Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.

有机半导体中载流子迁移率的测量方法

本文简要地介绍了有机半导体中载流子迁移率的几种模型,着重阐述了测量有机半导体中载流子迁移率的各种方法的测试原理。主要有如下几种:稳态(CW)直流电流-电压特性法(steady-state DC JV),飞行时间法(time of flight,TOF),瞬态电致发光法(transient electroluminescence,transient EL),瞬态电致发光法的修正方法即双脉冲方波法和线性增压载流子瞬态法(carrier extraction by linearly increasing voltage,CELIV),暗注入空间电荷限制电流(dark injection space charge limited current,DI SCLC),场效应晶体管方法(field-effect transistor,FET),时间分辨微波传导技术(time-resolved microwave conductivity technique,TRMC),电压调制毫米波谱(voltage-modulated millimeter-wave spectroscopy,VMS)光诱导瞬态斯塔克谱方法(photoi...

Observation of persistent photoconductivity in vanadyl phthalocyanine

Persistent photoconductivity (PPC) in vanadyl phthalocyanine (VOPc) organic light-emitting diodes was investigated using photoconductive time response, photocurrent-voltage characteristics and charge extraction in linearly increasing voltage (CELIV) measurements. The experiments were performed in phase 1 (amorphous) and in phase 2 (crystalline) samples obtained by the physical vapour deposition (PVD) technique over ITO/glass electrodes with an Al covering electrode. The results indicated a photoconductivity with a long decay time in phase 1 VOPc described by a stretched exponential relaxation. The device showed a rectifying behaviour and the mobility of holes was measured by CELIV, following a dispersive model. In crystalline samples the PPC effect was not observed and the dominant mechanism of transport of holes was hopping in a Gaussian density of states.

Observation of persistent photoconductivity in vanadyl phthalocyanine

Persistent photoconductivity (PPC) in vanadyl phthalocyanine (VOPc) organic light-emitting diodes was investigated using photoconductive time response, photocurrent-voltage characteristics and charge extraction in linearly increasing voltage (CELIV) measurements. The experiments were performed in phase 1 (amorphous) and in phase 2 (crystalline) samples obtained by the physical vapour deposition (PVD) technique over ITO/glass electrodes with an Al covering electrode. The results indicated a photoconductivity with a long decay time in phase 1 VOPc described by a stretched exponential relaxation. The device showed a rectifying behaviour and the mobility of holes was measured by CELIV, following a dispersive model. In crystalline samples the PPC effect was not observed and the dominant mechanism of transport of holes was hopping in a Gaussian density of states.

Determination of carrier mobility in MEH-PPV thin-films by stationary and transient current techniques

Charge transport and shelf-degradation of MEH-PPV thin-films were investigated through stationary (e.g. current versus voltage - JxV) and transient (e.g. Time-of-Flight - ToF, Dark-Injection Space-Charge-Limited Current - DI-SCLC, Charge Extraction by Linearly Increasing Voltage - CELN) current techniques. Charge carrier mobility in nanometric films was best characterized through JxV and DI-SCLC. It approaches 10(-6) cm(2)Ns under a SCLC regime with deep traps for light-emitting diode applications. ToF measurements performed on micrometric layers (i.e. - 3 mu m) confirmed studies in 100 nm-thick films as deposited in OLEDs. All results were comparable to a similar poly(para-phenylene vinylene) derivative, MDMO-PPV. Electrical properties extracted from thin-film transistors demonstrated mobility dependence on carrier concentration in the channel (similar to 10(-7)-10(-4) cm(2)/Vs). At low accumulated charge levels and reduced free carrier concentration, a perfect agreement to the previously cited techniques was observed. Degradation was verified through mobility reduction and changes in trap distribution of states. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and photovoltaic performance of a fluorene-bithiophene copolymer

We present the synthesis of a copolymer structure, poly(9,9′-n-di-hexyl-2,7-fluorene-alt-2,5- bithiophene), referred to herein as LaPPS43, and its physico-chemical characterization. Thin films of this polymer mixed with phenyl-C61-butyric acid methyl ester (PCBM) were used as the active layer in photovoltaic devices using the ITO/PEDOT:PSS/LaPPS43: PCBM/Ca/Al bulk heterojunction structure. The devices of different active layer thicknesses were electrically studied using J-V curves and the Photo-Celiv technique. The obtained results show that LaPPS43 combined with PCBM is a promising system for photovoltaic devices. Device performance is discussed in terms of the mean drift distance x for charge carriers. Photophysical data showed that the excitonic species are all localized in the aggregated forms. The mechanism of exciton formation and dissociation is also discussed.

Perylene Diimide Molecular Glass: Investigations of Charge Transport

A new glass-forming organic semiconductor material was synthesized using a known electron transport material, perylene diimide, and attaching it to a molecular glass in order to allow the material to be solution processed. Devices were made using a simple metal-semiconductor-metal structure and electrodes were selected to produce Schottky diodes. Experiments were carried out to characterize this new molecular glass perylene diimide. The new material shows evidence of traps, hysteresis, and other behaviours that are explored in this thesis. The material shows some potential as an electron transport layer with possibilities of memory storage behaviour.

Undersökning av dopning i organiska dioder och solceller

Organiska solceller har gjort stora framsteg med avseende på effektivitet och stabilitet under det senaste årtiondet. Oavsiktlig dopning är ett ofta förekommande fenomen i organiska halvledare. Orenheter och defekter i halvledarmaterialet kan ge upphov till dopning. Dessutom kan organiska halvledare dopas över tid då de kommer i kontakt med syre eller fukt. I takt med att andra egenskaper optimeras och effektiviteten stiger blir dopningen en allt viktigare förlustprocess att ta i beaktande i organiska solceller. Målet med detta arbete har varit att bättre förstå dopningens inverkan på organiska dioder och solceller. Tanken var att med hjälp av två olika dopningsmolekyler åstadkomma avsiktlig dopning och på så sätt kontrollerat undersöka och skapa en bättre förståelse av hur dopningen påverkar egenskaperna hos organiska halvledare i dioder och solceller. För att undersöka dopningen har en mätmetod som baserar sig på laddningsextraktion med hjälp av en linjärt ökande spänning, kallad CELIV, använts. Teorin för mätmetoden har utvecklats för att analysera godtyckliga dopningsprofiler och för att ta i beaktande dopningsprofilen vid bestämning av mobiliteten. Metoden har, genom de experiment som utförts, bekräftats fungera väl för undersökning av dopning i organiska tunnfilmsdioder. De två dopningsmolekyler som använts har testats framgångsrikt för dopning av polymererna P3HT och PBTTT. Under arbetets gång kunde en viktig orsak till oavsiktlig dopning identifieras. Som selektivt håltransportlager vid anoden är molybdentrioxid ett av de mest använda materialen. I detta arbete visas att molekyler från ett tunt lager av molybdentrioxid diffunderar in i halvledarlagret och orsakar dopning. Dopningen i P3HT:PCBM till följd av ett molybdentrioxidlager är så hög att även tunna solceller, kring 100 nm, kommer att påverkas negativt på grund av ökad rekombination. Dopningen till följd av diffusion av molybdentrioxid är ett resultat som visar på ett behov att hitta nya alternativa material för håltransport. Ett alternativ kunde vara att använda kraftigt dopade organiska halvledare. För detta ändamål kan den avsiktliga dopning som här testats vara relevant. De experimentella resultat som ingår i denna avhandling bekräftar att CELIV-metoden lämpar sig väl för att mäta dopningskoncentration och dopningsprofiler i organiska dioder samtidigt som man kan erhålla information om laddningstransporten i halvledarlagret.