Toward high-performance polymer solar cells: The importance of morphology control

Polymer solar cells have the potential to become a major electrical power generating tool in the 21st century. R&D endeavors are focusing on continuous roll-to-roll printing of polymeric or organic compounds from solution-like newspapers-to produce flexible and lightweight devices at low cost. It is recognized, though, that besides the functional properties of the compounds the organization of structures on the nanometer level-forced and controlled mainly by the processing conditions applied-determines the performance of state-of-the-art polymer solar cells. In such devices the photoactive layer is composed of at least two functional materials that form nanoscale interpenetrating phases with specific functionalities, a so-called bulk heterojunction. In this perspective article, our current knowledge on the main factors determining the morphology formation and evolution is introduced, and gaps of our understanding on nanoscale structure-property relations in the field of high-performance polymer solar cells are addressed. Finally, promising routes toward formation of tailored morphologies are presented.

Progress in polymer solar cell

This review outlines current progresses in polymer solar cell. Compared to traditional silicon-based photovoltaic (PV) technology, the completely different principle of optoelectric response in the polymer cell results in a novel configuration of the device and more complicated photovoltaic generation process. The conception of bulk-heterojunction (BHJ) is introduced and its advantage in terms of morphology is addressed. The main aspects including the morphology of photoactive layer, which limit the efficiency and stability of polymer solar cell, are discussed in detail. The solutions to boosting up both the efficiency and stability (lifetime) of the polymer solar cell are highlighted at the end of this review.

Organic photovoltaic cells using hexadecafluorophthalocyaninatocopper (F16CuPc) as electron acceptor material

We fabricated organic photovoltaic cells by using hexadecafluorophthalocyaninatocopper (F16CuPc) as electron acceptor material and para-sexiphenyl (p-6P) as electron donor material. F16CuPc has wide absorption spectrum from 550 nm to 850 nm, which covers the maximum of solar photo flux. The measurement of their external quantum efficiency (EQE) demonstrated that the photocurrent comes from the excitons created in F16CuPc, which were separated into free electrons and holes at heterojunction interface of p-6P and F16CuPc. Moreover, F(16)FuPc with excellent air-stability improved the environmental stability of photovoltaic cells, and the unencapsulated cells exhibited the shelf lifetime of exceeding a week.

Electronic structure of interfaces between copper-hexadecafluoro-phthalocyanine and 2,5-bis(4-biphenylyl) bithiophene

The interfaces formed between copper-hexadecafluoro-phthalocyanine (F16CuPc) and 2,5-bis(4-biphenylyl) bithiophene (BP2T) were examined using photoemission and inverse photoemission spectroscopy. It is observed that in F16CuPc/BP2T the heterojunction is characterized by band bending in both materials, while in BP2T/F16CuPc the band bending is confined in BP2T only. The combination of the band bending and finite Debye lengths provides an explanation to the observed ambipolar behavior of the organic thin film transistors based on such heterojunctions.

Weak epitaxy growth affording high-mobility thin films of disk-like organic semiconductors

Thin films of phthalocyanine compounds show weak epitaxial growth on a monodomain film of a rod-like molecule (see figure). The resulting organic electronic devices exhibit high charge carrier mobilities close to those of the single-crystal devices.

Ambipolar organic field-effect transistors with air stability, high mobility, and balanced transport

Ambipolar organic field-effect transistors (OFETs) based on the organic heterojunction of copper-hexadecafluoro-phthalocyanine (F16CuPc) and 2,5-bis(4-biphenylyl) bithiophene (BP2T) were fabricated. The ambipolar OFETs eliminated the injection barrier for the electrons and holes though symmetrical Au source and drain electrodes were used, and exhibited air stability and balanced ambipolar transport behavior. High field-effect mobilities of 0.04 cm(2)/V s for the holes and 0.036 cm(2)/V s for the electrons were obtained. The capacitance-voltage characteristic of metal-oxide-semiconductor (MOS) diode confirmed that electrons and holes are transported at F16CuPc and BP2T layers, respectively. On this ground, complementary MOS-like inverters comprising two identical ambipolar OFETs were constructed.

Interfacial electronic structure of copper phthalocyanine and copper hexadecafluorophthalocyanine studied by photoemission

Electronic structures of the heterojunction between copper phthalocyanine (CuPc) and copper hexadecafluorophthalocyanine (F16CuPc) were studied with ultraviolet photoemission spectroscopy. Band bending and an interface dipole were observed at the interface due to the formation of an electron accumulation layer and a depletion layer in F16CuPc and CuPc, respectively. Such an energy level alignment leads to interesting ambipolar characteristics for application of the CuPc/F16CuPc junction in organic field-effect transistors.

Improved efficiency by a graded emissive region in organic light-emitting diodes

Electrical and optical properties of organic light-emitting diodes (OLEDs) with a stepwise graded bipolar transport emissive layer for a better control of charge transport and recombination are presented. The graded bipolar transport layer was formed by co-evaporating a hole-transporting material N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4(')-diamine (NPB) and an electron-transporting/emissive material tris-(8-hydroxyquinoline) aluminum (Alq(3)) in steps, where each step has a different concentration ratio of NPB to Alq(3). Compared to a conventional heterojunction OLED, electroluminescence efficiency was enhanced by a factor of more than 1.5, whereas the turn-on voltage remained unchanged in the graded structure.

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment, D.A. Evans, H.J. Steiner, S. Evans, R. Middleton, T.S. Jones, S. Park, T.U. Kampen, D.R.T. Zahn, G. Cabailh and I.T. McGovern, J. Phys.: Condens. Matter, 15, S2729?S2740, (2003)

Novos compostos orgânicos reticuláveis para aplicações em células fotovoltaicas

Trabalho Final de Mestrado para obtenção do grau de mestre em Engenharia Química e Biológica

Demux devices based on A-SiC:H

In this paper we present results about the functioning of a multilayered a-SiC:H heterostructure as a device for wavelength-division demultiplexing of optical signals. The device is composed of two stacked p-i-n photodiodes, both optimized for the selective collection of photogenerated carriers. Band gap engineering was used to adjust the photogeneration and recombination rates profiles of the intrinsic absorber regions of each photodiode to short and long wavelength absorption and carrier collection in the visible spectrum. The photocurrent signal using different input optical channels was analyzed at reverse and forward bias and under steady state illumination. This photocurrent is used as an input for a demux algorithm based on the voltage controlled sensitivity of the device. The device functioning is explained with results obtained by numerical simulation of the device, which permit an insight to the internal electric configuration of the double heterojunction.These results address the explanation of the device functioning in the frequency domain to a wavelength tunable photocapacitance due to the accumulation of space charge localized at the internal junction. The existence of a direct relation between the experimentally observed capacitive effects of the double diode and the quality of the semiconductor materials used to form the internal junction is highlighted.

Signature optique d’effet Stark dans une bicouche de CuPc:C60

Les hétérojonctions formées de deux matériaux, un donneur et un accepteur (D/A), sont la base de la majorité des mélanges photovoltaïques organiques. Les mécanismes de séparation des charges dans ces systèmes représentent aujourd'hui l'un des sujets les plus chauds et les plus débattus dans ce domaine. Nous entrons au coeur de ce débat en choisissant un système D/A à base de phtalocyanine de cuivre (CuPc) et de fullerène (C60). Pour sonder les états excités de nos molécules et obtenir de l'information sur les phénomènes à l'interface D/A, nous réalisons une expérience pompe-sonde, appelée absorption photoinduite (PIA). Nous y mesurons le changement fractionnaire de transmission au travers de l'échantillon. Les mesures de PIA sont réalisées à l'état de quasi équilibre, à T=10K. Nous observons une modulation prononcée dans la région du photoblanchiment de l'état fondamental qui nous indique que la pompe induit un décalage du spectre d'absorption de l'état fondamental. Ce décalage peut être expliqué par deux processus : soit l'échantillon est chauffé par la pompe (effet thermique) ou bien des charges sont créées à l'interface entre les deux matériaux (effet Stark). La dépendance en température du spectre d'absorption entre 10K et 290K montre une signature thermique pour un changement de température de 80K. Grâce au ratio des raies Raman anti-Stokes et Stokes, nous démontrons que la pompe chauffe l'échantillon de 34 K, température insuffisante pour attribuer notre signal à un effet thermique. Nous évaporons ensuite la bicouche CuPc/C60 sur de l'ITO et du saphir, substrats qui possèdent des conductivités thermiques différentes et nous observons le même signal de PIA, excluant par le fait même l'hypothèse de l'effet thermique. Puisque notre étude est comparable à la spectroscopie à effet Stark, nous procédons à une analyse similaire en comparant notre signal de PIA au spectre de la transmittance et à ses dérivés première et seconde. Nous observons alors que notre signal reproduit presque parfaitement la dérivée seconde de la transmittance. Ces résultats sont conformes à une signature optique d'effet Stark due à la création de charges à l'interface D/A.

Preparation and characterisation of certain II-VI, I-III-VI2 semiconductor thin films and transparent conducting oxides

There is an increasing demand for renewable energies due to the limited availability of fossil and nuclear fuels and due to growing environmental problems. Photovoltaic (PV) energy conversion has the potential to contribute significantly to the electrical energy generation in the future. Currently, the cost for photovoltaic systems is one of the main obstacles preventing production and application on a large scale. The photovoltaic research is now focused on the development of materials that will allow mass production without compromising on the conversion efficiencies. Among important selection criteria of PV material and in particular for thin films, are a suitable band gap, high absorption coefficient and reproducible deposition processes capable of large-volume and low cost production. The chalcopyrite semiconductor thin films such as Copper indium selenide and Copper indium sulphide are the materials that are being intensively investigated for lowering the cost of solar cells. Conversion efficiencies of 19 % have been reported for laboratory scale solar cell based on CuInSe2 and its alloys. The main objective of this thesis work is to optimise the growth conditions of materials suitable for the fabrication of solar cell, employing cost effective techniques. A typical heterojunction thin film solar cell consists of an absorber layer, buffer layer and transparent conducting contacts. The most appropriate techniques have been used for depositing these different layers, viz; chemical bath deposition for the window layer, flash evaporation and two-stage process for the absorber layer, and RF magnetron sputtering for the transparent conducting layer. Low cost experimental setups were fabricated for selenisation and sulphurisation experiments, and the magnetron gun for the RF sputtering was indigenously fabricated. The films thus grown were characterised using different tools. A powder X-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive X-ray analysis (EDX) and scanning electron microscopy i (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UV-Vis-NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using the two probe and four probe electrical measurements. Nature of conductivity of the films was determined by thermoprobe and thermopower measurements. The deposition conditions and the process parameters were optimised based on these characterisations.

Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen