Effects of Ag doping on the crystallization properties of Sb-rich GeSb thin films

Ag-doped and un-doped Sb-rich GeSb thin films were deposited by DC magnetron co-sputtering. The electrical, structural, and optical properties of the thin films phase change were investigated using 4-point probe measurement, X-ray diffraction (XRD), transmission electron microscopy (TEM), and a static tester. With increasing Ag doping content, the crystallization temperature and sheet resistance of crystalline state decreased from 325 °C to 283 °C and from 187.33 Ω/□ to 114.62 Ω/□, respectively. XRD patterns of the films showed a Sb hexagonal structure, and the calculated grain size increased from 13.9 nm to 17 nm as the Ag concentration increased. Grain sizes of the Ag-doped thin films were larger than the grain sizes of un-doped thin films, as determined by TEM images. A static tester verified the decreased crystallization speed and optical contrast. Un-doped GeSb crystallization took 160 ns and 16 at.% Ag-doped GeSb crystallization took 200 ns when the laser power was 13 mW. Based on a power-time-effect diagram, the 12.6 at.% Ag-doped GeSb showed good thermal stability in a crystalline state.     

Study of Ge2Sb2Te5 Film for Nonvolatile Memory Medium

The amorphous Ge2Sb2Te5 film with stoichiometric compositions was deposited by co-sputtering of separate Ge, Sb, and Te targets on SiO2/Si (100) wafer in ultrahigh vacuum magnetron sputtering apparatus. The crystallization behavior of amorphous Ge2Sb2Te5 film was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and differential scanning calorimetry (DSC). With an increase of annealing temperature, the amorphous Ge2Sb2Te5 film undergoes a two-step crystallization process that it first crystallizes in face-centered-cubic (fcc) crystal structure and finally fcc structure changes to hexagonal (hex) structure. Activation energy values of 3.636±0.137 and 1.579±0.005 eV correspond to the crystallization and structural transformation processes, respectively. From annealing temperature dependence of the film resistivity, it is determined that the first steep decrease of the resistivity corresponds to crystallization while the second one is primarily caused by structural transformation from     

Crystallization studies on phase-change optical recording media by use of a two-dimensional periodic mark array

We present the results of crystallization studies in thin-film samples of amorphous and crystalline Ge(x)Sb(y)Te(z). The experiments, conducted at moderately elevated temperatures, are based on measurements of the first-order diffraction efficiency from a two-dimensional periodic array of recorded marks. When the samples are slowly heated above room temperature, changes in the efficiencies of various diffracted orders give information about the on-going crystallization process within the sample. Two different compositions of the GeSbTe alloy are used in these experiments. Measurements on Ge(2)Sb(2.3)Te(5) films show crystallization dominated by nucleation. For the Sb-rich eutectic composition Ge-(SbTe), crystallization is found to be dominated by growth from crystalline boundaries. We also show that crystalline marks written by relatively high-power laser pulses are different in their optical properties from the regions crystallized by slow heating of the sample to moderate temperatures.     

激光致溅射沉积Ge2Sb2Te5薄膜的结晶行为研究

利用XRD研究了激光致溅射沉积Ge2Sb2Te5薄膜的结晶行为，研究发现，与热致相变不同的是，激光致相变只发生从非晶态到FCC晶态结构的转变，从FCC与HCP的结构转变不再发生，这有利于提高相变光盘的信噪比。Ge2Sb2Te5薄膜的结晶程度受初始化功率和转速的影响。     

相变光盘记录介质Sb-Se系和Ge-Sb-Te系合金组织及结构

按照配方熔炼制成Sb-Se系和Ge-Sb-Te系合金,对其组织结构进行了观察测试,研究结果表明,制备的合金组织比较均匀,X射线衍射结果表明,Sb-Se系合金1＃样品有Sb析出,2＃样品有Se析出,符合化学计量比的3＃样品全部形成Sb2Se3共晶体。Ge-Sb-Te系合金5＃样品有Sb析出,而符合化学计量比的4＃样品形成GeSb2Te4共晶体。     

Crystal structure and magnetic properties of CuSb2O4

The crystal structure of a copper antimonite (CuSb₂O₄) was determined from X-ray powder diffraction data. The structure was solved by simulated annealing in direct space using the Rietveld method. The compound crystallizes in tetragonal symmetry and space group P4 ₂ bc (106); unit cell parameters a = b = 8.76033(5) Å, c = 5.79786(4) Å, Z = 4, V = 444.947(5) Å³ and density (calc.) = 5.539 g cm^?3. The CuO₆ polyhedra are strongly elongated due to Jahn–Teller distortion in a [2+2+2] coordination arrangement, i.e. there are two long axial Cu–O1 bonds of 2.447(13) Å and in the equatorial plane there are two intermediate Cu–O2 bonds of 2.07(3) Å and two short Cu–O2 bonds of 1.88(2) Å. The SbO₃ pyramidal arrangement is almost regular with Sb–O1 bonds of 1.97(2) Å (2×) and Sb–O2 of 1.959(5) Å. The experimentally obtained Raman spectrum is consistent with values obtained from theoretical modelling studies. The magnetic behaviour of this new compound suggests that it belongs to the class of S = 1/2 Heisenberg chain systems.     

Three distinct optical-switching states in phase-change materials containing impurities:From physical origin to material design

Ge2Sb2Tes is the most widely utilized chalcogenide phase-change material for non-volatile photonic applications,which undergoes amorphous-cubic and cubic-hexagonal phase transition under external excitations.However,the cubic-hexagonal optical contrast is negligible,only the amorphous-cubic phase transition of Ge2Sb2Te5 is available.This limits the optical switching states of traditional active dis-plays and absorbers to two.We find that increasing structural disorder difference of cubic-hexagonal can increase optical contrast close to the level of amorphous-cubic.Therefore,an amorphous-cubic-hexagonal phase transition with high optical contrast is realized.Using this phase transition,we have developed display and absorber with three distinct switching states,improving the switching perfor-mance by 50％.Through the combination of first-principle calculations and experiments,we reveal that the key to increasing structural disorder difference of amorphous,cubic and hexagonal phases is to intro-duce small interstitial impurities(like N)in Ge2Sb2Tes,rather than large substitutional impurities(like Ag)previously thought.This is explained by the formation energy and lattice distortion.Based on the impurity atomic radius,interstitial site radius and formation energy,C and B are also potential suit-able impurities.In addition,introducing interstitial impurities into phase-change materials with van der Waals gaps in stable phase such as GeSb4Te7,GeSb2Te4,Ge3Sb2Te6,Sb2Te3 will produce high optical con-trast amorphous-metastable-stable phase transition.This research not only reveals the important role of interstitial impurities in increasing the optical contrast between metastable-stable phases,but also proposes varieties of candidate matrices and impurities.This provides new phase-change materials and design methods for non-volatile optical devices with multi-switching states.     

Ferromagnetism of Mn/Ge Multilayers Grown by Molecular Beam Epitaxy

We report on novel ferromagnetic Mn/Ge multilayers for spintronics applications investigated both experimentally and theoretically. Two Mn/Ge multilayers are grown on GaAs (001) substrates by molecular beam epitaxy. The period of each multilayer consists of an Mn layer of varying thickness (0.6 and 5 Å) and a 10 Å thick Ge spacer layer. From temperature-dependent magnetization and hysteresis loop measurements, the Mn (0.6 Å)/Ge (10 Å) multilayer showed very weak ferromagnetic ordering, which is persistent up to 260 K, whereas the Mn (5 Å)/Ge (10 Å) multilayer exhibited strong ferromagnetism up to 305 K. The coercive field of the Mn (5 Å)/Ge (10 Å) multilayer was 277 Oe at 200 K. Density functional electronic band structure calculations on a number of Mn/Ge (001) multilayers determined them to be ferromagnetic, and estimates of their critical temperatures are reported.     

Crystallization kinetics of amorphous Ga-Sb films extended for phase-change memory

Performance of phase-change materials based on Ga-Te-Sb was found getting better with decreasing Te content in our earlier studies. We concerned much properties of Te-free, Sb-rich binary Ga-Sb, which has been known to possess extremely fast crystallization behavior. Non-isothermal and isothermal crystallization kinetics of amorphous Sb-rich Ga-Sb films were explored by temperature dependent electrical resistance measurements. The crystallization temperature (183 to 261 degrees C) increases with decreasing Sb content (91 to 77 at%). The activation energy and rate-factor vary with Sb contents and reach the maximum at Ga19Sb81. The kinetic exponent is smaller than 1.5 at Sb < 85 at% denoting that the mechanism is one-dimensional crystal-growth from nuclei. The temperature corresponding to 10-year data-retention, evaluated from films, is 180 degrees C (Ga19Sb81) and 137 degrees C (Ga13Sb87), respectively. We verified memory performance using test-devices made of Ga16Sb84 working at voltages with 100 ns pulse-width.     

Phase transformation and microstructural evolution after heat treatment of a terbium-doped lithium–aluminum phosphate glass

The crystallization kinetics and phase transformation of a transparent Tb³⁺-doped lithium–aluminum phosphate glass, prepared by melt quenching, were investigated. The energy associated to the glass transition and the crystallization parameters (activation energy for crystallization and Avrami exponent) were evaluated by different methods using the experimental data obtained by differential thermal analysis performed at different heating rates. Using an isoconversional method to determine the change of the activation energy for crystallization with the fraction of crystallization, it was verified that with the increase in the fraction of crystallization from 0.1 to 0.9, the value of the activation energy decreased slightly from ~370 to ~310 kJ mol^?1 and that the Avrami exponent varied from 0.8 to 1, suggesting a surface crystal growth mechanism. Observation of the microstructural evolution of heat-treated glass samples confirmed a surface crystallization process revealing spherulitic crystals constituted mainly by aluminum metaphosphate.     

Structural, electrical and optical properties of Si doped ZnO films grown by atomic layer deposition

Si doped ZnO (SZO) films with various Si concentrations were deposited by atomic layer deposition at 300 °C using triethyzinc, tris(dimethylamino)silane and H₂O₂ as the precursors. The influences of Si doping concentration on structural, electrical and optical properties of ZnO films have been investigated. All the films exhibited a highly preferential c-axis orientation. A minimum resistivity of 9.2 × 10^?4 Ω cm, with a carrier concentration of 4.3 × 10²⁰ cm^?3 and a Hall mobility of 15.8 cm²/Vs, was obtained for SZO film prepared with the Si concentration of 2.1 at%. The increase of conductivity with Si doping was attributed to the presence of Si in +3 valence state acting as donor in ZnO and the increases of oxygen vacancies with Si concentration as proven by XPS measurements. The optical bandgap of SZO films initially increased from 3.25 to 3.55 eV with increasing of Si concentration to 2.1 at%, then decreased with further increase of Si concentration. The blue shift of band gap of SZO films with increasing carrier concentration can be explained by the Burstein-Moss (B-M) effects.     

Crystal structure,ion transport and optical properties of new high-conductivity Ag7(Si1 − xGex)S5I solid solutions

Journal of Materials Science - The crystal structure of Ag7(Si0.8Ge0.2)S5I, Ag7(Si0.6Ge0.4)S5I, Ag7(Si0.4Ge0.6)S5I and Ag7(Si0.2Ge0.8)S5I solid electrolytes, grown by vertical zone crystallization...     

Effect of very low to high Sb-doping on the structural,electrical, photo-conductive and thermoelectric properties of fluorine-doped SnO<Subscript>2</Subscript> (FTO) thin films prepared by spray pyrolysis technique

Transparent conducting fluorine and Sb-doped [SnO₂: (F, Sb)] thin films have been deposited onto preheated glass substrates using the spray pyrolysis technique by the various dopant quantity of spray solution. The effect of antimony impurities on the structural, morphological, electrical, Thermo-electrical, optical and photoconductive properties of films has been investigated. The [F/Sn] atomic concentration ratio (x) in the spray solution is kept at value of 0.7 and the [Sb/Sn] atomic ratio (y) varied at values of 0, 0.0005, 0.001, 0.002, 0.01, 0.03, 0.05, 0.07 and 0.10. It is found that the films are polycrystalline in nature with a tetragonal crystal structure corresponding to SnO₂ phase having orientation along the (110) and (200) planes. SEM images indicated that nanostructure of the films has a particle type growth. The average grain size increases with increasing spraying quantity of Sb-dopant. The compositional analysis of SnO₂: (F, Sb) thin films were studied using EDAX. SEM and AFM study reveals the surface of SnO₂: (F, Sb) to be made of nanocrystalline particles. The Hall Effect measurements have shown n-type conductivity in all deposited films. The lowest sheet resistance and highest the carrier concentration about 7.7 Ω/□ and 6.6 × 10²², respectively, were obtained for the film deposited with y = [Sb/Sn] = 0.001 and x = [F/Sn] = 0.7. The maximum of the Seebeck coefficient equal to 12.8 μV K^?1 was obtained at 400 K for the film deposited with y = [Sb/Sn] = 0.10. The average transmittance of films varied over the range 10–80 % with change of Sb-concentration. The band gap values of samples were obtained in the range of 3.19–3.8 eV. From the photoconductive studies, the Sb-doped films exhibited sensitivity to incident light especially in y = 0.001. The electrical resistivity and carrier concentration vary in range 5.44 × 10^?4 to 1.02 × 10^?2Ω cm and 2.6 × 10²²–6.6 × 10²² cm^?3, respectively.     

Thick LPE layers of InAs1−x Sb x for 3–5 μm optoelectronic applications

A calculation of the In–As–Sb phase diagram in the low-temperature range 300–450 °C has been made. Liquid phase epitaxy was performed to grow InAs_1?x Sb _x layers on InAs substrates at temperatures as low as 300 °C. High-quality layers were grown on InAs with x up to 0.26. Scanning electron microscopy (SEM) X-ray microprobe compositional analysis was performed and Raman scattering proved the layer homogeneity and crystal perfection. Pd/Ge/Au ohmic contacts (OC) to InAsSb LPE solid solutions with a low Sb content, doped with group IV elements (Sn and Si) were thermally evaporated. The incorporation of Ge and the redistribution of Si and Sn on the groups III and V vacancies after annealing at T_ann=250–400 °C governs the contact behavior. The C–V characteristics and photosensitivity of the p-InAs/n-InAsSb heterostructures confirmed their device applicability in the 3–5 μm spectral range. The OC deposited on surfaces pre-treated with (NH₄)₂S solid solution exhibited improved ohmic behavior.     

Role of hydrogen in Sb film deposition and characterization of Sb and GexSby films deposited by cyclic plasma enhanced chemical vapor deposition using metal-organic precursors

To meet increasing demands for chemical vapor deposition methods for high performance phase-change memory, cyclic plasma enhanced chemical vapor deposition of Sb and Ge_xSb_y phase-change films and characterization of their properties were performed. Two cycle sequences were designed to investigate the role of hydrogen gas as a reduction gas during Sb film deposition. Hydrogen gas was not introduced into the reaction chamber during the purge step in cycle sequence A and was introduced during the purge step for cycle sequence B. The role of hydrogen gas was investigated by comparing the results obtained from these two cycle sequences and was concluded to exert an effect by a combination of precursor decomposition, surface maintenance as a hydrogen termination agent, and surface etching. These roles of hydrogen gas are discussed through consideration of changes in deposition rates, the oxygen concentration on the surface of the Sb film, and observations of film surface morphology. Based on these results, Ge_xSb_y phase-change films were deposited with an adequate flow rate of hydrogen gas. The Ge and Sb composition of the film was controlled with the designed cycle sequences. A strong oxygen affinity for Ge was observed during the X-ray photoelectron spectroscopy analysis of Sb 3d, Sb 4d, and Ge 3d orbitals. Based on the XPS results, the ratios of Ge to Sb were calculated to be Ge_0.32Sb_0.68, Ge_0.38Sb_0.62, Ge_0.44Sb_0.56, Ge_0.51Sb_0.49 and Ge_0.67Sb_0.33 for the G1S7, G1S3, G1S2, G1S1, and G2S1 cycles, respectively. Crystal structures of Sb, Ge, and the GeSb metastable phase were observed with various Ge_xSb_y film compositions. Sb crystallinity decreased with respect to Ge crystallinity by increasing the Ge fraction. A current-voltage curve was introduced, and an electro-switching phenomenon was clearly generated at a typical voltage, V_th. V_th values increased in conjunction with an increased proportion of Ge. The Sb crystallinity decrease and V_th increase were explained via the bonding characteristics of each element.     

The kinetics of isothermal cold crystallization and tensile properties of poly(ethylene terephthalate)

The exothermic peak that is frequently observed during the heating scan of a differential scanning calorimetry (DSC) experiment of poly(ethylene terephthalate) (PET) is due to a cold crystallization process, originating from the rearrangement of amorphous regions into a crystalline phase. In this work the isothermal cold crystallization kinetics of PET was investigated by using DSC, X-ray diffraction and tensile experiments. The isothermal crystallization rate was determined as a function of temperature, and the Avrami analysis was conducted. The results showed that at low temperatures the cold crystallization is a two-regime process, whereas at high temperatures just one stage is observed. The rate constant for isothermal crystallization K increased and the half time of crystallization (t_½) decreased with increasing crystallization temperature. The Avrami exponent n was close to 2, and this corresponds to a disc-like morphology formed by heterogeneous nucleation. Cold crystallization increased the crystallinity and therefore the tensile properties of the samples were enhanced.     

Phase transition characteristics and electrical properties of nitrogen-doped GeSb thin films for PRAM applications

We have investigated the nitrogen doping effect on phase transition characteristics and electrical property of nitrogen-doped GeSb (N-doped GS) thin films. The nitrogen gas flow rate changed from 0 sccm (GS(0)) to 6 sccm (GS(6)) during the deposition. The sheet resistance of crystalline state was increased from 2.6 to 5.1 kΩ/□ and thermal stability of amorphous was increased as nitrogen gas flow rate increased due to nitrogen doping effect. Moreover, the average grain size was decreased from 9.7 to 6.6 nm at 400 °C as nitrogen gas flow rate increased. However, the crystallization threshold time and laser power of GS(6) were shorter and lower than GS(0) caused by lower optical reflectivity. Nitrogen-doped GeSb showed the possibility of low RESET power and high speed PRAM operation.     

Solid-phase crystallization of amorphous SiGe films deposited by LPCVD on SiO2 and glass

The crystallization kinetics and film microstructure of poly-SiGe layers obtained by solid-phase crystallization (SPC) of amorphous SiGe with Ge fractions (x) in the 0 to 0.42 range have been studied in detail. Amorphous SiGe layers 100 nm thick were deposited by LPCVD at 450°C on thermally oxidized Si wafers and 7059 Corning glasses, using Si₂H₆ and GeH₄ as gas sources. The samples were crystallized at 550°C and low pressure (below 9 Pa). The evolution of the crystallization and the resulting film microstructure were characterized by X-ray diffractometry and transmission electron microscopy. The experimental results on growth kinetics fit the Avrami’s model. The characteristic crystallization time decreases with x, slowly for x<0.3 and more abruptly for higher values of x. The transient time depends exponentially on x in all the intervals. The crystallized films have a (111) preferred orientation for low values of x and evolve to a randomly oriented polycrystal as x increases. The grain size in the fully crystallized layers decreases with increasing x. The results are similar for the films deposited on silicon dioxide and glass.     

Temperature sensors based on multimode chalcogenide fibre Bragg gratings

In this work, a theoretical study was conducted on temperature sensing in Ge–Sb–Se multimode fibre Bragg grating (MM-FBG). The sensing characteristics of the designed MM-FBGs with different fibre parameters and operating wavelengths were calculated using a coupled model method. The temperature sensitivity of this MM-FBG was found to improve significantly by shifting the operating wavelength from telecom range to mid-infrared (MIR) and utilizing the wide transmission range of Ge–Sb–Se glasses. The temperature sensitivity of the proposed Ge–Sb–Se MM-FBG was calculated to be 0.0758 nm/°C at 1550 nm, which is 7.58 times higher than silica FBGs at 1550 nm, and the temperature sensitivity was calculated to be more than 0.16 nm/°C at 3390 nm, which is 2.2 times higher than that at 1550 nm. In addition, the proposed MM-FBGs provided multi-peak information, and the sensitivity of each peak was calculated to be comparable to the single-mode FBG. The proposed Ge–Sb–Se MM-FBG has great potential for temperature sensing in MIR because of its advantages of simple preparation, high coupling efficiency, multi-peak information and wide working window.     

表面接枝处理的n-HA充填PLGA等温结晶行为的研究

应用示差扫描量热计（DSC）研究了用低分子量聚乳酸（PDLLA）接枝与未接枝两种处理的纳米羟基磷灰石（n-HA）对聚乙丙交酯（PLGA）等温结晶行为及熔融行为的影响,采用Avrami方程处理其等温结晶过程,计算结晶动力学参数;同时用配带热台的偏光显微镜（POM）研究了其结晶的晶核形态。结果表明该体系等温结晶行为可以用Avrami方程来描述;加入n-HA的两种复合材料及PLGA其结晶最快的温度都是110℃,且都是随着结晶温度的提高结晶速率变慢,但接枝的n-HA对提高PLGA基体的结晶速率、熔点及结晶活化能都比未接枝处理的要小。偏光显微镜研究得出加入n-HA的两种复合材料及PL-GA其球径形态相似,且都随温度升高而使结晶速度降低,但加入未接枝的n-HA比接枝后的结晶更快。以上结果说明接枝处理后的n-HA提高了两相界面结合,因而n-HA的异相成核能力比未接枝处理的要差。