Influence of crystallinity of as-deposited Ge film on formation of quantum dot in carbon-mediated solid-phase epitaxy

The influence of crystallinity of as-deposited Ge films on Ge quantum dot (QD) formation via carbon (C)-mediated solid-phase epitaxy (SPE) was investigated. The samples were fabricated by solid-source molecular beam epitaxy (MBE). Ge/C/Si structure was formed by sequential deposition of C and Ge at deposition temperature (T_D) of 150–400 °C, and it was heat-treated in the MBE chamber at 650 °C. In the case of amorphous or a mixture of amorphous and nano-crystalline Ge film grown for T_D ≤250 °C, density of QDs increased with increasing T_D due to the increase of C-Ge bonds in Ge layer. Ge QDs with diameter of 9.2±2.1 nm were formed in the highest density of 8.3×10¹¹ cm⁻² for T_D =250 °C. On the contrary, in the case of polycrystalline Ge film for T_D ≥300 °C, density of QDs decreased slightly. This is because C incorporation into Ge layer during SPE was suppressed due to the as-crystallized columnar grains. These results suggest that as-deposited Ge film in a mixture of amorphous and nano-crystalline state is suitable to form small and dense Ge QDs via C-mediated SPE.     

Effects of carbon coverage on Ge quantum dots formation on Si(100) using C-Si reaction and transition of Ge growth mode

Effects of carbon (C) coverage on C-mediated Ge quantum dots (QDs) formation on a Si(100) substrate changing a state of surface reconstruction were investigated by using solid-source molecular beam epitaxy. For C=0–2.0 monolayers (MLs), the Ge QD scaled down and its density increased with C coverage. In addition, growth mode of Ge QDs changed from Volmer-Weber (VW) mode without a wetting layer to Stranski-Krastanov (SK) mode with the wetting layer for C=0.50–0.75 ML. This transition was induced by decrease in interfacial energy between Ge and Si surface due to the formation of C-Ge bonds near the Ge/Si interface. For C≥2.5 MLs, the Ge QD enlarged slightly and its density decreased with increasing C coverage, and he Ge growth mode went back to the VW mode. The Raman spectroscopy and X-ray photoelectron spectroscopy revealed the formation of a mixture of amorphous C and nano-crystalline graphite on the Si surface. Thus, the formation of a large amount of C–C (sp²) bonds induced the growth transition of QDs from the SK mode to the VW mode due to the decrease in surface energy of C.     

Thermal desorption of Ge native oxides and loss of Ge from the surface

The authors have identified oxidation and desorption processes of Ge native oxide by chemical bonding states measured by X-ray photoemission spectroscopy. Ge oxidation occurs at the temperatures of 450–500 °C in an oxidizing ambient. Ge desorption in nitrogen ambient is observed at the temperatures of 500–550 °C, which is higher than the oxidation temperature by 50 °C. Combined oxidation and desorption processes proceed subsequently and cause a loss of Ge from the surface when Ge is annealed in oxidizing ambient at a temperature higher than desorption temperature. The surface loss is avoided when Ge is annealed with SiO₂ cap layer in an identical annealing condition.     

Ultra-low-energy ion-beam-synthesis of Ge nanocrystals in thin ALD Al2O3 layers for memory applications

Structural and electrical properties of ALD-grown 5 and 7 nm-thick Al₂O₃ layers before and after implantation of Ge ions (1 keV, 0.5–1 × 10¹⁶ cm^?2) and thermal annealing at temperatures in the 700–1050 °C range are reported. Transmission Electron Microscopy reveals the development of a 1 nm-thick SiO₂-rich layer at the Al₂O₃/Si substrate interface as well as the formation of Ge nanocrystals with a mean diameter of ～5 nm inside the implanted Al₂O₃ layers after annealing at 800 °C for 20 min. Electrical measurements performed on metal–insulator–semiconductor capacitors using Ge-implanted and annealed Al₂O₃ layers reveal charge storage at low-electric fields mainly due to location of the Ge nanocrystals at a tunnelling distance from the substrate and their spatial dispersion inside the Al₂O₃ layers.     

Optical study of germanium nanostructures grown on a Si(118) vicinal substrate

Photoluminescence (PL) measurements were carried out on Si/Ge(n)/Si_0.7Ge_0.3/Si structures (n is varying from 1 to 7 ML) deposed by gas source molecular beam epitaxy (GS-MBE) on Si(100) surfaces and high index Si(118) vicinal surfaces. Ge nanostructures were confined on the top of the undulation of the Si_0.3Ge_0.7 wetting layer, according to the Stranski–Krastanov growth mode. PL measurements reveal a correlation between the substrate orientation and the island morphology: square dots for (001) and wires for (118) surface orientation. The results suggest that the SiGe wetting layer is required to ensure a good dot size uniformity. The dependence of the luminescence on the excitation power and the PL decay time indicate that the luminescence transitions likely occur in a type-II band line up. Finally, the dot-related PL persists up to room temperature which is very promising for optoelectronic device applications.     

Improvement in negative differential conductance characteristics of hole resonant-tunneling diodes with high Ge fraction Si/strained Si1−xGex/Si(1 0 0) heterostructure

Hole resonant-tunneling diodes (RTD) with Si/strained Si_1?xGe_x heterostructures epitaxially grown on Si(1 0 0) have been fabricated and improvement in negative differential conductance (NDC) characteristics for high Ge fraction such as x = 0.5 was investigated. It is clearly shown that SiH₄ exposure at low temperatures of 400–450 °C just after Si_1?xGe_x epitaxial growth is effective to suppress surface roughness in atomic order. In the case of the RTD with x = 0.48, NDC characteristics for 1.4-nm thick Si barriers were observed at higher temperatures around 270 K than that for 2.4-nm thick Si barriers. By increasing the Ge fraction to x = 0.58, NDC characteristics were also observed at higher temperatures around 290 K than that with x = 0.48.     

Photoluminescence of phosphorous doped Ge on Si (100)

Photoluminescence (PL) of selectively grown phosphorus (P) doped germanium (Ge) is investigated. 350–600 nm thick P-doped Ge is grown on 100 nm thick P-doped Ge buffer layer, which is annealed at 800 °C before the main part of Ge deposition. In the case of Ge deposited at 325 °C, approximately two times higher PL intensity is observed by P doping of ~3.2×10¹⁹ cm⁻³. Further increase of PL intensity by a factor of 1.5 is observed by increasing the growth temperature from 325 °C to 400 °C due to improved crystal quality. Varying PH₃ partial pressure at 400 °C, red shift of the PL occurred with increasing P concentration due to higher bandgap narrowing. With increasing P concentration up to ~1.4×10¹⁹ cm⁻³ at 400 °C the PL peak intensity increases by filling electrons into the L valley and decreases due to enhanced point defect concentration and degraded crystallinity. By post-annealing at 500–800 °C, the PL intensity is further increased by a factor of 2.5 because of increased active P concentration and improved crystal quality. Reduced direct bandgap energy by introducing tensile strain is also observed.     

Effect of substrate temperature on indium tin oxide (ITO) thin films deposited by jet nebulizer spray pyrolysis and solar cell application

This study focused on the effect of substrate temperature (350 °C, 400 °C, and 450 °C) on morphological, optical, and electrical properties of indium tin oxide (ITO) films deposited onto porous silicon/sodalime glass substrates through jet nebulizer spray pyrolysis for use in heterojunction solar cells. X-ray diffraction analysis confirmed the formation of pure and single-phase In₂O₃ for all the deposited films whose crystallinity was enhanced with increasing substrate temperature, as shown by the increasing (222) peak intensity. Morphological observations were conducted using scanning electron microscopy to reveal the formation of continuous dense films composed of nanograins. The UV–vis spectra revealed that the transmittance increased with increasing substrate temperature, reaching a value of over 80% at 450 °C. The photoelectric performance of the solar cell was studied using the I–V curve by illuminating the cell at 100 mW/cm². A high efficiency (η) of 3.325% with I_sc and V_oc values of 14.8 mA/cm² and 0.60 V, respectively, was attained by the ITO solar cell annealed at 450 °C.     

Investigation of Si/SiGe/Si heterostructure implanted by H ion and annealed in vacuum and dry O2 ambient

The 20-nm-thick Si cap layer/74-nm-thick Si_0.72Ge_0.28 epilayer/Si heterostructures implanted by 25 keV H⁺ ion to a dose of 1×10¹⁶ cm⁻² were annealed in ultra-high vacuum ambient and dry O₂ ambient at the temperature of 800 °C for 30 min, respectively. Rutherford backscattering/ion channeling (RBS/C), Raman spectra, high-resolution X-ray diffraction (HRXRD) and atomic force microscopy (AFM) were used to characterize the structural characteristics of the Si_0.72Ge_0.28 layer. Investigations by RBS/C demonstrated that the crystal quality of the Si/Si_0.72Ge_0.28/Si heterostructure sample implanted by 25 keV H⁺ in conjunction with subsequent annealing in dry O₂ ambient is superior to that of identical sample annealing in ultra-high vacuum ambient. The less strain relaxation of SiGe layer of the Si/Si_0.72Ge_0.28/Si heterostructures implanted by H ion and annealed in dry O₂ ambient at the temperature of 800 °C for 30 min could be doublechecked by Raman spectra as well as HRXRD, which was compared with that in an identical sample annealed in ultra-high vacuum ambient for identical thermal budget. In addition, the SiGe layer of the H-implanted Si/SiGe/Si heterostructural sample annealed in dry O₂ ambient accompanied by better crystal quality and less strain relaxation made its surface morphology superior to that of the sample annealed in ultra-high vacuum ambient at the temperature of 800 °C for 30 min, which was also verified by AFM images.     

Growth temperature dependence of epitaxial Gd2O3 films on Si(1 1 1)

This article reports on the epitaxy of crystalline high κ oxide Gd₂O₃ layers on Si(1 1 1) for CMOS gate application. Epitaxial Gd₂O₃ thin films have been grown by Molecular Beam Epitaxy (MBE) on Si(1 1 1) substrates between 650 and 750 °C. The structural and electrical properties were investigated depending on the growth temperature. The C–V measurements reveal that equivalent oxide thickness (EOT) equals 0.7 nm for the sample deposited at the optimal temperature of 700 °C with a relatively low leakage current of 3.6 × 10^?2 A/cm² at |V_g ? V_FB| = 1 V.     

Direct bonding of Si wafer pairs with SiO2 and Si3N4 films with a fast linear annealing

2000 Å-SiO₂/Si(1 0 0) and 560 Å-Si₃N₄/Si(1 0 0) wafers, that are 10 cm in diameter, were directly bonded using a rapid thermal annealing method, so-called fast linear annealing (FLA), in which two wafers scanned with a high-power halogen lamp. It was demonstrated that at lamp power of 550 W, corresponding to the surface temperature of ∼450°C, the measured bonded area was close to 100%. At the same lamp power, the bond strength of the SiO₂∥Si₃N₄ wafer pair reached 2500 mJ/m², which was attained only above 1000°C with conventional furnace annealing for 2 h. The results clearly show that the FLA method is far superior in producing high-quality directly bonded Si wafer pairs with SiO₂ and Si₃N₄ films (Si/SiO₂∥Si₃N₄/Si) compared to the conventional method.     

Epitaxial growth of Ge thin film on Si (001) by DC magnetron sputtering

We have demonstrated that sub-10 nm-thick heteroepitaxial Ge films on Si (001) having smooth surfaces can be obtained by DC magnetron sputtering. Ge films grown at 350 °C preserve the smooth surfaces with a roughness root mean square (RMS) of 0.39 nm, whereas, the Ge films grown at 500 °C show significant roughness with an island-like morphology. In samples grown at 350 °C, it is confirmed that the Ge films are grown epitaxially by cross-section transmission electron microscopy (TEM) and X-ray diffraction (XRD) rocking curve measurements. Rapid thermal annealing (RTA) at 720 °C is effective in improving the crystalline quality and the degradation in the roughness is negligible. Raman spectra and an XRD reciprocal space map reveal that the epitaxial Ge grown at 350 °C show an in-plane compressive strain and that the strain continues to remain after a 720 °C RTA.     

Ge integration on Si via rare earth oxide buffers: From MBE to CVD (Invited Paper)

Single crystalline rare earth oxide heterostructures are flexible buffer systems to achieve the monolithic integration of Ge thin film structures on Si. The development of engineered oxide systems suitable for mass-production compatible CVD processes is hereby of special importance. In this paper, the interaction of Ge with PrO₂(1 1 1)/Si(1 1 1) heterostructures is studied in detail to achieve this goal. MBE based in situ growth studies unveil the chemical reduction of the PrO₂ buffer during the initial Ge deposition, the occurrence of a Volmer Weber growth mode of Ge on the resulting Pr₂O₃ heterostructure and the final formation of single crystalline, atomically smooth and c(2 × 8) reconstructed Ge(1 1 1) film structures. Comparative CVD Ge heteroepitaxy studies on MBE grown PrO₂(1 1 1)/Si(1 1 1) and Pr₂O₃(1 1 1)/Si(1 1 1) buffer systems indicate that the highly reactive lattice oxygen of PrO₂ plays an active role to avoid during initial exposure to the reducing ambient of the GeH₄ precursor chemistry the decomposition of the oxide buffer system.     

Structural and electrical characterization of CoNiO monolayer as copper diffusion barrier in integrated circuits

Diffusion barrier properties of CoNiO monolayer, deposited by Langmuir Blodgett (LB) technique, were studied against the diffusion of copper through SiO₂. Cu/CoNiO/SiO₂/Si and Cu/SiO₂/Si test structures were prepared and compared for this purpose. These test structures were annealed at temperatures starting from 100 °C up to 650 °C in vacuum. Samples were characterized using Energy Dispersive X-ray Spectroscopy (EDS), Atomic force microscopy (AFM), X-ray diffraction (XRD), scanning electron microscope (SEM), four probe resistivity measurement, Capacitance-Voltage (C‒V), Current-Voltage (I‒V) characterization techniques. EDS and AFM confirmed the composition and structure of the deposited monolayer. Thermal stability was studied using X-ray diffraction (XRD), Scanning Electron Microscope (SEM) and four probe techniques. Results indicated that structure with barrier was stable up to 600 °C whereas its counterpart could sustain only up to 300 °C. Sheet resistance of Cu/SiO₂/Si structure starts increasing at 300 °C and that of Cu/CoNiO/SiO₂/Si test structure was almost unchanged up to 600 °C in. SEM analysis of samples annealed at different temperatures also confirmed the XRD and four probe results. Biased Thermal Stress (BTS) was applied to the samples and its effect was observed using C‒V analysis. C‒V curves showed that in the presence of CoNiO barrier layer there was no shift in the C‒V curve even after 120 min of BTS while in the absence of barrier there was a significant shift in the C‒V curve even after 30 min of BTS. Leakage current density (j_L) was plotted against the BTS duration under same BTS conditions. It was found that the Cu/CoNiO/SiO₂/Si stack could survive about two times more than the Cu/SiO₂/Si stack.     

Effect of high-temperature annealing on lanthanum aluminate thin films grown by ALD on Si(1 0 0)

Amorphous lanthanum aluminate thin films were deposited by atomic layer deposition on Si(1 0 0) using La(ⁱPrCp)₃, Al(CH₃)₃ and O₃ species. The effects of post-deposition rapid thermal annealing on the physical and electrical properties of the films were investigated. High-temperature annealing at 900 °C in N₂ atmosphere leads to the formation of amorphous La-aluminosilicate due to Si diffusion from the substrate. The annealed oxide exhibits a uniform composition through the film thickness, a large band gap of 7.0 ± 0.1 eV, and relatively high dielectric constant (κ) of 18 ± 1.     

Role of a Si0.95Ge0.05 epilayer cap on boron diffusion in silicon under inert and dry oxidizing ambient annealing

Silicon (Si) and Si with a 60 nm Si_0.95Ge_0.05 epilayer cap (Si_0.95Ge_0.05/Si) were implanted with 60 keV, 1×10¹³ cm⁻² boron (B) followed by annealing in nitrogen (N₂) or dry oxygen (O₂) in two different anneal conditions. B⁺implantation energy and dose were set such that the B peak is placed inside Si in Si_0.95Ge_0.05/Si samples and concentration independent B diffusion is achieved upon annealing. For samples annealed above 1075 °C, Ge diffusing from the Si_0.95Ge_0.05 epilayer cap in Si_0.95Ge_0.05/Si samples reached the B layer inside Si and resulted in retarded B diffusion compared to the Si samples. For annealing done at lower temperatures, diffusion of Ge from Si_0.95Ge_0.05 epilayer cap does not reach the B layer inside Si. Thus B diffusion profiles in the Si and Si_0.95Ge_0.05/Si samples appear to be similar. B diffusion in dry oxidizing ambient annealing of Si_0.95Ge_0.05/Si samples further depends on the nature of Si_0.95Ge_0.05 oxidation which is set by the duration and the thermal budget of the oxidizing anneal.     

Effect of UV light irradiation on photovoltaic characteristics of inverted polymer solar cells containing sol–gel zinc oxide electron collection layer

An inverted organic bulk-heterojunction solar cell containing a zinc oxide (ZnO) based electron collection layer with a structure of ITO/ZnO/[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM): regioregular poly(3-hexylthiophene) (P3HT)/poly(3,4-ethylenedioxylenethiophene): poly(4-styrene sulfonic acid)/Au (ZnO cell) was fabricated. We examined the relationship between the heating temperature of the ZnO layer and the device performance under irradiation by simulated sunlight while cutting the UV light. The effects of the UV light contained in simulated sunlight were investigated by photocurrent–voltage (I–V) and alternating current impedance spectroscopy (IS) measurements. When the ZnO cells were irradiated with simulated sunlight, they exhibited a maximum power conversion efficiency (PCE) of over 3%, which hardly varied with the heating temperature of ZnO layers treated at 250 °C, 350 °C, and 450 °C. In contrast, when the ZnO cells were irradiated with simulated sunlight without UV content, their photovoltaic characteristics were very different. In the case of the cell with ZnO prepared by heating at 250 °C, PCE of 2.7% was maintained even under continuous irradiation with simulated sunlight without UV. However, for the cells with ZnO prepared by heating at 350 °C and 450 °C, the shapes of the I–V curves changed with the UV-cut light irradiation time, accompanying an increase in their series resistance. Overall, after UV-cut light irradiation for 1 h, the PCE of the cell with ZnO prepared by heating at 350 °C decreased to 1.80%, while that of the cell with ZnO prepared by heating at 450 °C fell to 1.35%. The photo IS investigations suggested that this performance change was responsible for the formation of charge-trapping sites at the ZnO/PCBM:P3HT interface which act as recombination centers for photo-produced charges in the PCBM:P3HT layer.     

Thermal stability of compressively strained Si/relaxed Si1-xCx heterostructures formed on Ar ion implanted Si (100) substrates

Thermal stability of compressively strained Si/relaxed Si_1-xC_x heterostructure formed with the defect control by Ar ion implantation was investigated. It was found that compressive strain is sustained up to 900 °C without prominent change in surface roughness. From the X-ray diffraction reciprocal space mapping, it was found that relaxed Si_1-xC_x layer is stable up to at least 800 °C, and compressively strained Si_1-xC_x with relatively large thickness is formed by annealing at temperatures higher than 900 °C owing to redistribution of C atoms. These results indicate that the compressively strained Si/relaxed Si_1-xC_x heterostructure formed by Ar ion implantation technique is available up to at least 800 °C and has a potential to be used at more than 900 °C.     

Epitaxial growth of nonpolar GaN films on r-plane sapphire substrates by pulsed laser deposition

Single-crystalline nonpolar GaN epitaxial films have been successfully grown on r-plane sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) with an in-plane epitaxial relationship of GaN[1-100]//Al₂O₃[11-20]. The properties of the ~500 nm-thick nonpolar GaN epitaxial films grown at temperatures ranging from 450 to 880 °C are studied in detail. It is revealed that the surface morphology, the crystalline quality, and the interfacial property of as-grown ~500 nm-thick nonpolar GaN epitaxial films are firstly improved and then decreased with the growth temperature changing from 450 to 880 °C. It shows an optimized result at the growth temperature of 850 °C, and the ~500 nm-thick nonpolar GaN epitaxial films grown at 850 °C show very smooth surface with a root-mean-square surface roughness of 5.5 nm and the best crystalline quality with the full-width at half-maximum values of X-ray rocking curves for GaN(11-20) and GaN(10-11) of 0.8° and 0.9°, respectively. Additionally, there is a 1.7 nm-thick interfacial layer existing between GaN epitaxial films and r-plane sapphire substrates. This work offers an effective approach for achieving single-crystalline nonpolar GaN epitaxial films for the fabrication of nonpolar GaN-based devices.