Grafene: proprietà, sintesi e trasferimento con il ciclododecano

Il grafene è un cristallo bidimensionale di atomi di carbonio, isolato per la prima volta nel 2004 da due fisici che per questo risultato vinsero il premio Nobel per la Fisica nel 2010. Il grafene possiede proprietà chimiche e fisiche superiori, quali un’elevata resistenza chimica e meccanica e un’eccellente conducibilità termica ed elettrica. Inoltre possiede altre due caratteristiche che lo rendono particolarmente promettente in diversi ambiti applicativi: leggerezza e trasparenza ottica. In questo elaborato ho descritto le attività svolte seguendo le ricerche che vengono svolte al CNR-IMM di Bologna, dove questo materiale viene prodotto tramite la tecnica di Chemical Vapor Deposition e studiato per l’integrazione in dispositivi elettronici ed elettro-meccanici innovativi. Durante la mia esperienza di laboratorio all’IMM ho seguito i procedimenti che portano al trasferimento del grafene sintetizzato su substrati catalitici di rame sui substrati finali per la successiva integrazione nella tecnologia del silicio. Nell’elaborato vengono da prima descritte la struttura cristallina ed elettronica e successivamente presentate alcune proprietà di cui gode e messe in relazione con i materiali attualmente in uso. Segue una breve trattazione bibliografica di alcune delle principali tecniche di produzione del grafene, trattando più nel dettaglio la tecnica CVD attualmente in uso per la sintesi di grafene all’interno dei laboratori del CNR-IMM di Bologna. La parte principale di questa esperienza di laboratorio è stato di seguire in prima persona le attuali ricerche del gruppo di lavoro per la messa a punto di un metodo alternativo che utilizza il ciclododecano per il trasferimento del grafene sintetizzato su rame al posto del classico strato sacrificale polimerico di PMMA. Nell’elaborato il confronto tra le due tecniche viene eseguito confrontando i risultati del trasferimento analizzando la morfologia dei campioni finali con tecniche di microscopia elettronica in scansione

Hydrogenated amorphous silicon deposited by high pressure sputtering for HIT solar cells

Hydrogenated amorphous silicon thin films were deposited using a high pressure sputtering (HPS) system. In this work, we have studied the composition and optical properties of the films (band-gap, absorption coefficient), and their dependence with the deposition parameters. For films deposited at high pressure (1 mbar), composition measurements show a critical dependence of the purity of the films with the RF power. Films manufactured with RF-power above 80W exhibit good properties for future application, similar to the films deposited by CVD (Chemical Vapor Deposition) for hydrogenated amorphous silicon.

The intermediate band approach in the third solar cell generation context

Hydrogenated amorphous silicon thin films were deposited using a high pressure sputtering (HPS) system. In this work, we have studied the composition and optical properties of the films (band-gap, absorption coefficient), and their dependence with the deposition parameters. For films deposited at high pressure (1 mbar), composition measurements show a critical dependence of the purity of the films with the RF power. Films manufactured with RF-power above 80W exhibit good properties for future application, similar to the films deposited by CVD (Chemical Vapor Deposition) for hydrogenated amorphous silicon.

CVD of CrO(2): Towards a lower temperature deposition process

The deposition of highly oriented a-axis CrO(2) films onto Al(2)O(3)(0001) by atmospheric pressure (AP)CVD at temperatures as low as 330 C is reported. Deposition rates strongly depend on the substrate temperature, whereas for film surface microstructures the dependence is mainly on film thickness. For the experimental conditions used in this work, CrO(2) growth kinetics are dominated by a surface reaction mechanism with an apparent activation energy of (121.0 +/- 4.3) kJ mol(-1). The magnitude and temperature dependence of the saturation magnetization, up to room temperature, is consistent with bulk measurements.

Shutterless deposition of phosphorous doped microcrystalline silicon by Cat-CVD

In this paper we present results on phosphorous-doped μc-Si:H by catalytic chemical vapour deposition in a reactor with an internal arrangement that does not include a shutter. An incubation phase of around 20 nm seems to be the result of the uncontrolled conditions that take place during the first stages of deposition. The optimal deposition conditions found lead to a material with a dark conductivity of 12.8 S/cm, an activation energy of 0.026 eV and a crystalline fraction of 0.86. These values make the layers suitable to be implemented in solar cells.

Exploring polysilicon deposition conditions through a laboratory CVD prototype

Cost and energy consumption related to obtaining polysilicon impact significantly on the total photovoltaic module cost and its energy payback time. Process simplifications can be performed, leading to cost reductions. Nowadays, among several approaches currently pursued to produce the so called Solar Grade Silicon, the chemical route, named Siemens process, is the dominant one. At the Instituto de Energía Solar research on this topic is focused on the chemical route, in particular on the polysilicon deposition step by chemical vapor deposition (CVD) from Trichlorosilane through a laboratory prototype. Valuable information about the phenomena involved in the polysilicon deposition process and the operating conditions is obtained from our experiments. A particular feature of our system is the inclusion of a mass spectrometer. The present work comprises spectra characterization of the polysilicon deposition chemical reaction, temperature and inlet gas mixture composition influence on the deposition rate and analysis of polysilicon deposition conditions for the ?pop-corn' phenomenon to appear, based on experimental experience (Actas de la Special Issue: E-MRS 2012 Spring Meeting ? Symposium A

Deposition of Intrinsic a-Si:H by ECR-CVD to Passivate the Crystalline Silicon Heterointerface in HIT Solar Cells

We have deposited intrinsic amorphous silicon (a-Si:H) using the electron cyclotron resonance (ECR) chemical vapor deposition technique in order to analyze the a-Si:H/c-Si heterointerface and assess the possible application in heterojunction with intrinsic thin layer (HIT) solar cells. Physical characterization of the deposited films shows that the hydrogen content is in the 15-30% range, depending on deposition temperature. The optical bandgap value is always comprised within the range 1.9- 2.2 eV. Minority carrier lifetime measurements performed on the heterostructures reach high values up to 1.3 ms, indicating a well-passivated a-Si:H/c-Si heterointerface for deposition temperatures as low as 100°C. In addition, we prove that the metal-oxide- semiconductor conductance method to obtain interface trap distribution can be applied to the a-Si:H/c-Si heterointerface, since the intrinsic a-Si:H layer behaves as an insulator at low or negative bias. Values for the minimum of D_it as low as 8 × 10^10 cm^2 · eV^-1 were obtained for our samples, pointing to good surface passivation properties of ECR-deposited a-Si:H for HIT solar cell applications.

Design and Characterization of Novel Wear Resistant Multilayer CVD Coatings with Improved Adhesion Between Al(2)O(3) and Ti(C,N)

Multilayer CVD coatings for high speed cutting applications were designed to achieve high wear and heat resistance during machining of steel alloys. In this work the microstructure and cutting performance of these novel multilayer CVD coatings are investigated and compared with standard CVD multilayer coatings. 3D-FIB tomography is used to characterize the microstructure of the layers, especially the transition between the Ti(C,N) and the Al(2)O(3) layer. The 3D reconstruction of the surface of the Ti(C,N) layer shows the formation of protruded Ti(C,N) grains with a very particular architecture, which penetrate into the Al(2)O(3) top-layer, providing a mechanical anchoring between both layers. Cemented carbides coated with the novel CVD multilayer present reduced crater and flank wear as well as improved adherence between the Al(2)O(3) top-layer and the Ti(C,N) layer leading to a dramatic improvement of cutting performance.

Novel silica gel supported TiO2 photocatalyst synthesized by CVD method

TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve the recovery rate of TiO2 photocatalysts, which in most cases are in fine powder form, the chemical vapor deposition (CVD) method was used to load TiO2 onto a bigger particle support, silica gel. The amount of titania coating was found to depend strongly on the synthesis parameters of carrier gas flow rate and coating time. XPS and nitrogen ads/desorption results showed that most of the TiO2 particles generated from CVD were distributed on the external surface of the support and the coating was stable. The photocatalytic activities of TiO2/silica gel with different amounts of titania were evaluated for the oxidation of phenol aqueous solution and compared with that of Degussa P25. The optimum titania loading rate was found around 6 wt % of the TiO2 bulk concentration. Although the activity of the best TiO2/silica gel sample was still lower than that of P25, the synthesized TiO2/silica gel catalyst can be easily separated from the treated water and was found to maintain its TiO2 content and catalytic activity.

Morphological and structural characterization of CrO2/Cr2O3 films grown by laser-CVD

This work reports on the synthesis of chromium (III, IV) oxides films by KrF laser-assisted CVD. Films were deposited onto sapphire substrates at room temperature by the photodissociation of Cr(CO)(6) in dynamic atmospheres containing oxygen and argon. A study of the processing parameters has shown that partial pressure ratio Of O-2 to Cr(CO)(6) and laser fluence are the prominent parameters that have to be accurately controlled in order to co-deposit both the crystalline oxide phases. Films consistent with such a two-phase system were synthesised for a laser fluence of 75 mJ cm(-2) and a partial pressure ratio of about 1. (c) 2005 Elsevier B.V. All rights reserved.

Effect of argon ion energy on the performance of silicon nitridemultilayer permeation barriers grown by hot-wire CVD on polymers

One of the authors (S.M.) acknowledges Direction des Relations Extérieures of Ecole Polytechnique for financial support.

Development of laser-fired contacts for amorphous silicon layers obtained by Hot-Wire CVD

In this work we study aluminium laser-fired contacts for intrinsic amorphous silicon layers deposited by Hot-Wire CVD. This structure could be used as an alternative low temperature back contact for rear passivated heterojunction solar cells. An infrared Nd:YAG laser (1064 nm) has been used to locally fire the aluminium through the thin amorphous silicon layers. Under optimized laser firing parameters, very low specific contact resistances (ρc ∼ 10 mΩ cm2) have been obtained on 2.8 Ω cm p-type c-Si wafers. This investigation focuses on maintaining the passivation quality of the interface without an excessive increase in the series resistance of the device.

Uniformity Study of Amorphous and Microcrystalline Silicon Thin Films Deposited on 10cmx10cm Glass Substrate using Hot Wire CVD Technique

The scaling up of the Hot Wire Chemical Vapor Deposition (HW-CVD) technique to large deposition area can be done using a catalytic net of equal spaced parallel filaments. The large area deposition limit is defined as the limit whenever a further increment of the catalytic net area does not affect the properties of the deposited film. This is the case when a dense catalytic net is spread on a surface considerably larger than that of the film substrate. To study this limit, a system able to hold a net of twelve wires covering a surface of about 20 cm x 20 cm was used to deposit amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon over a substrate of 10 cm x 10 cm placed at a filament-substrate distance ranging from 1 to 2 cm. The uniformity of the film thickness d and optical constants, n(x, λ) and α(x,¯hω), was studied via transmission measurements. The thin film uniformity as a function of the filament-substrate distance was studied. The experimental thickness profile was compared with the theoretical result obtained solving the diffusion equations. The optimization of the filament-substrate distance allowed obtaining films with inhomogeneities lower than ±2.5% and deposition rates higher than 1 nm/s and 4.5 nm/s for (μc-Si:H) and (a-Si:H), respectively.

Low temperature amorphous and nanocrystalline silicon thin film transistors deposited by Hot-Wire CVD on glass substrate

Amorphous and nanocrystalline silicon films obtained by Hot-Wire Chemical Vapor Deposition have been incorporated as active layers in n-type coplanar top gate thin film transistors deposited on glass substrates covered with SiO 2. Amorphous silicon devices exhibited mobility values of 1.3 cm 2 V - 1 s - 1, which are very high taking into account the amorphous nature of the material. Nanocrystalline transistors presented mobility values as high as 11.5 cm 2 V - 1 s - 1 and resulted in low threshold voltage shift (∼ 0.5 V).

Substrate influence on the properties of doped thin silicon layers grown by Cat-CVD

We present structural and electrical properties for p- and n-type layers grown close to the transition between a-Si:H and nc-Si:H onto different substrates: Corning 1737 glass, ZnO:Al-coated glass and stainless steel. Structural properties were observed to depend on the substrate properties for samples grown under the same deposition conditions. Different behaviour was observed for n- and p-type material. Stainless steel seemed to enhance crystallinity when dealing with n-type layers, whereas an increased crystalline fraction was obtained on glass for p-type samples. Electrical conduction in the direction perpendicular to the substrate seemed to be mainly determined by the interfaces or by the existence of an amorphous incubation layer that might determine the electrical behaviour. In the direction perpendicular to the substrate, n-type layers exhibited a lower resistance value than p-type ones, showing better contact properties between the layer and the substrate.