MOCVD growth andproperties of GaN and AlGaN layers

In this work GaN and AlGaN layers were grown by metal-organic chemical vapor deposition (MOCVD) on sapphire substrates. The research was carried out at Micro and Nanoscience Laboratory of Helsinki University of Technology. The objective of this thesis is the study of MOCVD technique for the growth of GaN and AlGaN films and optimization of growth parameters in purpose to improve crystal quality of the films. The widely used two-step and the new multistep methods have been used for GaN, AlGaN MOCVD growth on c-plane sapphire. Properties of the GaN and AlGaN layers were studied using in-situ reflectance monitoring during MOCVD growth, atomic force microscopy and x-ray diffraction. Compared to the two step method, the multistep method has produced even better qualities of the GaN and AlGaN layers and significant reduction of threading dislocation density.

Growth and functionalization of carbon nanotubes on quartz filter for environmental applications

Background: Air pollution has become an important issue worldwide due to its adverse health effects. Among the different air contaminants, volatile organic compounds (VOCs) are liquids or solids with a high vapor pressure at room temperature that are extremely dangerous for human health. Removal of these compounds can be achieved using nanomaterials with tailored properties such as carbon nanotubes. Methods: Vertically-aligned multiwall carbon nanotubes (CNTs) were successfully grown on quartz filters by means of plasma enhanced chemical vapor deposition (PECVD). Furthermore, a plasma treatment was performed in order to modify the surface properties of the CNTs. The adsorption/desorption processes of three chlorinated compounds (trichloroethylene, 1,2-dichlorobenzene and chloroform) on the CNTs were studied using mass spectrometry measurements with a residual gas analyzer. Results: The adsorption capability of the CNTs increased after functionalization of their surface with a water plasma treatment. In addition, it was found that the presence of aromatic rings, water solubility and polarity of the VOCs play an important role on the adsorption/desorption kinetics at the CNTs surface. Conclusions: This study demonstrates the applicability of CNTs deposited on quartz filters for the removal or selective detection of volatile organic compounds (VOCs). The presence of aromatic rings in VOCs results in π -stacking interactions with a significant increase of their adsorption. On the other hand, it was found that CNTs surface interactions increase with water solubility and polarity of the VOC.

Hiilinanoputkireaktorin suunnittelu

Hiilinanoputki on vasta 90-luvun alussa löydetty uusi hiilestä koostuva materiaali, jonka erinomaiset mekaaniset ja fysikaaliset ominaisuudet tarjoavat niiden käytölle useita mahdollisia sovelluskohteita. Teknologian puute ja valmistusmenetelmien korkeat kustannukset ovat kuitenkin estäneet tehokkaasti niiden käytön nykyisten materiaalien ja puolijohteiden korvaajana. Tämän työn tarkoituksena on esitellä yleisimmät menetelmät hiilinanoputkien syntetisoimiseksi sekä suunnitella laite yksiseinäisten hiilinanoputkien tuottamiseen kemiallisen höyrydeposition avulla. Lisäksi tavoitteena on luoda laitteelle modulaarinen rakenne, jolloin sen eri osien korvaaminen rajapintojen sallimissa rajoissa on helppoa. Reaktorin mekaanisen suunnittelun ja komponenttien valinnan lisäksi työssä käsitellään laitteen kaasu- ja lämpövirtauksia, prosessissa tärkeiden katalyyttipartikkelien tuotantoa sekä laitteessa tarvittavien jäähdytysjärjestelmien mitoituksia. Tuloksena syntyi helposti toteutettava suunnitelma yksiseinäisiä nanoputkia tuottavan reaktorin valmistamiseksi. Työ jatkuu laitteen rakentamisella, testaamisella sekä jatkokehittelyllä.

Optimization of KOH etching process to obtain textured substrates suitable for heterojunction solar cells fabricated by HWCVD

In this work, we have studied the texturization process of (100) c-Si wafers using a low concentration potassium hydroxide solution in order to obtain good quality textured wafers. The optimization of the etching conditions have led to random but uniform pyramidal structures with good optical properties. Then, symmetric heterojunctions were deposited by Hot-Wire CVD onto these substrates and the Quasi-Steady-State PhotoConductance technique was used to measure passivation quality. Little degradation in the effective lifetime and implicit open circuit voltage of these devices (< 20 mV) was observed in all cases. It is especially remarkable that for big uniform pyramids, the open-circuit voltage is comparable to the values obtained on flat substrates.

Progress in a-Si:H/c-Si heterojunction emitters obtained by Hot-Wire CVD at 200°C

In this work, we investigate heterojunction emitters deposited by Hot-Wire CVD on p-type crystalline silicon. The emitter structure consists of an n-doped film (20 nm) combined with a thin intrinsic hydrogenated amorphous silicon buffer layer (5 nm). The microstructure of these films has been studied by spectroscopic ellipsometry in the UV-visible range. These measurements reveal that the microstructure of the n-doped film is strongly influenced by the amorphous silicon buffer. The Quasy-Steady-State Photoconductance (QSS-PC) technique allows us to estimate implicit open-circuit voltages near 700 mV for heterojunction emitters on p-type (0.8 Ω·cm) FZ silicon wafers. Finally, 1 cm 2 heterojunction solar cells with 15.4% conversion efficiencies (total area) have been fabricated on flat p-type (14 Ω·cm) CZ silicon wafers with aluminum back-surface-field contact.

Investigation of defect formation and electronic transport in microcrystalline silicon deposited by hot-wire CVD

We have investigated doped and undoped layers of microcrystalline silicon prepared by hot-wire chemical vapour deposition optically, electrically and by means of transmission electron microscopy. Besides needle-like crystals grown perpendicular to the substrate's surface, all of the layers contained a noncrystalline phase with a volume fraction between 4% and 25%. A high oxygen content of several per cent in the porous phase was detected by electron energy loss spectrometry. Deep-level transient spectroscopy of the crystals suggests that the concentration of electrically active defects is less than 1% of the undoped background concentration of typically 10^17 cm -3. Frequency-dependent measurements of the conductance and capacitance perpendicular to the substrate surface showed that a hopping process takes place within the noncrystalline phase parallel to the conduction in the crystals. The parasitic contribution to the electrical circuit arising from the porous phase is believed to be an important loss mechanism in the output of a pin-structured photovoltaic solar cell deposited by hot-wire CVD.

Studies on grain boundaries in nanocrystalline silicon grown by Hot-Wire CVD

The use of a tantalum wire in hot-wire chemical vapour deposition (HWCVD) has allowed the deposition of dense nanocrystalline silicon at low filament temperatures (1550 °C). A transition in the crystalline preferential orientation from (2 2 0) to (1 1 1) was observed around 1700 °C. Transmission electron microscopy (TEM) images, together with secondary ion mass spectrometry (SIMS) measurements, suggested that no oxidation occurred in materials obtained at low filament temperature due to the high density of the tissue surrounding grain boundaries. A greater concentration of SiH 3 radicals formed at these temperatures seemed to be responsible for the higher density.

In situ spectroellipsometric study of the nucleation and growth of amorphous silicon

A detailed in situ spectroellipsometric analysis of the nucleation and growth of hydrogenated amorphous silicon (a:Si:H) is presented. Photoelectronic quality a‐Si:H films are deposited by plasma‐enhanced chemical vapor deposition on smooth metal (NiCr alloy) and crystalline silicon (c‐Si) substrates. The deposition of a‐Si:H is analyzed from the first monolayer up to a final thickness of 1.2 μm. In order to perform an improved analysis, real time ellipsometric trajectories are recorded, using fixed preparation conditions, at various photon energies ranging from 2.2 to 3.6 eV. The advantage of using such a spectroscopic experimental procedure is underlined. New insights into the nucleation and growth mechanisms of a‐Si:H are obtained. The nucleation mechanism on metal and c‐Si substrates is very accurately described assuming a columnar microstructural development during the early stage of the growth. Then, as a consequence of the incomplete coalescence of the initial nuclei, a surface roughness at the 10-15 Å scale is identified during the further growth of a‐Si:H on both substrates. The bulk a‐Si:H grows homogeneously beneath the surface roughness. Finally, an increase of the surface roughness is evidenced during the long term growth of a‐Si:H. However, the nature of the substrate influenced the film growth. In particular, the film thickness involved in the nucleation‐coalescence phase is found lower in the case of c‐Si (67±8 Å) as compared to NiCr (118±22 Å). Likewise films deposited on c‐Si present a smaller surface roughness even if thick samples are considered (>1 μm). More generally, the present study illustrates the capability of in situ spectroellipsometry to precisely analyze fundamental processes in thin‐film growth, but also to monitor the preparation of complex structures on a few monolayers scale.

Progress in single junction microcrystalline silicon solar cells deposited by Hot-Wire CVD

Hot-Wire Chemical Vapor Deposition has led to microcrystalline silicon solar cell efficiencies similar to those obtained with Plasma Enhanced CVD. The light-induced degradation behavior of microcrystalline silicon solar cells critically depends on the properties of their active layer. In the regime close to the transition to amorphous growth (around 60% of amorphous volume fraction), cells incorporating an intrinsic layer with slightly higher crystalline fraction and [220] preferential orientation are stable after more than 7000 h of AM1.5 light soaking. On the contrary, solar cells whose intrinsic layer has a slightly lower crystalline fraction and random or [111] preferential orientation exhibit clear light-induced degradation effects. A revision of the efficiencies of Hot-Wire deposited microcrystalline silicon solar cells is presented and the potential efficiency of this technology is also evaluated.

Surface passivation of crystalline silicon by Cat-CVD amorphous and nanocrystalline thin silicon films

In this work, we study the electronic surface passivation of crystalline silicon with intrinsic thin silicon films deposited by Catalytic CVD. The contactless method used to determine the effective surface recombination velocity was the quasi-steady-state photoconductance technique. Hydrogenated amorphous and nanocrystalline silicon films were evaluated as passivating layers on n- and p-type float zone silicon wafers. The best results were obtained with amorphous silicon films, which allowed effective surface recombination velocities as low as 60 and 130 cms -1 on p- and n-type silicon, respectively. To our knowledge, these are the best results ever reported with intrinsic amorphous silicon films deposited by Catalytic CVD. The passivating properties of nanocrystalline silicon films strongly depended on the deposition conditions, especially on the filament temperature. Samples grown at lower filament temperatures (1600 °C) allowed effective surface recombination velocities of 450 and 600 cms -1 on n- and p-type silicon.

Control of doped layers in p-i-n microcrystalline solar cells fully deposited with HWCVD

In this paper, the influence of the deposition conditions on the performance of p-i-n microcrystalline silicon solar cells completely deposited by hot-wire chemical vapor deposition is studied. With this aim, the role of the doping concentration, the substrate temperature of the p-type layer and of amorphous silicon buffer layers between the p/i and i/n microcrystalline layers is investigated. Best results are found when the p-type layer is deposited at a substrate temperature of 125 °C. The dependence seen of the cell performance on the thickness of the i layer evidenced that the efficiency of our devices is still limited by the recombination within this layer, which is probably due to the charge of donor centers most likely related to oxygen.

Stability of hydrogenated nanocrystalline silicon thin-film transistors

Hydrogenated nanocrystalline silicon thin-films were obtained by catalytic chemical vapour deposition at low substrate temperatures (150°C) and high deposition rates (10 Å/s). These films, with crystalline fractions over 90%, were incorporated as the active layers of bottom-gate thin-film transistors. The initial field-effect mobilities of these devices were over 0.5 cm 2/V s and the threshold voltages lower than 4 V. In this work, we report on the enhanced stability of these devices under prolonged times of gate bias stress compared to amorphous silicon thin-film transistors. Hence, they are promising candidates to be considered in the future for applications such as flat-panel displays.

Electronic transport in low temperature nanocrystalline silicon thin-film transistors obtained by Hot-Wire CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) obtained by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature (150 °C) has been incorporated as the active layer in bottom-gate thin-film transistors (TFTs). These devices were electrically characterised by measuring in vacuum the output and transfer characteristics for different temperatures. The field-effect mobility showed a thermally activated behaviour which could be attributed to carrier trapping at the band tails, as in hydrogenated amorphous silicon (a-Si:H), and potential barriers for the electronic transport. Trapped charge at the interfaces of the columns, which are typical in nc-Si:H, would account for these barriers. By using the Levinson technique, the quality of the material at the column boundaries could be studied. Finally, these results were interpreted according to the particular microstructure of nc-Si:H.

Microcrystalline silicon thin film transistors obtained by Hot-Wire CVD

Polysilicon thin film transistors (TFT) are of great interest in the field of large area microelectronics, especially because of their application as active elements in flat panel displays. Different deposition techniques are in tough competition with the objective to obtain device-quality polysilicon thin films at low temperature. In this paper we present the preliminary results obtained with the fabrication of TFT deposited by hot-wire chemical vapor deposition (HWCVD). Some results concerned with the structural characterization of the material and electrical performance of the device are presented.

Thin Film Transistors obtained by Hot-Wire CVD

Hydrogenated microcrystalline silicon films obtained at low temperature (150-280°C) by hot wire chemical vapour deposition at two different process pressures were measured by Raman spectroscopy, X-ray diffraction (XRD) spectroscopy and photothermal deflection spectroscopy (PDS). A crystalline fraction >90% with a subgap optical absortion 10 cm -1 at 0.8 eV were obtained in films deposited at growth rates >0.8 nm/s. These films were incorporated in n-channel thin film transistors and their electrical properties were measured. The saturation mobility was 0.72 ± 0.05 cm 2/ V s and the threshold voltage around 0.2 eV. The dependence of their conductance activation energies on gate voltages were related to the properties of the material.