Structure, stability and photoelectronic properties of transition films from amorphous to microcrystalline silicon

A series of hydrogenated silicon films near the threshold of crystallinity was prepared by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) from a mixture of SiH4 diluted in H, The effect of hydrogen dilution ratios R-H = [H-2]/[SiH4] on microstructure of the films was investigated. Photoelectronic properties and stability of the films were studied as a function of crystalline fraction. The results show that more the crystalline volume fraction in the silicon films, the higher mobility life-time product (mu tau), better the stability and lower the photosensitivity. Those diphasic films contained 8%-31% crystalline volume fraction can gain both the fine photoelectronic properties and high stability. in the diphasic (contained 12% crystalline volume fraction) solar cell, we obtained a much lower light-induced degradation of similar to 2.9%, with a high initial efficiency of 10.01% and a stabilized efficiency of 9.72% (AM1.5, 100 mW/cm(2)). (c) 2005 Elsevier B.V. All rights reserved.

Reliable concentrated photovoltaic system with compound concentrator

Concentrated photovoltaic systems (CPVSs) draw more and more attention because of high photovoltaic conversion efficiency, low consumption of solar cell, and low cost of power generation. However, the fallibility of the tracker in such systems has hindered their practical application for more than twenty years. The tracker is indispensable for a CPVS since only normal-incident sunlight can be focused on the solar cell chips, even a slight deviation of incident light will result in a significant loss of solar radiation, and hence a distinct decrease in electricity output. Generally, the more accurate the tracker is, the more reliable the system is. However, it is not exactly the case for a CPVS reliability, because the more accurate the tracker is, the better environment it demands. A CPVS is usually has to subjected to harsh environmental conditions, such as strong wind, heavy rain or snow, and huge changes of temperature, which leads to the invalidation of the system's high-accuracy tracker. Hence, the reliability of a CPVS cannot be improved only by enhancing the tracker's accuracy. In this paper, a novel compound concentrator, combination of Fresnel lens and photo-funnel, has been adopted in a prototype CPVS. Test results show that the compound concentrator can relax the angle tolerance from one tenth to five degrees of arc at 400 suns, which can help a CPVS endure serious environment and remain its reliability over long period. The CPVS with compound concentrator is attractive for commercial application.

Improved diphasic nc-si/a-si : H I-layer materials using PECVD

Two series of films has been prepared by using a new regime of plasma enhanced chemical vapor deposition (PECVD) in the region adjacent to the phase transition from amorphous to crystalline state. The photoelectronic properties of the films have been investigated as a function of crystalline fraction. In comparison with typical a-Si:H, these diphasic films with a crystalline fraction less than 0.3 show a similar optical absorption coefficient, higher mobility life-time product ( LT) and higher stability upon light soaking. By using the diphasic nc-Si/a-Si films as the intrinsic layer, a p-i-n junction solar cell has been prepared with an initial efficiency of 9. 10 % and a stabilized efficiency of 8.56 % (AM 1.5, 100 mW/cm(2)).

Comparative study of the surface passivation on crystalline silicon by silicon thin films with different structures

Si thin films with different structures were deposited by plasma enhanced chemical vapor deposition (PECVD), and characterized via Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The passivation effect of such different Si thin films on crystalline Si surface was investigated by minority carrier lifetime measurement via a method, called microwave photoconductive decay (mu PCD), for the application in HIT (heterojunction with intrinsic thin-layer) solar cells. The results show that amorphous silicon (a-Si:H) has a better passivation effect due to its relative higher H content, compared with microcrystalline (mu c-Si) silicon and nanocrystalline silicon (nc-Si). Further, it was found that H atoms in the form of Si-H bonds are more preferred than those in the form of Si-H-2 bonds to passivate the crystalline Si surface. (C) 2009 Elsevier B.V. All rights reserved.

INVESTIGATION OF GAAS/SI MATERIAL BY X-RAY DOUBLE-CRYSTAL DIFFRACTION

GaAs epilayer films on Si substrates grown by molecular-beam epitaxy were investigated by the x-ray double-crystal diffraction method. The rocking curves were recorded for different diffraction vectors of samples. The results show that the unit-cell volumes of GaAs epilayers are smaller than that of the GaAs bulk material. The strained-layer superlattice buffer layer can improve the quality of the film, especially in the surface lamella. The parameter W' = W(expt)/(square-root \gamma-h\/gamma-0/sin 2-theta-B) is introduced to describe the quality of different depths of epilayers. As the x-ray incident angle is increased, W' also increases, that is, the quality of the film deteriorates with increasing penetration distance of the x-ray beam. Therefore, W' can be considered as a parameter that describes the degree of perfection of the epilayer along the depth below the surface. The cross-section transmission electron microscopy observations agree with the results of x-ray double-crystal diffraction.

A room-temperature ionic-liquid-templated proton-conducting gelatinous electrolyte

Novel proton-conducting gelatinous electrolytes templated by room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF(4)) have been prepared in methylsisesquioxane backbone containing H3PO4, and the influences of the RTIL on the structure, morphology, thermal stability, and electrochemical properties of the gelatinous electrolytes have been examined. X-ray diffraction and scanning electron microscopy proved that BMImBF(4) acted as structure-directing template during the sol-gel process of methyl-trimethoxysilane. X-ray photoelectron spectra and infrared spectroscopy demonstrated that the hydrogen-bonding was formed between BMImBF(4) and H3PO4. The electrolytes had good thermal stability up to 300 degreesC and showed superior mechanical and electrochemical properties. A room-temperature conductivity of 1.2 x 10(-3) S cm(-1) was obtained for the electrolyte at the molar ratio of RTIL/Si/H3PO4 0.3/1/1, and its electrochemical window was up to 1.5 V.

STUDIES ON INTERFACIAL PHENOMENA OF POLYCRYSTALLINE HG1-XCDXTE THIN-FILM ELECTRODE POLYSULFIDE REDOX SOLUTION

Electrode capacitance and photocurrent spectra of electrodeposited polycrystalline Hg1-xCdxTe thin films of varying (1-x) were measured in polysulfide redox solution, hence the flatband potentional PHI(fb) and the bandgap E(g) of Hg1-xCdxTe thin films obtained. It was of interest to find out that only the location of conduction band E(c) shifts negatively with increasing (1-x) while the valence band E(v), is almost constant. The experimental open circuit photovoltage V0 is smaller than theoretical value V(max) calculated through flatband potential PHI(fb), therefore there is a possibility of promoting the experimental open circuit photovoltage.

First principles simulation of amorphous silicon bulk, interfaces, and nanowires for photovoltaics

Amorphous silicon has become the material of choice for many technologies, with major applications in large area electronics: displays, image sensing and thin film photovoltaic cells. This technology development has occurred because amorphous silicon is a thin film semiconductor that can be deposited on large, low cost substrates using low temperature. In this thesis, classical molecular dynamics and first principles DFT calculations have been performed to generate structural models of amorphous and hydrogenated amorphous silicon and interfaces of amorphous and crystalline silicon, with the ultimate aim of understanding the photovoltaic properties of core-shell crystalline amorphous Si nanowire structures. We have shown, unexpectedly, from the simulations, that our understanding of hydrogenated bulk a-Si needs to be revisited, with our robust finding that when fully saturated with hydrogen, bulk a-Si exhibits a constant optical energy gap, irrespective of the hydrogen concentration in the sample. Unsaturated a-Si:H, with a lower than optimum hydrogen content, shows a smaller optical gap, that increases with hydrogen content until saturation is reached. The mobility gaps obtained from an analysis of the electronic states show similar behavior. We also obtained that the optical and mobility gaps show a volcano curve as the H content is varied from 7% (undersaturation) to 18% (mild oversaturation). In the case of mild over saturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structures shows the extra H atoms in this case form a bridge between neighboring silicon atoms which increases the corresponding Si-Si distance and promotes bond length disorder in the sample. That has the potential to enhance the Staebler-Wronski effect. Planar interface models of amorphous-crystalline silicon have been generated in Si (100), (110) and (111) surfaces. The interface models are characterized by structure, RDF, electronic density of states and optical absorption spectrum. We find that the least stable (100) surface will result in the formation of the thickest amorphous silicon layer, while the most stable (110) surface forms the smallest amorphous region. We calculated for the first time band offsets of a-Si:H/c-Si heterojunctions from first principles and examined the influence of different surface orientations and amorphous layer thickness on the offsets and implications for device performance. The band offsets depend on the amorphous layer thickness and increase with thickness. By controlling the amorphous layer thickness we can potentially optimise the solar cell parameters. Finally, we have successfully generated different amorphous layer thickness of the a-Si/c-Si and a-Si:H/c-Si 5 nm nanowires from heat and quench. We perform structural analysis of the a-Si-/c-Si nanowires. The RDF, Si-Si bond length distributions, and the coordination number distributions of amorphous regions of the nanowires reproduce similar behaviour compared to bulk amorphous silicon. In the final part of this thesis we examine different surface terminating chemical groups, -H, - OH and –NH2 in (001) GeNW. Our work shows that the diameter of Ge nanowires and the nature of surface terminating groups both play a significant role in both the magnitude and the nature of the nanowire band gaps, allowing tuning of the band gap by up to 1.1 eV. We also show for the first time how the nanowire diameter and surface termination shifts the absorption edge in the Ge nanowires to longer wavelengths. Thus, the combination of nanowire diameter and surface chemistry can be effectively utilised to tune the band gaps and thus light absorption properties of small diameter Ge nanowires.

Improving Photovoltaics with High Luminescence Efficiency Quantum Dot Layers

A solar cell relies on its ability to turn photons into current. Because short wavelength photons are typically absorbed near the top surface of a cell, the generated charge carriers recombine before being collected. But when a layer of quantum dots (nanoscale semiconductor particles) is placed on top of the cell, it absorbs short wavelength photons and emits them into the cell at longer wavelengths, which enables more efficient carrier collection. However, the resulting power conversion efficiency of the system depends critically on the quantum dot luminescence efficiency – the nature of this relationship was previously unknown. Our calculations suggest that a quantum dot layer must have high luminescence efficiency (at least 80%) to improve the current output of existing photovoltaic (PV) cells; otherwise, it may worsen the cell’s efficiency. Our quantum dot layer (using quantum dots with over 85% quantum yield) slightly reduced the efficiency of our PV cells. We observed a decrease in short circuit current of a commercial-grade cell from 0.1977 A to 0.1826 A, a 7.6% drop, suggesting that improved optical coupling from the quantum dot emission into the solar cell is needed. With better optical coupling, we predict current enhancements between ~6% and ~8% for a solar cell that already has an antireflection coating. Such improvements could have important commercial impacts if the coating could be deployed in a scalable fashion.

Prospect for EPM application to environmental technology

EPM seems to have good prospects for the future not only in the materials processing but also in environmental technologies by the help of superior features like contactless processing, clean heating and melting, and good controllability. In the present paper, the authors commentate on the possibility of EPM to avoid environmental issues of energy, resources and hazardous wastes by the use of the functions of Lorentz force and Joule heating. Firstly, the present situation and future trend of electric power generation is outlined, and then some examples of the application of EPM to environmental technologies are introduced, which have been performed by the author’s group. Examples are as follows: production of spherical solar cell from a liquid jet by using intermittent electromagnetic force; fabrication of semi-solid Al-Si slurry for die-casting of vehicle-parts to reduce the weight of vehicle; electromagnetic separation of nonmetallic inclusions from liquid Al scrap and its application to the fabrication of partially particle-reinforced aluminum alloy; electromagnetic melting of hazardous wastes from power plants to stabilize wastes in glass state.

Orientation effects in copper phthalocyanine films studied by EPR

Organic semiconductors have already found commercial applications in for example displays with organic light-emitting diodes (OLEDs) and great advances are also being made in other areas, such as organic field-effect transistors and organic solar cells. [1] The organic semicondutor group of materials known as metal phthalocyanines (MPc’s) is interesting for applications such as large area solar cells due to their optoelectronic properties coupled with the possibility of easily and cheaply fabricating thin films of MPc’s. [1, 2]

Many of the properties of organic semiconductors, such as magnetism, light absorption and charge transport, show orientational anisotropy. [2, 3] To maximise the efficiency of a device based on these materials it is therefore important to study the molecular orientation in films and to assess the influence of different growth conditions and substrate treatments. X-ray diffraction is a well established and powerful technique for studying texture (and hence molecular orientation)_in crystalline materials, but cannot provide any information about amorphous or nanocrystalline films. In this paper we present a continuous wave X-band EPR study using the anisotropy of the CuPc EPR spectrum [4] to determine the orientation effects in different types of CuPc films. From these measurements we also gain insight into the molecular arrangement of films of CuPc mixed with the isomorphous H2Pc and with C60 in films typical of real solar cell systems.

Rapid, simple method for determining the porosity of mesoporous TiO2 films using a quartz crystal microbalance (QCM)

Two different mesoporous films of TiO2 were coated onto a QCM disc and fired at 450o C for 30 min. The first film was derived from a sol-gel paste that was popular in the early days of dye-sensitised solar cell, i.e. dssc, research, a TiO2(sg) film. The other was a commercial colloidal paste used to make examples of the current dssc cell; a TiO2(ds) film. A QCM was used to determine the mass of the TiO2 film deposited on each disc and the increase in the mass of the film when immersed in water/glycerol solutions with wt% values spanning the range 0-70%. The results of this work reveal that with both TiO2 mesoporous films the solution fills the film's pores and acts as a rigid mass, thereby allowing the porosity of each film to be calculated as: 59.1% and 71.6% for the TiO2(sg) and TiO2(ds) films, respectively. These results, coupled with surface area data, allowed the pore radii of the two films to be calculated as: 9.6 and 17.8 nm, respectively. This method is then simplified further, to just a few frequency measurements in water and only air to reveal the same porosity values. The value of the latter ‘one point’ method for making porosity measurements is discussed briefly.

Células solares de Cu2ZnSnS4 por sulfurização de camadas metálicas

As energias renováveis têm estado em destaque desde o fi nal do século XX. São vários os motivos para que isto esteja a acontecer. As previsões apontam para problemas de depleção das reservas de combustíveis fósseis, nomeadamente o petróleo e gás natural, durante o presente século. O carvão, ainda abundante, apresenta problemas ambientais signi cativos. Os perigos associados à energia nuclear estão fazer com que os governos de vários países repensem as suas políticas energéticas . Todas estas tecnologias têm fortes impactos ambientais. Considerando o conjunto das energias renováveis, a energia solar fotovoltaica tem ainda um peso menor no panorama da produção energética actual. A explicação para este facto deve-se ao custo, ainda elevado, dos sistemas fotovoltaicos. Várias iniciativas governamentais estão em curso, a SET for 2020 (UE) e a Sunshot (EUA), para o desenvolvimento de tecnologias que façam frente a este problema. A fatia de mercado que a tecnologia de filmes fi nos representa ainda é pequena, mas tem vindo a aumentar nos últimos anos. As vantagens relativamente à tecnologia tradicional baseada em Si são várias, como por ex. os custos energéticos e materiais para a fabricação das células. Esta dissertação apresenta um processo de fabricação de células solares em fi lmes finos usando como camada absorvente um novo composto semicondutor, o Cu2ZnSnS4, que apresenta como grande argumento, relativamente aos seus predecessores, o facto de ser constituído por elementos abundantes e de toxicidade reduzidas. Foi realizado um estudo sobre as condições termodinâmicas de crescimento deste composto, bem como a sua caracterização e das células solares finais. Este trabalho inclui um estudo dos compostos ternários, CuxSnSx+1 e compostos binários SnxSy, justi cado pelo facto de surgirem como fases secundárias no crescimento do Cu2ZnSnS4. Em seguida são descritos resumidamente os vários capítulos que constituem esta tese. No capítulo 1 é abordada de forma resumida a motivação e o enquadramento da tecnologia no panorama energético global. A estrutura da célula solar adoptada neste trabalho é também descrita. O capítulo 2 é reservado para uma descrição mais detalhada do composto Cu2ZnSnS4, nomeadamente as propriedades estruturais e opto-electrónicas. Estas últimas são usadas para explicar as composições não estequiométricas aplicadas no crescimento deste composto. São também descritas as várias técnicas de crescimento apresentadas na literatura. A última secção deste capítulo apresenta os resultados da caracterização publicados pelos vários grupos que estudam este composto. O método que foi implementado para crescer a camada absorvente, bem como os efeitos que a variação dos vários parâmetros têm neste processo são abordados no capítulo 3. Neste é também incluída uma descrição detalhada dos equipamentos usados na caraterização da camada absorvente e das células solares finais. As fases calcogêneas binária e ternárias são estudadas no capítulo 4. É apresentada uma descrição do método de crescimento, quer para as fases do tipo CuxSnSx+1, quer para as fases do tipo SnxSy e a sua caracterização básica, nomeadamente a sua composição e as propriedades estruturais, ópticas e eléctricas. No caso dos compostos binários são também apresentados os resultados de uma célula solar. No capítulo 5 são reportados os resultados da caracterização dos fi lmes de Cu2ZnSnS4. Técnicas como a dispersão Raman, a fotoluminescência, a efi ciência quântica externa e a espectroscopia de admitância são usadas para analisar as propriedades quer da camada absorvente quer da célula solar. No capítulo 6 é apresentada uma conclusão geral do trabalho desenvolvido e são referidas sugestões para melhorar e complementar os estudos feitos.

Multiphysics Simulation of Nanostructured Semiconductor Devices

Thesis (Ph.D.)--University of Washington, 2013

Nanotech thin film photovoltaics

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Electrónica e Telecomunicações