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The aim of this work is to study the optical properties of crystal defects in multicrystalline solar silicon and poly-/microcrystalline silicon thin films on glass substrate.
First a setup for photoluminescence imaging on multicrystalline silicon solar wafers was developed. This system is suitable for detecting band-to-band luminescence as well as defect-related luminescence at room temperature on large-scale wafers at different stages of their processing.
Spectroscopic photoluminescence investigations of multicrystalline silicon solar wafers indicated a new intense luminescence line at ≈ 0.91 eV at room temperature. The origin of this line is probably found in a specific grain boundary. Furthermore, luminescence in the region of 0.8 eV was investigated in detail, and it was found that probably oxygen is responsible for a peak at 0.77 eV at 80 K.
Electroluminescence investigations at room temperature at both materials exhibit extended defect structures such as grain boundaries. Furthermore, it can be concluded that electroluminescence imaging in reverse bias mode indicate on serious breakdown points in solar cells, which can lead to destruction of solar cells and modules. By comparing defect-related and reverse bias electroluminescence images, a difference in the spatial distribution of defects emitting D1 radiation and defects emitting light under reverse bias beyond -12 V is detectable.
In addition, there seems to be a correlation in the distribution of non-doping impurities and photoluminescence. Concerning this, vertical slabs of two silicon blocks were examined by means of Fourier-transform infrared spectroscopy and photoluminescence. A correlation of the distributions of interstitial oxygen and the band-to-band luminescence profiles could be found. Additionally, a correlation between D3/D4 luminescence profile and nitrogen distribution in the blocks was observed.
Finally, the growth process, particularly the transition from amorphous to microcrystalline silicon by PECVD, was studied by combined photoluminescence and Raman investigations. Formation of silicon nano-grains was detected by means of photoluminescence and Raman spectroscopy.
The aim of this work is to describe and explain the properties of defects in multicrystalline (mc) and thin-film solar silicon (Si). For this reason, investigations with scanning electron microscope methods were performed, namely cathodoluminescence (CL), electron beam induced current (EBIC), electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). Additionally, photoluminescence (PL) and reverse-biased electro luminescence (ReBEL) measurements were also conducted. Through correlation of PL, ReBEL and EBIC, it was possible to localize breakdown sites at mc-Si solar cells. Problems that occurred during the thin-film EBIC investigations could be demonstrated and explained. For the first time cross sectional EBIC investigations could be performed on thin-film silicon tandem cells. At mc-Si, it was possible to observe the oxygen related P-line next to the common D1-line luminescence at 10 K clearly distinguishable from each other at once. Furthermore, a hitherto not comprehensively discussed intense luminescence line at 0.93 eV could be described in detail. Through correlation of PL, CL, EBIC, EBSD, and TEM measurements, the origin of the now named Di luminescence at 0.93 eV is postulated to be in connection with Frank partial dislocations, with two energetic levels inside the band gap, one at 112±9 meV below the conduction band and the other at 93±10 meV above the valence band. Finally, it was attempted to explain the behavior of twin boundaries at temperatures below 30 K, where these show an enhanced collection efficiency in comparison to the surrounding grains. An alteration of the local “freeze out” temperature, possibly by a local band gap narrowing, is suggested as a reason. Another conceivable explanation is a breakdown of the diode potential at the grains.
Current memory technologies, such as DRAM, SRAM, and NAND Flash, which are approaching very difficult issues related to the continuous scaling to and beyond the 16 nm generation, has led research over the past two decades to the discovery of several new memory technologies. In recent years, new emerging nonvolatile memories (NVMs), such as phase-change random access memory (PCRAM), ferroelectric random access memory (FRAM), magnetic random access memory (MRAM), and resistive random access memory (RRAM), have been intensively studied. Among these candidates, RRAM is a very promising and worldwide studied candidate for alternative NVM and a high potential successor for Flash in terms of energy consumption (write current in the μA range compared to mA) and simplicity of process integration.
A fully CMOS compatible TiN/Ti/HfO2/TiN RRAM module was successfully integrated with a select transistor (1T1R memory) in IHP’s technology. Nonetheless, reliability and insufficient understanding of the resistive switching mechanism are the two main issues limiting this memory technology development for e.g. wireless sensor network (WSN) applications. The still unclear atomic-scale mechanism of HfO2-based resistive switches and the identification of the material changes within the insulator must be addressed to suggest a knowledge-based improvement of device performance. In this frame, the Ti/HfO2 interface is thoroughly investigated in this Thesis by complementary materials science techniques.
First, the investigation of the as-deposited Ti/HfO2/TiN cells revealed that: (1) the Ti layer scavenges oxygen atoms stronger from amorphous (a-HfO2) than from monoclinic (m-HfO2) HfO2 films; (2) not only oxygen vacancies but also other impurities in the atomic vapor deposited (AVD) a-HfO2 film, such like nitrogen and carbon (probably resulting from the used AVD precursor chemistry) are present in the HfO2 insulator.
Next, the electrical characterization of Ti/AVD a-HfO2/TiN cells (with voltage applied to the Ti top electrode while TiN bottom electrode was grounded) revealed a clockwise bipolar resistive switching behavior after an electroforming process at positive voltage polarity. Besides, the chemical and electronic changes observed by hard X-ray photoelectron spectroscopy (HAXPES), indicate the creation of n-type dopants in the a-HfO2 film during the electroforming process, probably related to the formation of positively charged oxygen vacancies in a-HfO2 by the electrochemically induced Ti/a-HfO2 interface oxidation.
In order to directly compare electrical with electronic and chemical changes of one and the same RRAM cell, an in-operando HAXPES technique was developed. These unique studies have revealed the following characteristics of the Ti/AVD a-HfO2/TiN cells: (1) the as-deposited cells are able to switch at low electrical power; (2) However, this resistive switching is not stable and an electroforming process with a slightly increased power is required to stabilize the switching event; (3) Electrical changes correlated with HAXPES results and literature indicate that (i) the forming/set electrical power defines the oxygen vacancies concentration in the a-HfO2 and thus the stability of the resistive switching properties and (ii) the stable resistive switching can be described by a push-pull model of oxygen vacancies migration under the influence of an electrical field; (4) Besides, carbon segregation at the Ti/a-HfO2 interface – while increasing the electrical power or cycling the device – shows that the defects physics is not limited only to oxygen vacancies; other defects may thus contribute under electrical stress to the resistive switching phenomenon and need to be included in theoretical models to correctly describe the switching characteristics.
Finally, according to the presented HAXPES results, the Ti/AVD a-HfO2/TiN RRAM cells are classified to the valence change mechanism. The resistive switching mechanism is attributed to the creation and rupture of oxygen vacancies-based conducting filaments and the Ti/HfO2 interface oxidation is of central importance for the defect balance of the RRAM cell. Most importantly, a reduction of carbon content in the AVD-deposited HfO2 improved the reliability of these memory cells.