) and regular NCs (RNCs) is investigated. With proper tuning of the synthesis conditions, the formation of various PbSe MSNCs versus RNCs is monitored in situ with versus without the addition of DPP, or at different reaction temperatures but otherwise identical synthetic formulation and reaction parameters. Accordingly, the degree of supersaturation (DS) of the PbSe monomer affecting the development of these PbSe MSNCs versus RNCs is proposed; the higher the DS, the more the MSNCs are favored. Also, surface-determined cluster-cluster aggregation is proposed to be the growth mechanism for both the RNCs and MSNCs. For the former, quantized growth is followed by continuous growth. For the latter, the sizes of the magic-sized families are calculated.     

Determining the internal quantum efficiency of PbSe nanocrystal solar cells with the aid of an optical model

We determine the internal quantum efficiency (IQE) of the active layer of PbSe nanocrystal (NC) back-contact Schottky solar cells by combining external quantum efficiency (EQE) and total reflectance measurements with an optical model of the device stack. The model is parametrized with the complex index of refraction of each layer in the stack as calculated from ellipsometry data. Good agreement between the experimental and modeled reflectance spectra permits a quantitative estimate of the fraction of incident light absorbed by the NC films at each wavelength, thereby yielding well-constrained QE spectra for photons absorbed only by the NCs. Using a series of devices fabricated from 5.1+/-0.4 nm diameter PbSe NCs, we show that thin NC cells achieve an EQE and an active layer IQE as high as 60+/-5% and 80+/-7%, respectively, while the QE of devices with NC layers thicker than about 150 nm falls, particularly in the blue, because of progressively greater light absorption in the field-free region of the films and enhanced recombination overall. Our results demonstrate that interference effects must be taken into account in order to calculate accurate optical generation profiles and IQE spectra for these thin film solar cells. The mixed modeling/experimental approach described here is a rigorous and powerful way to determine if multiple exciton generation (MEG) photocurrent is collected by devices with EQE<100%. On the basis of the magnitudes and shapes of the IQE spectra, we conclude that the 1,2-ethanedithiol treated NC devices studied here do not produce appreciable MEG photocurrent.     

CdSe/Cd(x)Zn1-xS core/shell nanocrystals: core morphology and luminescent property

CdSe cores with rod (an aspect ratio of 1.8, d-5 nm) and spherical (an aspect ratio of 1, d-5 nm) morphologies were fabricated by two kinds of organic approaches through adjusting growth processes. Because of large difference of size and morphology, two kinds of cores revealed different absorption spectra. However, these cores exhibited almost same photoluminescence (PL) spectra with a red-emitting PL peak of around 625 nm. This is ascribed that they have a similar size in diameter. A graded Cd(x)Zn1-xS shell of larger band gap was grown around CdSe rods and spheres using oleic acid as a capping agent. Based on the growth kinetics of CdS and ZnS, interfacial segregation was created to preferentially deposit CdS near the core, providing relaxation of the strain at the core/shell interface. For spherical CdSe cores, the homogeneous deposition of the Cd(x)Zn1-xS shell created spherical core/shell nanocrystals (NCs) with a size of 7.1 nm in diameter. In the case of using CdSe cores with rod morphology, the anisotropic aggregation behaviors of CdS monomers on CdSe rods led to the size (approximately 10 nm in diameter) of spherical CdSe/Cd(x)Zn1-xS core/shell NCs with a small difference to the length of the CdSe rod (approximately 8.9 nm). The resulting spherical core/shell NCs created by the rod and spherical cores exhibited almost same PL peak wavelength (652 and 653 nm for using rod and spherical cores, respectively), high PL efficiency up to 50%, and narrow PL spectra (36 and 28 nm of full with at half maximum of PL spectra for the core/shell NCs with CdSe spheres and rods, respectively). These core/shell NCs provide an opportunity for the study of the evolution of PL properties as the shape of semiconductor NCs.     

The peculiar electronic structure of PbSe quantum dots

PbSe is a pseudo-II-VI material distinguished from ordinary II-VI's (e.g., CdSe, ZnSe) by having both its valence band maximum (VBM) and its conduction band minimum (CBM) located at the fourfold-degenerate L-point in the Brillouin zone. It turns out that this feature dramatically affects the properties of the nanosystem. We have calculated the electronic and optical properties of PbSe quantum dots using an atomistic pseudopotential method, finding that the electronic structure is different from that of ordinary II-VI's and, at the same time, is more subtle than what k.p or tight-binding calculations have suggested previously for PbSe. We find the following in PbSe dots: (i) The intraband (valence-to-valence and conduction-to-conduction) as well as interband (valence-to-conduction) excitations involve the massively split L-manifold states. (ii) In contrast to previous suggestions that the spacings between valence band levels will equal those between conduction band levels (because the corresponding effective-masses me approximately mh are similar), we find a densely spaced hole manifold and much sparser electron manifold. This finding reflects the existence of a few valence band maxima in bulk PbSe within approximately 500 meV. This result reverses previous expectations of slow hole cooling in PbSe dots. (iii) The calculated optical absorption spectrum reproduces the measured absorption peak that had previously been attributed to the forbidden 1Sh --> 1Pe or 1Ph --> 1Se transitions on the basis of k.p calculations. However, we find that this transition corresponds to an allowed 1Ph --> 1Pe excitation arising mainly from bulk states near the L valleys on the Gamma-L lines of the Brillouin zone. We discuss this reinterpretation of numerous experimental results.     

Effect of strain in PbSe/ZnPc stacked layers prepared by thermal evaporation method

The article investigates the structural and optical properties of ZnPc/PbSe hybrid multilayer (HML) structure deposited by using thermal evaporation technique. The X-ray diffraction pattern reveals the formation of ZnPc–PbSe composite and strain induced quantum size effect. Scanning electron microscope image shows the spherical grains for as-deposited film and nanorod like structure for the annealed film. The rods are oriented along one direction and stacking axis changes with the function of annealing temperature. The optical spectra show strong absorption in UV–Visible region and the optical absorption edge was red shifted for annealed samples. The luminescence properties were enhanced with broad emission in the range of 375–400 nm in HMLs. The optical band gap values are calculated and it varies from 3.2 to 3.04 eV with the function of annealing temperature and the band gap splitting was observed for a higher temperature of annealed samples. Strain-induced effect on ZnPc/PbSe HML has been reported using Raman spectra.     

Excited-state absorption at 1.57 μm in U:CaF2 and Co:ZnSe saturable absorbers

Appreciable excited-state absorption (ESA) in U²⁺:CaF₂ and Co²⁺:ZnSe saturable absorbers was measured at λ=1.573 μm by optical transmission versus light fluence curves of 30–40 ns long pulses. The ground- and excited-state absorption cross-sections obtained were (9.15±0.3)×10⁻²⁰ and (3.6±0.2)×10⁻²⁰ cm², respectively, for U²⁺:CaF₂, and (57±4)×10⁻²⁰ and (12.5±1)×10⁻²⁰ cm² for Co²⁺:ZnSe. Thus, ESA is not negligible in U²⁺:CaF₂ and Co²⁺:ZnSe, as previously estimated.     

Optical investigation of quantum confinement in PbSe nanocrystals at different points in the Brillouin zone

We present detailed investigations on the optical properties of PbSe nanocrystals. The absorption spectra of monodisperse, quasispherical nanocrystals exhibit sharp features as a result of distinct optical transitions. To study the size dependence, absorption spectra of nanocrystals ranging from 3.4 to 10.9 nm in diameter are analysed and a total of 11 distinct optical transitions are identified. The assignment of the various optical transitions is discussed and compared to theoretically calculated transition energies. By plotting all transitions as a function of nanocrystal size (D) we find that the energy (E) changes with the following relationship [Formula: see text] for the lowest energy transitions. The transition energy extrapolates to approximately 0.3 eV for infinite crystal size, in agreement with the bandgap of bulk PbSe at the L-point in the Brillouin zone. In addition, high-energy transitions are observed, which extrapolate to 1.6 eV for infinite crystal size, which is in good agreement with the bulk bandgap of PbSe at the Sigma-point in the Brillouin zone. Tight-binding calculations confirm that the high-energy transitions originate from the Sigma-point in the Brillouin zone. The Sigma-character of the high-energy transitions may be of importance to explain the mechanism behind multiple exciton generation in PbSe nanocrystals.     

Tuning the band gap of PbSe quantum dots in glasses by TiO doping

Titanium monoxide (TiO) was added to host glass, which was heat-treated at 520 °C for 10 h to incorporate Ti²⁺ into PbSe quantum dots (QDs) to control their band gaps. Incorporation of Ti²⁺ ions into PbSe QDs was confirmed using electron energy loss spectroscopy analysis. Addition of TiO caused blue-shift of the absorption and photoluminescence (PL) bands of the QDs. Absorption bands moved from 1621 nm at TiO concentration [TiO] = 0.0% to 1418 nm at [TiO] = 0.4 mol%. Average diameters of QDs remained mostly unaffected (i.e., 6.25 ± 0.14 nm at [TiO] = 0.0% to 6.03 ± 0.1 nm at [TiO] = 0.4 mol%). The changes in absorption and PL bands originated from the incorporation of Ti²⁺ ions into PbSe QDs. Band gaps of PbSe QDs increased from 0.76 eV at [TiO] = 0% to 0.88 eV at [TiO] = 0.4 mol%. This simple method to tune the band gap of PbSe QDs has possible applications in optical communication fiber amplifiers, infrared laser sources and saturable absorbers.