Band Alignments and Interfaces in Kesterite Photovoltaics

The kesterite materials, Cu2ZnSn(S,Se)4, represent a promising class of absorber materials, for cheap, earth-abundant, non-toxic photovoltaic cells. However, the record efficiency of a device based on these materials is only 12.6 %, compared to 15 % required for the material to be commercially viable and 22.6 % for the related chalcopyrite material, CIGS. In this thesis, we consider the architecture of a typical kesterite solar cell, from the back contact to the window layer and identify possible causes of the open-circuit voltage deficit, and how this deficit can be reduced. We begin by investigating the necessity for photovoltaics as a result of climate change, caused by our use of fossil fuels, and how the technology of photovoltaics has developed. We also consider the physical principles of photovoltaics and then discuss kesterite materials and architecture and compare them to chalcopyrites. Thus, we begin by investigating the photoelectron spectroscopy of kesterite materials obtained from different synthetic routes, and determine, the band alignments of kesterite/buffer interfaces by the Anderson electron affinity rule and the more reliable Kraut method. Using the results, it is shown that the band offsets between CdS and the kesterite materials considered in this work are inappropriate for high-efficiency photovoltaics. In contrast, In2S3 shows advantageous band offsets in all cases. Simulations are then used to compare the CdS and In2S3 devices Another limit on the efficiency of kesterite photovoltaics is the formation of the n-type Mo(S,Se)2 at the back contact. The formation of this layer typically results in the formation of a reverse diode, opposed to the main photodiode, thus increasing the recombination rate of the photoholes. However, in CdTe devices, Mo is often used as a back contact, which can result in the formation of an analogous MoTe2 layer which does not seem to have this effect. By considering the effects of Ar+ ion induced defects upon single crystals or multilayers exfoliated from a single crystal, the possible reasons why MoTe2 does not have the same effect as the Mo(S,Se)2 layer are investigated. We will also consider the uppermost layer of the photovoltaic cell, the window layer, which usually consists of a transparent conducting oxide (TCO). However, most of the widely-used TCOs have considerable issues, such as scarcity, cost, and self-compensating defects. Hence the final experimental chapter will consider an alternative TCO: Ga2O3. This material has a considerably larger band gap than that of the other TCOs, making it of interest for a wide range of applications Despite this widespread interest, fundamental properties of the material are still poorly understood. Thus, in the final chapter we begin by investigating the fundamental surface properties of a β-Ga2O3 single crystal with a (2 ̅01) surface termination and show that contrary to previous reports, the material exhibits surface accumulation. We also investigate the properties of several of the other polymorphs of Ga2O3 later in the chapter. This thesis concludes by considering the impact of these findings upon the future of kesterite photovoltaics and describe the likely future development of the material and its prospects for commercial deployment

Band alignments at Ga₂O₃ heterojunction interfaces with Si and Ge

Amorphous Ga2O3 thin films were deposited on p-type (111) and (100) surfaces of silicon and (100) germanium by atomic layer deposition (ALD). X-ray photoelectron spectroscopy (XPS) was used to investigate the band alignments at the interfaces using the Kraut Method. The valence band offsets were determined to be 3.49± 0.08 eV and 3.47± 0.08 eV with Si(111) and Si(100) respectively and 3.51eV± 0.08 eV with Ge(100). Inverse photoemission spectroscopy (IPES) was used to investigate the conduction band of a thick Ga2O3 film and the band gap of the film was determined to be 4.63±0.14 eV. The conduction band offsets were found to be 0.03 eV and 0.05eV with Si(111) and Si(100) respectively, and 0.45eV with Ge(100). The results indicate that the heterojunctions of Ga2O3 with Si(100), Si(111) and Ge(100) are all type I heterojunctions

Schottky Diodes on ZnO Thin Films Grown by Plasma-Enhanced Atomic Layer Deposition

Enhancement of the properties of zinc oxide (ZnO)-based Schottky diodes has been explored using a combination of plasma-enhanced atomic layer deposition (PE-ALD) ZnO thin films and silver oxide Schottky contacts deposited by reactive radio-frequency sputtering. The electrical properties of the ZnO thin films were systematically tuned by varying the deposition temperature and oxygen plasma time during PE-ALD to optimize the performance of the diode. Low temperature (80 °C) coupled with relatively long oxygen plasma time (>30 s) PE-ALD is the key to produce ZnO films with net doping concentration lower than 10 17 cm -3 . Under the optimal deposition conditions identified, the diode shows an ideality factor of 1.33, an effective barrier height of 0.80 eV, and an ON/OFF ratio of 3.11 × 10 5

Enhanced switching stability in Ta 2 O 5 resistive RAM by fluorine doping

The effect of fluorine doping on the switching stability of Ta2O5 resistive random access memory devices is investigated. It shows that the dopant serves to increase the memory window and improve the stability of the resistive states due to the neutralization of oxygen vacancies. The ability to alter the current in the low resistance state with set current compliance coupled with large memory window makes multilevel cell switching more favorable. The devices have set and reset voltages of <1V with improved stability due to the fluorine doping. Density functional modelling shows that the incorporation of fluorine dopant atoms at the two-fold O vacancy site in the oxide network removes the defect state in the mid bandgap, lowering the overall density of defects capable of forming conductive filaments. This reduces the probability of forming alternative conducting paths and hence improves the current stability in the low resistance states. The doped devices exhibit more stable resistive states in both dc and pulsed set and reset cycles. The retention failure time is estimated to be a minimum of 2 years for F-doped devices measured by temperature accelerated and stress voltage accelerated retention failure methods

The role of nitrogen doping in ALD Ta2O5 and its influence on multilevel cell switching in RRAM

The role of nitrogen doping on the stability and memory window of resistive state switching in N-doped Ta2O5 deposited by atomic layer deposition is elucidated. Nitrogen incorporation increases the stability of resistive memory states which is attributed to neutralization of electronic defect levels associated with oxygen vacancies. The density functional simulation with screened exchange hybrid functional approximation finds that the incorporation of nitrogen dopant atoms in the oxide network removes the O vacancy midgap defect states, thus nullifying excess defects and eliminating alternative conductive paths. By effectively reducing the density of vacancy-induced defect states through N doping, 3-bit multilevel cell switching is demonstrated, consisting of eight distinctive resistive memory states achieved by either controlling the set current compliance or the maximum voltage during reset. Nitrogen doping has a threefold effect; widening the switching memory window to accommodate more intermediate states, improving the stability of states, and providing gradual reset for multi-level cell switching during reset. The N-doped Ta2O5 devices have relatively small set and reset voltages (< 1 V) with reduced variability due to doping

Speech rhythm: a metaphor?

Is speech rhythmic? In the absence of evidence for a traditional view that languages strive to coordinate either syllables or stress-feet with regular time intervals, we consider the alternative that languages exhibit contrastive rhythm subsisting merely in the alternation of stronger and weaker elements. This is initially plausible, particularly for languages with a steep ‘prominence gradient’, i.e. a large disparity between stronger and weaker elements; but we point out that alternation is poorly achieved even by a ‘stress-timed’ language such as English, and, historically, languages have conspicuously failed to adopt simple phonological remedies that would ensure alternation. Languages seem more concerned to allow ‘syntagmatic contrast’ between successive units and to use durational effects to support linguistic functions than to facilitate rhythm. Furthermore, some languages (e.g. Tamil, Korean) lack the lexical prominence which would most straightforwardly underpin prominence alternation. We conclude that speech is not incontestibly rhythmic, and may even be antirhythmic. However, its linguistic structure and patterning allow the metaphorical extension of rhythm in varying degrees and in different ways depending on the language, and that it is this analogical process which allows speech to be matched to external rhythms

Low temperature growth and optical properties of alpha-Ga2O3 deposited on sapphire by plasma enhanced atomic layer deposition

Plasma enhanced atomic layer deposition was used to deposit thin films of Ga2O3 on to c-plane sapphire substrates using triethylgallium and O2 plasma. The influence of substrate temperature and plasma processing parameters on the resultant crystallinity and optical properties of the Ga2O3 films were investigated. The deposition temperature was found to have a significant effect on the film crystallinity. At temperatures below 200°C amorphous Ga2O3 films were deposited. Between 250°C and 350°C the films became predominantly α-Ga2O3. Above 350°C the deposited films showed a mixture of α-Ga2O3 and ε-Ga2O3 phases. Plasma power and O2 flow rate were observed to have less influence over the resultant phases present in the films. However, both parameters could be tuned to alter the strain of the film. Ultraviolet transmittance measurements on the Ga2O3 films showed that the bandgaps ranges from 5.0 eV to 5.2 eV with the largest bandgap of 5.2 eV occurring for the α-Ga2O3 phase deposited at 250°C

Reducing bias in auditory duration reproduction by integrating the reproduced signal

Duration estimation is known to be far from veridical and to differ for sensory estimates and motor reproduction. To investigate how these differential estimates are integrated for estimating or reproducing a duration and to examine sensorimotor biases in duration comparison and reproduction tasks, we compared estimation biases and variances among three different duration estimation tasks: perceptual comparison, motor reproduction, and auditory reproduction (i.e. a combined perceptual-motor task). We found consistent overestimation in both motor and perceptual-motor auditory reproduction tasks, and the least overestimation in the comparison task. More interestingly, compared to pure motor reproduction, the overestimation bias was reduced in the auditory reproduction task, due to the additional reproduced auditory signal. We further manipulated the signal-to-noise ratio (SNR) in the feedback/comparison tones to examine the changes in estimation biases and variances. Considering perceptual and motor biases as two independent components, we applied the reliability-based model, which successfully predicted the biases in auditory reproduction. Our findings thus provide behavioral evidence of how the brain combines motor and perceptual information together to reduce duration estimation biases and improve estimation reliability

Core Levels, Band Alignments, and Valence-Band States in CuSbS2 for Solar Cell Applications

The earth-abundant material CuSbS2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa(1–x)Se2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies