Pressure Metalorganic Chemical Vapor Deposition Research Articles

The action of silicon doping in the first two to five barriers of eight periods In0.2Ga0.8N/GaN multiple quantum wells of blue LEDs

First two to five barriers in the growth sequence having silicon (Si) doping of eight periods In0.2Ga0.8N/GaN quantum wells (QWs) on twenty pairs of In0.02Ga0.98N/GaN superlattice strain relief layers (SRLs) of blue LEDs were prepared by low pressure metal–organic chemical vapor deposition (LPMOCVD) system on patterned sapphire substrates (PSSs). The effect of doping layers on the luminescence properties of QWs of blue LEDs was investigated. For the sample with first four barriers having Si doping, formation of soft confinement of QWs potential and strong carrier localization inside QWs were occurred. There is better spread of carriers among eight QWs and strong radiative recombination of carriers inside QWs. The increase of output power and external quantum efficiency (EQE) is due to decrease of Auger processes, leakage of carriers out of QWs, and nonradiative recombination centers. The consequences demonstrate that first four barriers with Si doping possess the favorable doping condition for eight periods In0.2Ga0.8N/GaN QWs.

Increasing Polycrystalline Zinc Oxide Grain Size by Control of Film Preferential Orientation

We investigate the structural evolution of polycrystalline zinc oxide films grown by low pressure metal-organic chemical vapor deposition. The goal is to achieve larger grains-leading to higher charge carrier mobility from lower grain boundary density-by controlling the grain orientation during growth. The results are 2-fold. First we describe how the combination of deposition temperature and gas flow influences the nucleation and film thickening stages: low temperature and high gas flow favor a high nucleation density and the development of c-textured films, whereas high temperature and low gas flow lead to a lower nucleation density and a-textured films. Second we demonstrate how a fine control of the film preferential orientation at the different growth stages allows the fabrication of films with grains that are 25% larger, hence improving the carrier mobility with respect to the reference film.

Characteristics of the epitaxy of InGaN-based light-emitting diodes grown by nanoscale epitaxial lateral overgrowth using a nitrided titanium buffer layer

In this work, a buffer layer of nitrided titanium (Ti) achieved through the nitridation of a Ti metal layer on a sapphire substrate was used for the epitaxial growth of InGaN-based light-emitting diodes (LEDs) achieved by low pressure metal-organic chemical vapor deposition. The effect of in-situ Ti metal nitridation on the performance of these InGaN-based LEDs was then investigated. It was very clear that the use of the nitrided Ti buffer layer (NTBL) induced the formation of a nanoscale epitaxial lateral overgrowth layer during the epitaxial growth. When evaluated by Raman spectroscopy, this epi-layer exhibited large in-plane compressive stress releasing with a Raman shift value of 567.9 cm-1. Cathodoluminescence spectroscopy and transmission electron microscopy results indicated that the InGaN-based LEDs with an NTBL have improved crystal quality, with a low threading dislocations density being yielded via the strain relaxation in the InGaN-based LEDs. Based on the results mentioned above, the electroluminescence results indicate that the light performance of InGaN-based LEDs with an NTBL can be enhanced by 45% and 42% at 20 mA and 100 mA, respectively. These results suggest that the strain relaxation and quality improvement in the GaN epilayer could be responsible for the enhancement of emission power.

Improved output power of GaN-based ultraviolet light-emitting diodes with sputtered AlN nucleation layer

In this work, the ultraviolet light-emitting diodes (UV-LEDs) at 380nm were grown on patterned sapphire substrate (PSS) by atmospheric pressure metal organic chemical vapor deposition (AP-MOCVD). A sputtered AlN nucleation layer was utilized on the PSS to enhance the quality of the epitaxial layer. By using high-resolution X-ray diffraction, the full-width at half-maximum of the rocking curve shows that the UV-LEDs with sputtered AlN nucleation layer had better crystalline quality when compared to conventional GaN nucleation samples. From the scanning electron microscope (SEM) and transmission electron microscopy (TEM) images, it can be observed that the tip and sidewall portion of the pattern was smooth using the sputtered AlN nucleation layer. The threading dislocation densities (TDDs) are reduced from 6×107cm−2 to 2.5×107cm−2 at the interface between the u-GaN layers for conventional and AlN PSS devices, respectively. As a result, a much higher light output power was achieved. The light output power at an injection current of 20mA was enhanced by 30%. Further photoluminescence (PL) measurement and numerical simulation confirm that this increase of output power can be attributed to the improvement of material quality and light extraction.

The effect of free-standing GaN substrate on carrier localization in ultraviolet InGaN light-emitting diodes.

In this study, we have grown 380-nm ultraviolet light-emitting diodes (UV-LEDs) based on InGaN/AlInGaN multiple quantum well (MQW) structures on free-standing GaN (FS-GaN) substrate by atmospheric pressure metal-organic chemical vapor deposition (AP-MOCVD), and investigated the relationship between carrier localization degree and FS-GaN. The micro-Raman shift peak mapping image shows low standard deviation (STD), indicating that the UV-LED epi-wafer of low curvature and MQWs of weak quantum-confined Stark effect (QCSE) were grown. High-resolution X-ray diffraction (HRXRD) analyses demonstrated high-order satellite peaks and clear fringes between them for the UV-LEDs grown on the FS-GaN substrate, from which the interface roughness (IRN) was estimated. The temperature-dependent photoluminescence (PL) measurement confirmed that the UV-LEDs grown on the FS-GaN substrate exhibited better carrier confinement. Besides, the high-resolution transmission electron microscopy (HRTEM) and energy-dispersive spectrometer (EDS) mapping images verified that the UV-LEDs on FS-GaN have fairly uniform distribution of indium and more ordered InGaN/AlInGaN MQW structure. Clearly, the FS-GaN can not only improve the light output power but also reduce the efficiency droop phenomenon at high injection current. Based on the results mentioned above, the FS-GaN can offer UV-LEDs based on InGaN/AlInGaN MQW structures with benefits, such as high crystal quality and small carrier localization degree, compared with the UV-LEDs on sapphire.

Thickness dependent stresses and thermal expansion of epitaxial LiNbO3 thin films on C-sapphire

LiNbO3 films of high epitaxial quality and with thicknesses of 120–500 nm were deposited at 650 °C on C-sapphire by atmospheric pressure metal-organic chemical vapour deposition. Li nonstoichiometry, residual stresses, twinning, and thermal expansion of the films as a function of the film thickness were investigated by means of Raman spectroscopy and X-ray diffraction. The relaxation of residual stresses, Li2O loss, inelastic deformation and elastic hysteresis during cycles of heating up to 860 °C and cooling down to room temperature were studied, as well. The residual stresses and thermal expansion of films were highly thickness dependent. It was shown that the {011¯2} twinning contributed to the stress relaxation in the thick LiNbO3 films.

Structural, electrical, and optical properties of CoxNi1-xO films grown by metalorganic chemical vapor deposition

Thin films of cobalt-nickel oxide (CoxNi1-xO, x=0.01, 0.02, 0.08, 0.17, 0.22, 0.35, 0.56, 0.72) were grown on Al2O3 substrate by atmospheric pressure metalorganic chemical vapor deposition (APMOCVD). The effect of the cobalt composition on the structural, morphological, optical, and electrical properties of the films was investigated. X-ray diffraction (XRD) analysis revealed that all of the films grew with a preferred orientation towards [111]NiO and a twinned structure. Cobalt was well dispersed in the NiO structure up to x=0.08. CoxNi1-xO alloys were formed from x=0.17 to x=0.22, while phase-separated NiO and CoxNi1−xO formed when x≥0.35. The bandgap of the CoxNi1−xO film was found to decrease with increasing cobalt composition. Four-point probe measurements showed that the resistivity of the film also decreased with increasing cobalt composition, reaching a minimum of 0.006Ωcm. Hall measurements of the films revealed n-type conductivity. The correlation between the presence of cobalt in different ionization states and the observed decrease in resistivity as well as the type of conductivity in CoxNi1−xO is discussed.

Optically-pumped 285 nm edge stimulated emission from AlGaN-based LED structures grown by MOCVD on sapphire substrates

285 nm stimulated emission (SE) is demonstrated at room temperature from optically-pumped AlGaN multiple quantum wells (MQWs) deposited between a Si-doped AlGaN current spreading layer and a 25 nm Mg-doped p-type AlGaN clad layer. The epitaxial structures were grown by low pressure metalorganic chemical vapor deposition (MOCVD) on high-quality AlN/sapphire templates and a pulsed ArF excimer laser was used as the excitation source for lasing experiments. The threshold power density (Pth) was measured to be 970 kW/cm2 and the SE was strongly polarized in transverse electric (TE) mode. The minimum emission linewidth was ∼2 nm. The high value of Pth is primarily attributed to optical losses due to pump laser absorption in the top p-AlGaN. Our results show the viability of the MOCVD growth technology in conjunction with c-plane sapphire substrates to develop electrically-pumped deep-UV laser diodes.

Efficiency improvement of GaN-based ultraviolet light-emitting diodes with reactive plasma deposited AlN nucleation layer on patterned sapphire substrate.

The flip chip ultraviolet light-emitting diodes (FC UV-LEDs) with a wavelength of 365 nm are developed with the ex situ reactive plasma deposited (RPD) AlN nucleation layer on patterned sapphire substrate (PSS) by an atmospheric pressure metal-organic chemical vapor deposition (AP MOCVD). The ex situ RPD AlN nucleation layer can significantly reduce dislocation density and thus improve the crystal quality of the GaN epitaxial layers. Utilizing high-resolution X-ray diffraction, the full width at half maximum of the rocking curve shows that the crystalline quality of the epitaxial layer with the (RPD) AlN nucleation layer is better than that with the low-temperature GaN (LT-GaN) nucleation layer. The threading dislocation density (TDD) is estimated by transmission electron microscopy (TEM), which shows the reduction from 6.8 × 107 cm−2 to 2.6 × 107 cm−2. Furthermore, the light output power (LOP) of the LEDs with the RPD AlN nucleation layer has been improved up to 30 % at a forward current of 350 mA compared to that of the LEDs grown on PSS with conventional LT-GaN nucleation layer.

Performance enhancement of GaN-based flip-chip ultraviolet light-emitting diodes with a RPD AlN nucleation layer on patterned sapphire substrate

In this work, flip-chip ultraviolet light-emitting diodes (FCUV-LEDs) on patterned sapphire substrate (PSS) at 375 nm were grown by an atmospheric pressure metal organic chemical vapor deposition (AP-MOCVD). A specialized reactive plasma deposited (RPD) AlN nucleation layer was utilized on the PSS to enhance the quality of the epitaxial layer. By using high-resolution X-ray diffraction, the full-width at half-maximum of the rocking curve shows that the FCUV-LEDs with RPD AlN nucleation layer had better crystalline quality when compared to conventional GaN nucleation samples. From the transmission electron microscopy (TEM) image, it can be observed that the tip and incline portion of the pattern was smooth using the RPD AlN nucleation layer. The threading dislocation densities (TDDs) are reduced from 7 × 107 cm−2 to 2.5 × 107 cm−2 at the interface between the u-GaN layers for conventional and AlN PSS devices, respectively. As a result, a much higher light output power was achieved. The improvement of light output power at an injection current of 20 mA was enhanced by 30%. Further photoluminescence measurement and numerical simulation confirm such increase of output power can be attributed to the improvement of material quality and light extraction.

High performance 380-nm ultraviolet light-emitting-diodes with 3% efficiency droop by using free-standing GaN substrate manufacturing from GaAs substrate

We investigated the influence of free-standing GaN (FS-GaN) substrates on the performance of ultraviolet light-emitting-diodes (UV-LEDs) grown on top by atmospheric pressure metal-organic chemical vapor deposition. High-resolution double-crystal x-ray diffraction (HRDCXD) analysis demonstrated high-order satellite peaks and clear fringes between them for UV-LEDs grown on the FS-GaN substrate, from which the interface roughness was estimated. In addition, the full width at half maximum of the HRDCXD rocking curve in the (0002) and the (101¯2) reflections were reduced to below 90 arc sec. The Raman results indicated that the GaN-based epilayer of strain free was grown. Additionally, the effect of the FS-GaN substrate on the crystal quality of the UV-LEDs was examined in detail by transmission electron microscopy (TEM). The TEM characterizations revealed no defects and V-pits were found in the scanned area. Based on the results mentioned above, the light output power of UV-LEDs on the FS-GaN substrate can be enhanced drastically by 80% and 90% at 20 and 100 mA, respectively. Furthermore, an ultralow efficiency degradation of about 3% can be obtained for the UV-LEDs on the FS-GaN substrate at a high injection current. The use of an FS-GaN substrate is suggested to be effective for improving the emission efficiency and droop of UV-LEDs grown thereon.

Nucleation of GaSb on GaAs (001) by low pressure metal—organic chemical vapor deposition

The initial growth stage of GaSb on GaAs (001) by low pressure metal—organic chemical vapor deposition (MOCVD) is investigated. The dependence of the nucleation on growth temperature, growth pressure, and vapor V/III ratio is studied by means of atomic force microscopy. The nucleation characteristics include the island density, size, and size uniformity distribution. The nucleation mechanism is discussed by the effects of growth temperature, growth pressure, and vapor V/III ratio on the density, size, and size uniformity of GaSb islands. With the growth temperature increasing from 500 °C to 610 °C and the growth pressure increasing from 50 mbar to 1000 mbar (1 mbar = 105 Pa), the island density first increases and then decreases; with the V/III ratio increasing from 0.5 to 3, the trend is contrary.

Inline atmospheric pressure metal-organic chemical vapour deposition for thin film CdTe solar cells

A detailed study has been undertaken to assess the deposition of CdTe for thin film devices via an inline atmospheric pressure metal-organic chemical vapour deposition (AP-MOCVD) reactor. The precursors for CdTe synthesis were released from a showerhead assembly normal to a transparent conductive oxide (TCO)/glass substrate, previously coated with a CdZnS window layer using a conventional batch AP-MOCVD reactor with horizontal flow delivery. Under a simulated illumination with air mass coefficient 1.5 (AM1.5), the initial best cell conversion efficiency (11.2%) for such hybrid cells was comparable to a reference device efficiency (~13%), grown entirely in the AP-MOCVD batch reactor. The performance and structure of the hybrid and conventional devices are compared for spectral response, CdTe grain morphology and crystal structure. These preliminary results reported on the transfer from a batch to an inline AP-MOCVD reactor which holds a good potential for the large-scale production of thin film photovoltaics devices and related materials.

Effect of band alignment on photoluminescence and carrier escape from InP surface quantum dots grown by metalorganic chemical vapor deposition on Si

A detailed analysis of photoluminescence (PL) from InP quantum dots (QDs) grown on Si has been carried out to understand the effect of substrate/host material in the luminescence and carrier escape process from the surface quantum dots. Such studies are required for the development of monolithically integrated next generation III-V QD based optoelectronics with fully developed Si microelectronics. The samples were grown by atmospheric pressure metalorganic chemical vapor deposition technique, and the PL measurements were made in the temperature range 10–80 K. The distribution of the dot diameter as well as the dot height has been investigated from atomic force microscopy. The origin of the photoluminescence has been explained theoretically. The band alignment of InP/Si heterostructure has been determined, and it is found be type II in nature. The positions of the conduction band minimum of Si and the 1st excited state in the conduction band of InP QDs have been estimated to understand the carrier escape phenomenon. A blue shift with a temperature co-efficient of 0.19 meV/K of the PL emission peak has been found as a result of competitive effect of different physical processes like quantum confinement, strain, and surface states. The corresponding effect of blue shift by quantum confinement and strain as well as the red shift by the surface states in the PL peaks has been studied. The origin of the luminescence in this heterojunction is found to be due to the recombination of free excitons, bound excitons, and a transition from the 1st electron excited state in the conduction band (e1) to the heavy hole band (hh1). Monotonic decrease in the PL intensity due to increase of thermally escaped carriers with temperature has been observed. The change in barrier height by the photogenerated electric-field enhanced the capture of the carriers by the surface states rather than their accumulation in the QD excited state. From an analysis of the dependence of the PL intensity, peak position, and line width with temperature and excitation source, the existence of free and bound excitonic recombination together with e1 → hh1 transitions in the QDs is established.

Structure and composition analysis of the Cu–Zn–Se ternary compounds by TEM/EDS

The structure and chemical composition of Cu1−xZn1−ySe2−δ (Cu–Zn–Se) ternary alloy semiconductors were examined by transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy (EDS), a TEM/EDS analytical technique. Polycrystalline Cu–Zn–Se thin films were prepared by atmospheric pressure metal–organic chemical vapor deposition. The TEM/EDS technique has made an elemental analysis focused on a microscopic region possible. Therefore, the spatial distribution of constituent elements of Cu–Zn–Se polycrystal within both grains and grain boundaries could be investigated and the compound stoichiometry was evaluated. Conclusively, the cross-sectional TEM images characterized the fabricated Cu–Zn–Se layers as a polycrystalline film of about 70–80nm thick and composed of grains with sizes ranging from 0.3 to 1.7μm. The chalcopyrite structure of Cu–Zn–Se films was confirmed by the selected area electron diffraction patterns. Moreover, the EDS point analyses conducted at optionally chosen positions showed quite comparable chemical compositions for the grains examined, yielding an average composition ratio of about 0.92:1.44:2 for Cu:Zn:(Se+O) within grains. However, the replacement of Cu atoms for Zn atoms in elemental composition was found at grain boundaries, resulting in an average composition ratio of about 1.26:1.24:2 for Cu:Zn:(Se+O) over there. It is suggested that the enhanced diffusion of Cu along the grain boundaries and the segregation of Cu to the grain boundaries increase the mean composition of Cu at these paths.

Effects of TMSb overpressure on InSb surface morphology for InSb epitaxial growth using low pressure metalorganic chemical vapor deposition

We investigated the effects of antimony (Sb) overpressure during thermal cleaning (TC) on the surface morphology of InSb substrates using low pressure metalorganic chemical vapor deposition (LP-MOCVD). During the TC process under H2 ambient, indium (In) droplets were observed inside etch pits on InSb(001) surfaces due to the Sb evaporation from InSb substrates. On the other hand, when InSb substrates were thermally cleaned under trimethylantimony (TMSb) ambient, the formation of In droplets and the etch pits were suppressed, resulting in the smooth InSb surface. The surface morphology of InSb was dependent on TC temperature. Rough surface morphology was observed at low TC temperature of 435°C and it became smoother with increasing TC temperature. The improvement of surface morphology was caused by the surface stabilization with increasing Sb flux and the increase of adatom migration. The dependence of TMSb flow rate on the surface morphology was also investigated. The TMSb overpressure during the TC of InSb must be maintained to grow high quality InSb epitaxial layers with smooth surface using MOCVD.

Fabrication of Cu3Zn3Se ternary compounds by AP-MOCVD

I–II–VI Ternary chalcopyrite semiconductors of Cu1−xZn1−ySe2−δ (Cu3Zn3Se) were successfully fabricated by the atmospheric pressure metal-organic chemical vapor deposition method for the first time. Four major peaks of (112), (220)/(204), (312)/(116), and (400), accompanied by three minor peaks of (103), (211) and (301) were observable in the X-ray diffraction spectra. In particular, the presence of those latter low-intensity peaks featured the formation of the chalcopyrite type Cu3Zn3Se compound. Typical absorption coefficients of the films produced were found to vary from 2.75×104cm−1 to 5.75×104cm−1 over all visible light range and from the same optical absorption spectra the energy gap of the material was extracted to be about 2.02eV. Moreover, the photoluminescence measurement conducted at room temperature also exhibited a strong orange-colored emission line at 1.94eV, which further confirmed that the Cu3Zn3Se ternary compound has been prepared. In addition, the cross-sectional and top-view scanning electron microscopy images characterized the fabricated Cu3Zn3Se compound as a polycrystalline film of thickness about 1–1.3μm and consisting of 1–2.5μm sized grains.

Study of the thermal stability of the H-related donors in high resistivity ZnO:Cu thin films by high-pressure H2 treatment

High resistivity ZnO:Cu thin films were fabricated on c-plane sapphire substrate by low pressure metal-organic chemical vapor deposition (MOCVD). The samples were treated in H2 ambient at high pressure and the thermal stability of the hydrogen-related donor-like defects was studied. Hall-effect measurement results presented that the high resistivity ZnO:Cu samples turn into n-type conductivity after H incorporation. The annealing results indicated that the hydrogenated ZnO:Cu could not recover high resistivity even after annealed at 750°C. It is proposed that some unknown H-related donor-like defects still exist in the film after annealing.

Effect of Silicon Doping on GaN Nanorods during Vapor–Liquid–Solid Growth

High optical quality and reproducible Si-doped GaN nanorods (NRs) were grown by low pressure metal–organic chemical vapor deposition. Different fluxes of SiH4 were introduced and at 2.7×10-9 mol/min the optimized morphology was obtained. Clear improvement of GaN NRs morphology characterized by smooth side walls and straightness was achieved after Si-doping. Near-band edge (NBE) emission at 356.88 nm (3.474 eV) and small full width at half maximum (FWHM) of 27.3 meV, measured by room temperature photoluminescence, confirmed the high optical and crystalline qualities. For Si-doped GaN NRs, a small blue-shift of NBE emission peak was observed, which was attributed to the band-filling effects.

Growth of ZnO Films on Si(111) by Metalorganic Chemical Vapor Deposition with AlN and Low-Temperature ZnO Double Buffers

To enhance the quality of ZnO films on Si(111) substrate, single layers of low-temperature ZnO (LT-ZnO) and AlN, as well as a combination of AlN and LT-ZnO layer, were used as intermediate layers by atmospheric pressure metalorganic chemical vapor deposition system. Only polycrystalline ZnO film was formed when a LT-ZnO single buffer was used. Crystal quality was enhanced when LT-ZnO was replaced by 20 nm AlN as the single buffer. The full width at half maximum (FWHM) of ZnO(0002) x-ray diffraction ω-rocking curve was 642 arcsec. Cracks began to appear on the film surface as crystallinity was enhanced. A ZnO mosaic single-crystal film with a mirror-like surface was successfully fabricated when a combined AlN and LT-ZnO served as buffer, and its FWHM of ZnO(0002) ω-rocking curve peak was only 460 arcsec. The film surface was smoother but cracks were still evident on the film. Contrary to the three-dimensional growth mode of samples with a single buffer, a quasi-two-dimensional growth mode was realized for the double-buffered high-temperature ZnO layer. Calculated film thickness was 2.14 μm, and the growth rate reached 4.3 μm/h based on the laser in situ laser reflectance trace.