Structural and optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>O thin films synthesized with metal organic chemical vapor deposition

We present the structural and optical properties of Zn_1?xMg_xO thin films studied using x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and photoluminescence (PL) measurements. The Zn_1?xMg_xO films on sapphire [0001] substrates were fabricated with metal organic chemical vapor deposition (MOCVD). The XRD measurements showed that the Zn_1?xMg_xO films (x≤0.05) had a wurtzite structure without any MgO phase and were epitaxially grown along the c-axis of the Al₂O₃ substrate. The lattice constant of the Zn_0.95Mg_0.05O film shrank by 0.023 Å, compared with that of ZnO crystals. From the EXAFS measurements on the Zn_1?xMg_xO films at Zn K-edge, we found a substantial amount of distortion in the bond length of Zn-Zn pairs with a small amount of Mg substitution on the Zn site. The PL measurements showed a gradual increment of the main exciton transitions from 3.36 eV (x=0.0) to 3.57 eV (x=0.05) at 10 K. We also observed a strong deep-level emission near 2.3 eV from the specimen with x=0.05.     

Electrodeposition of <Emphasis Type="Italic">p</Emphasis>-Type Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films

Thermoelectric Sb _x Te _y films were potentiostatically electrodeposited in aqueous nitric acid electrolyte solutions containing different concentrations of TeO₂. Stoichiometric Sb _x Te _y films were obtained by applying a voltage of −0.15 V versus saturated calomel electrode (SCE) using a solution consisting of 2.4 mM TeO₂, 0.8 mM Sb₂O₃, 33 mM tartaric acid, and 1 M HNO₃. The nearly stoichiometric Sb₂Te₃ films had a rhombohedral structure, R[`3]m R\bar{3}m , with a preferred orientation along the (015) direction. The films had hole concentration of 5.8 × 10¹⁸/cm³ and exhibited mobility of 54.8 cm²/Vs. A more negative potential resulted in higher Sb content in the deposited Sb _x Te _y films. Furthermore, it was observed that the hole concentration and mobility decreased with increasingly negative deposition potential, and eventually showed insulating properties, possibly due to increased defect formation. The absolute value of the Seebeck coefficient of the as-deposited Sb₂Te₃ thin film at room temperature was 118 μV/K.     

Formation and crystallization of silicon nanoclusters in SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>:H films using femtosecond pulsed laser annealings

SiN _x :H films of different compositions grown on glass and silicon substrates using plasma-chemical vapor deposition at a temperature of 380°C have been subjected to pulsed laser annealings. The treatments are performed using titanium-sapphire laser radiation with a wavelength of 800 nm and a pulse duration of 30 fs. Structural changes in the films are studied using Raman spectroscopy. Amorphous silicon nanoclusters are detected in as-grown films with molar fractions of excess silicon of ∼1/5 and larger. Conditions required for pulsed crystallization of nanoclusters were determined. According to the Raman data, no silicon clusters were detected in as-grown films with a small amount of excess silicon (x > 1.25). Pulsed treatments resulted in the formation of silicon nanoclusters 1–2 nm in size in these films.     

Effect of erbium fluoride doping on the photoluminescence of SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films

The photoluminescence of SiO _x films deposited on c-Si wafers by the thermal evaporation of SiO in a vacuum and, for the first time, doped with ErF₃ by coevaporation is studied. It is shown that, like undoped SiO _x films, the unannealed SiO _x :ErF₃ films passivate the surface of the Si wafers and, thus, increase their edge photoluminescence intensity almost fivefold. A similar increase is observed after annealing of the doped films in air at 750°C. Doping with ErF₃ suppresses the photoluminescence of Si nanoclusters, if the films have been subjected to high-temperature annealing (at 750°C). In this case, the PL intensity of the band with a peak at ∼890 nm decreases as well. The ∼890 nm band is observed for the first time and, due to its features, is attributed to transitions in SiO _x matrix defects. The experimentally observed effect of ErF₃ doping on SiO _x film photoluminescence is interpreted. An intense photoluminescence signal from Er³⁺ ions in the nearinfrared spectral region (the ⁴ I _11/2 → ⁴ I _15/2 and ⁴ I _13/2 → ⁴ I _15/2 transitions) is observed in the SiO _x :ErF₃ films annealed in air at 750°C. This finding shows that 1.54 μm luminescent emitters, which are currently in popular demand, can be produced by a simple low-cost method.     

Preparation and Thermoelectric Properties of LaGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> and SmGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript>

Thermoelectric materials are attractive since they can recover waste heat directly in the form of electricity. In this study, the thermoelectric properties of ternary rare-earth sulfides LaGd_1+x S₃ (x = 0.00 to 0.03) and SmGd_1+x S₃ (x = 0.00 to 0.06) were investigated over the temperature range of 300 K to 953 K. These sulfides were prepared by CS₂ sulfurization, and samples were consolidated by pressure-assisted sintering to obtain dense compacts. The sintered compacts of LaGd_1+x S₃ were n-type metal-like conductors with a thermal conductivity of less than 1.7 W K⁻¹ m⁻¹. Their thermoelectric figure of merit ZT was improved by tuning the chemical composition (self-doping). The optimized ZT value of 0.4 was obtained in LaGd_1.02S₃ at 953 K. The sintered compacts of SmGd_1+x S₃ were n-type hopping conductors with a thermal conductivity of less than 0.8 W K⁻¹ m⁻¹. Their ZT value increased significantly with temperature. In SmGd_1+x S₃, the ZT value of 0.3 was attained at 953 K.     

Visible photoluminescence of selectively etched porous <Emphasis Type="Italic">nc</Emphasis>-Si-Sio<Subscript>x</Subscript> structures

The results of the first studies of the effect of selective etching on photoluminescence in porous nc- Si–SiO_x structures containing Si nanoclusters (nc-Si) in the SiO_x matrix are reported. In the initial samples at room temperature, intense photoluminescence bands are observed with peaks at 840 and 660 nm corresponding to radiative recombination of free charge carriers (or charge carriers bound to excitons) excited in nc- Si. After selective etching of the nc- Si–SiO_x structures in 1% HF solution, these bands are noticeably shifted to higher energies of the spectrum. It is suggested that the evolution of the spectra is due to the decrease in the Si nanoparticle dimensions on etching of the oxide and additional oxidation of nc- Si. The results show that selective etching of the oxide matrix can be used to control the radiation spectra of porous nc- Si–SiO_x structures.     

Specific Features and Nature of the 890 nm Photoluminescence Band Detected in SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Films after Low-Temperature Annealing

A band with a peak at 890 nm is detected in the photoluminescence spectra of SiO _x (x ≈ 1.3) films deposited by thermal evaporation of SiO and annealed in air at 650–1150°C. The 890-nm band appears after low-temperature (∼650°C) annealing and exhibits a number of features: (i) as the annealing temperature is elevated to 1150°C, the position of the band peak remains unchanged, whereas the intensity increases by two orders of magnitude; (ii) the effects of the annealing atmosphere (air, vacuum) and the excitation wavelength and power density on the intensity of the 890-nm band differ from the corresponding effects on the well-known bands observable in the ranges 600–650 and 700–800 nm; and (iii) the photoluminescence decay is first fast and then much slower, with corresponding lifetimes of ∼9 and ∼70 μs. The observed features are inconsistent with the interpretation of photoluminescence observed in SiO _x so far. Specifically, the earlier observed photoluminescence was attributed to transitions between the band and defect states in the matrix and between the states of band tails, transitions inside Si nanoclusters, and intraion transitions in rare-earth impurity ions. Therefore, we consider here the possibility of attributing the 890-nm band to transitions in local centers formed by silicon ions twofold- and/or threefold-coordinated with oxygen; i.e., we attempt to interpret the 890-nm band in the same manner as was done for luminescence in SiO₂ glasses and films slightly deficient in oxygen.     

Microstructure and Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>- and <Emphasis Type="Italic">p</Emphasis>-Type Doped Mg<Subscript>2</Subscript>Sn Compounds Prepared by the Modified Bridgman Method

Mg₂Sn compounds were prepared by the modified vertical Bridgman method, and were doped with Bi and Ag to obtain n- and p-type materials, respectively. Excess Mg was also added to some of the ingots to compensate for the loss of Mg during the preparation process. The Mg₂Sn samples were characterized by x-ray diffraction (XRD) and scanning electron microscopy (SEM), and their power factors were calculated from the Seebeck coefficient and electrical conductivity, measured from 80 K to 700 K. The sample prepared with 4% excess Mg, which contains a small amount of Mg₂Sn + Mg eutectic phase, had the highest power factor of 12 × 10⁻³ W m⁻¹ K⁻² at 115 K, while the sample doped with 2% Ag, in which a small amount of eutectics also exists, has a power factor of 4 × 10⁻³ W m⁻¹ K⁻² at 420 K.     

Thermoelectric Properties of <Emphasis Type="Italic">p</Emphasis>-Type Mg<Subscript>2.00</Subscript>Si<Subscript>0.25</Subscript>Sn<Subscript>0.75</Subscript> with Li and Ag Double Doping

Mg₂Si_1−x Sn _x -system solid solutions are ecofriendly semiconductors that are promising materials for thermoelectric generators in the middle temperature range. To produce a thermoelectric device, high-performance p- and n-type materials must be balanced. In this paper, p-type Mg_2.00Si_0.25Sn_0.75 with Li and Ag double doping was prepared by the liquid–solid reaction method and hot-pressing. Effects of Li and Ag double doping on thermoelectric properties were investigated in the temperature range from room temperature to 850 K. All sintered compacts were identified as single-phase solid solutions with anti-fluorite structure. The carrier concentration increased with the double doping. The temperature dependence of resistivity of the double-doped samples was similar to that of a metal. The seebeck coefficient increased with temperature to a maximum value and then decreased in the intrinsic region. Thermal conductivity decreased linearly with increasing temperature, reaching a minimum near the intrinsic region, and then increased rapidly because of the contribution of the bipolar component. The dimensionless figure of merit reached 0.32 at 610 K for Mg_2.00Si_0.25Sn_0.75 double-doped with Li-5000 ppm and Ag-20000 ppm.     

Accurate Determination of the Matrix Composition Profile of Hg<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te by Secondary Ion Mass Spectrometry

In this report, we present a new secondary ion mass spectrometry (SIMS) analysis technique to provide accurate Cd composition profiles based on the measurement of HgCs⁺ and CdCs⁺ cluster ions. Study of Hg_1–x Cd _x Te samples with different x values shows that x/(1 − x) is linearly proportional to HgCs⁺/CdCs⁺ over the range of x = 0.2 to x = 0.9. This technique allows us to obtain an accurate Cd profile for a multilayer HgCdTe sample with different x values for each layer using a single standard with known x value. (Received 10/15/06; accepted 2/14/07)     

Ultraviolet Photodetection Properties of a Pt Contact on a Mg<Subscript>0.1</Subscript>Zn<Subscript>0.9</Subscript>O/ZnO Composite Film

We report on the ultraviolet (UV) photodetection properties of a Pt contact on a sol-gel Mg_0.1Zn_0.9O/ZnO composite structure on a glass substrate. In the dark, the current–voltage (I–V) characteristics between the Pt and Ag contacts on the top of the ZnO film were linear while that on the Mg_0.1Zn_0.9O/ZnO composite film were rectifying, suggesting the formation of a Schottky diode on the latter. The ideality factor, n, and the reverse leakage current density, J _R , of the Schottky diode were greater than 2 and 2.36 × 10⁻² A cm⁻² at −5 V, respectively. Under ultraviolet light, the I–V characteristics become linear. The maximum photo-to-dark current ratio observed was about 63. The composite film showed good sensitivity to UV light with wavelengths of less than 400 nm, though the photoresponse process was found to be slow.     

Effect of Hydrogen Free Radicals on Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te

The effects of atomic hydrogen (H) and Br/methanol etching on Hg_1−x Cd _x Te films were investigated using x-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Exposure of an as-received Hg_1−x Cd _x Te sample to H + H₂ resulted in H-induced TeO₂ reduction. The oxide reduction was first order with respect to H + H₂ exposure. Exposure to H + H₂ after etching the Hg_1−x Cd _x Te film in a Br/methanol solution induced Hg and C depletion. Hg and C removal was also observed after completely reducing the TeO₂ on the as-received sample. The removal process was hindered by the formation of a Cd-rich overlayer on both etched and unetched surfaces.     

Al ohmic contacts to HCI-treated Mg<Subscript>x</Subscript>Zn<Subscript>1−x</Subscript>O

The Al nonalloyed ohmic contacts were fabricated on Mg_xZn_1−xO (0≤x≤0.2) thin films. HCl surface treatment significantly reduced the specific contact resistances to value around 10⁻⁴ Ω cm². X-ray photoelectron spectroscopy (XPS) analysis revealed that the HCl treatment increased the oxygen vacancy density and introduced chlorine to the semiconductor surface, resulting in a thin conductive layer and thus reduced specific contact resistance. A subsequent oxygen plasma treatment reduced the oxygen vacancy density, and correspondingly increased the specific contact resistance. Al-ZnO contacts were insensitive to the HCl treatment, due to the formation of a highly conductive Al-doped thin interface layer.     

Synthesis of Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Alloy Thin Films Using Ion Implantation and Pulsed Laser Melting (II-PLM)

Ge_1−x Sn _x thin films are interesting for all-group-IV optoelectronics because of a crossover to a direct bandgap with dilute Sn alloying. However, Sn has vanishing room-temperature equilibrium solubility in Ge, making their synthesis very challenging. Herein, we report on our attempts to synthesize Ge_1−x Sn _x films on Ge (001) using ion implantation and pulsed laser melting (II-PLM). A maximum of 2 at.% Sn was incorporated with our experimental conditions in the samples as determined by Rutherford back scattering spectroscopy. A red-shift in the Ge optical phonon branch and increased absorption below the Ge bandgap with increasing Sn concentration indicate Sn-induced lattice- and band-structure changes after II-PLM. However, ion-channeling and electron microscopy show that the films are not of sufficient epitaxial quality for use in devices.     

Interfacial Reactions between Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Alloy Underbump Metallurgy and Sn-Ag-<Emphasis Type="Italic">z</Emphasis>Cu Solders

A reaction study of Cu _x Ni _y alloy (x = 0.2–0.95) under bump metallization (UBM) with Sn-Ag-zCu solder (z = 0–0.7) was conducted. Formation and separation of intermetallic compounds (IMCs), effect of Cu addition to the Cu _x Ni _y alloy and the solders, and compatibility of reaction products with currently available phase diagrams are extensively investigated. The increase of Cu content both in the Cu _x Ni _y alloy and in the solder promoted IMC growth and Cu _x Ni _y consumption; though, with regard to solder composition, the reverse trend was true of the solder reactions in the literature. The liquid + Cu₆Sn₅ area in the Sn-rich corner needs to be larger compared to the currently available Cu-Ni-Sn ternary phase diagram, and the maximum simultaneous soluble point of Ni and Cu in Sn needs also to be moved to the Ni-Sn side (e.g., Sn-0.6Cu-0.3Ni).     

Characterization of Zn1?xMgxO Films Prepared by the Sol–Gel Process and Their Application for Thin-Film Transistors

Transparent semiconductor thin films of Zn_1−x Mg _x O (0 ≤ x ≤ 0.36) were prepared using a sol–gel process; the crystallinity levels, microstructures, and optical properties affected by Mg content were studied. The experimental results showed that addition of Mg species in ZnO films markedly decreased the surface roughness and improved transparency in the visible range. A Zn_1−x Mg _x O film with an x-value of 0.2 exhibited the best average transmittance, namely 93.7%, and a root-mean-square (RMS) roughness of 1.63 nm. Therefore, thin-film transistors (TFTs) with a Zn_0.8Mg_0.2O active channel layer were fabricated and found to have n-type enhancement mode. The Zn_0.8Mg_0.2O TFT had a field-effect mobility of 0.1 cm²/V s, threshold voltage of 6.0 V, and drain current on/off ratio of more than 10⁷.     

Thermoelectric Properties of NdGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> Prepared by CS<Subscript>2</Subscript> Sulfurization

Ternary rare-earth sulfides NdGd_1+x S₃, where 0 ≤ x ≤ 0.08, were prepared by sulfurizing Ln₂O₃ (Ln = Nd, Gd) with CS₂ gas, followed by reaction sintering. The sintered samples have full density and homogeneous compositions. The Seebeck coefficient, electrical resistivity, and thermal conductivity were measured over the temperature range of 300 K to 950 K. All the sintered samples exhibit a negative Seebeck coefficient. The magnitude of the Seebeck coefficient and the electrical resistivity decrease systematically with increasing Gd content. The thermal conductivity of all the sintered samples is less than 1.9 W K⁻¹ m⁻¹. The highest figure of merit ZT of 0.51 was found in NdGd_1.02S₃ at 950 K.     

Annealing-induced evolution of optical properties of the multilayered nanoperiodic SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/ZrO<Subscript>2</Subscript> system containing Si nanoclusters

The photoluminescence, infrared absorption, and Raman spectra of amorphous multilayered nanoperiodic a-SiO _x /ZrO₂ structures produced by vacuum evaporation and then annealed at different temperatures (500–1100°C) are studied. It is established that the evolution of the optical properties with increasing annealing temperature is controlled by sequential transformation of Si clusters formed in the SiO _x layers from nonphase inclusions to amorphous clusters and then to nanocrystals. The finally formed nanocrystals are limited in sizes by the thickness of the initial SiO _x layers and by chemical reactions with ZrO₂.     

A Scanning Probe Microscopy Study of Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te

The effects of several ex vacuo methods used in the surface preparation of Cd_1−x Zn _x Te (CZT) have been studied using noncontact atomic force microscopy, scanning tunneling microscopy, and scanning tunneling spectroscopy. Preparation techniques include mechanical lapping, hydroplane bromine-methanol polishing, and in vacuo annealing. The morphology, electrical homogeneity, and local density of states (LDOS) have been studied for each preparation method. Impurities and oxides quickly form on the surface after each preparation method. Annealing in ultrahigh vacuum causes the surface electronic structure to become inhomogeneous whilst the LDOS suggests a compositional change from an oxide surface to p-type CZT.     

High-Performance (Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>SbTe<Subscript><Emphasis Type="Italic">x</Emphasis>/2+1.5</Subscript>)<Subscript>15</Subscript>(GeTe)<Subscript>85</Subscript> Thermoelectric Materials Prepared by Melt Spinning

A new preparation process combining melt spinning and hot pressing has been developed for the (Ag _x SbTe _x/2+1.5)₁₅(GeTe)₈₅ (TAGS-85) system. Compared with samples prepared by the traditional air-quenching and hot-pressing method, electrical conductivity and thermal conductivity are lowered. The thermoelectric performance of the TAGS-85 samples varied with changing Ag content and reached the highest ZT of 1.48 when x was 0.8 for the melt-spun sample, compared with the maximum ZT of 1.36 for the air-quenched sample. The Seebeck coefficient of the melt-spun TAGS-85 alloys was improved, while both the electrical conductivity and thermal conductivity were decreased. The net result of this process is to effectively enlarge the temperature span of ZT > 1, which will benefit industrial application.