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Technology

Static, transient or modulated light excitation pro and con

Static, transient or modulated light excitation pro and con The time-resolved or frequency-modulated, surface photovoltage spectroscopy (SPS) is based on a time-resolved/frequency modulated measurement of the spectral dependence of the surface photovoltage (SPV). It is a powerful non-destructive and contactless characterization method. It is mainly used to study the electronic transitions and optical properties of bulk materials, thin films and heterostructures. High sensitivity and the possibility of room temperature measurements are the key advantages of the SPV method. Another advantage is that there is no need for the preparation of a front contact on the investigated sample. In general, there is no need for preparing the sample for the measurement, allowing to investigate the sample under operation/process conditions in a wide temperature range under different atmospheric conditions. The information depth and thereby the possibility to extract bulk properties is limited by the lights penetration depth and the diffusion length. In comparison to other spectroscopic methods, such as but not limited to optical transmission, deep level transient spectroscopy, photoluminescence or Raman spectroscopy, the time-resolved/frequency modulated SPS or SPV (fixed wavelength) method is fast and uncomplicated and is thus an ideal tool for production floor decisions of sample quality. We distinguish between 3 different excitation modes, but common to all of them is that the relaxation aspect of states in the samples are resolved under ideal conditions. A static SPV measurement is sensitive to any fast or slow process that lead to the separation of photogenerated carriers in space. The sample is illuminated until a saturation of the SPV signal is observed, after which the light is switched of. Measuring 1) the static SPV signal and 2) the time-resolved relaxation time gives a lot of useful information about the state of the material. A SPV measurement that is performed under modulated illumination in a fixed capacitor arrangement is very sensitive to small changes in the SPV signal. And, only those SPV signals, which can follow the modulation frequency are contributing to the measured signal. The response of processes with relaxation times much longer than the modulation period are simply filtered out. The most sensitive SPV measurement that can be made is a transient measurement, where illumination pulse of different pulse width are followed by a time dependent measurement of the decay of the SPV signal – in this way charge separation distances in the nanometre range can be investigated. This is particular important for surface or tunnelling dominated processes in the material. Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more DPM series DPM100 Wide range double prism monochromator Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Technology

SPV-Picts SPV temperature dependence measurements

SPV-Picts SPV temperature dependence measurements Use this option to make SPV measurements at different temperatures between room temperature and 200°C. Temperature-dependent SPV measurements can be applied to measure activation energies or to investigate temperature dependent reactions/processes in situ. As an example heeling or introduction of defects at surfaces or in the bulk can be investigated in this way. For wide-bandgap semiconductors the onset energy of the SPV signal associated with the bandgap edge is normally not sharp and well defined. By varying the temperature, the onset energy can be measured at different temperatures, resulting in a better estimation of the bandgap edge energies. Some photocatalytic materials have engineered defect states that accelerate the separation of charges. In a high-volume production setup of photocatalytic materials with engineered defect states, the control plan for the activity of the defect states is critical-to-yield. By varying the temperature over a relatively narrow range (say 10°C), the activity can be efficiently tested. Furthermore, the photocatalyst material need to work over broad range of temperatures. This makes the SPV-Picts option almost indispensable for any research programme aiming to develop efficient photocatalytic materials. Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more DPM series DPM100 Wide range double prism monochromator Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Technology

Materials

Materials Any photoactive material from raw material to finished device: From powder-based samples over wafers to boules or ingots. From 10 x 10 mm 2 and up to 300 mm diameter From titanium dioxide over silicon and to aluminium nitride (1000+ materials) Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more DPM series DPM100 Wide range double prism monochromator Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Technology

Software - SPS Studio

Software - SPS Studio Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Application

Defects and charge dynamics in 3C- and 4H-SiC investigated by surface

Defects and charge dynamics in 3C- and 4H-SiC investigated by surface Photoelectrochemical (PEC) and photocatalytic (PC) water splitting for hydrogen and/or oxygen generation is leading the way not only to green hydrogen production, but also to oxygen generators working solely on water basis. The quest for stable materials that can work with solar light as a basis has identified two superior photoactive material candidates, namely silicon carbide (SiC) and copper oxide (Cu 2 O) materials, based on a number of criteria such as cost, abundancy, toxicity and sustainability. The optimum photoelectrical conversion electrode is often a very complex system, where the focus is on a very fast separation of the generated charges in order to increase the current densities out of the cells. The charge dynamics of the complex systems, be it on SiC, Cu 2 O or any other photoactive material, can best be measured using time resolved surface photovoltage spectroscopy/measurements. The SPVcheck tool is again the optimum choice, because it can be configured in a flexible way concerning sample geometry and energy selection range. A 2 UV/VIS light source (480 and 660 nm) approach can give a lot information about the charge dynamics in the photoelectrode and can be used to check the quality of the photoelectrical conversion electrodes in a high-volume production setup. 4H-SiC under UV light 3C-SiC under normal light (solar spectrum) Related Solutions and Industries: Epitaxial Layers & Thin Films Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Application

Defects in 4H-SiC

Defects in 4H-SiC Investigated by surface photovoltage spectroscopy Defects in 4H-SiC investigated by surface photovoltage spectroscopy – power semiconductors Silicon carbide (SiC) high power, high voltage semiconductor devices lead the way not only for superfast chargers and on-board chargers for electrical vehicles (EV), but also power drive trains and power converters for traction applications such as light rails, trams and subways. Traction applications, as well as industrial motor drives, require power semiconductor switches with blocking voltages of 1200 V, 1700 V, 3300 V or even 4500 V (6500 V is still being explored). Reliability, lifetime and safety of the high power, high voltage semiconductor devices are the key parameters to control at the moment, where the commercially available 150 mm SiC wafers still suffer from some fundamental quality issues related to defects in bandgap of the SiC semiconductor. These issues will still remain on 200 mm SiC wafers, and it is therefore of extreme importance to be able to measure and report the state of the defects before, during and after device fabrication. The SPVcheck tool equipped with 3 UV light sources with centre wavelengths 355 nm, 365 nm and 450/660 nm is the ideal platform for epitaxial SiC wafer characterization, because it can be used to check the fundamental bandgap edge in a very elegant and fast way. The 450 nm or 660 nm wavelength is used as a baseline reference measurement, because the energy is too low to excite carriers in the SiC material. The 355 nm and 365 nm UV light sources are applied at the same time to the epitaxial SiC wafer, thereby creating a broad square like pulse covering energies in 3.25 to 3.55 eV in one shot. The transient SPV is measured in the time range from 10 ns and up to 10 ms. If the epitaxial layer on the SiC wafer has too many defects, the excitation of carriers will be weakened and the change in signal over time will be smaller. A perfect epitaxial layer, on the other hand, will have a higher output signal and, more importantly, sharp energy transition peaks in the ms range. An additional advantage of the square like energy pulse is the fact that the absorption coefficient of SiC is growing linearly with the square of the energy and is heavily temperature dependent. Therefore, by adding a temperature stage, the penetration depth of the UV light can be varied over a large range. Obviously the 355 nm and the 365 nm light sources does not need to switched on at the same time – they can be switched on and off in a modulated pattern with up to 1 kHz switching frequency or very long on and off cycles. Perfect 4H-SiC; Such a sharp transition will generate a large time-resolved signal change, probably around 10-100 µs 4H-SiC with defects; no sharp transitions will result in a small time-resolved signal change, probably < 1 µs Related Solutions and Industries: Epitaxial Layers & Thin Films Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Application

Contactless characterization of SiC, GaN and AlGaN

Contactless characterization of SiC, GaN and AlGaN Aim SiC, GaN and AlGaN belong to the class of wide band gap semiconductors and are applied especially in power electronics, optoelectronic devices and transistors such as HEMTs (high electron mobility transistor. The contactless optoelectronic characterization of wide band gap semiconductors and heterostructures under production conditions and in fields of R&D is often challenging. Solution SPV spectroscopy in the dc (Kelvin probe, measurement of the contact potential difference, DCPD) and ac (modulated) modes provides information about preferential directed charge separation in relation to electronic transitions and carrier dynamics [1]. The application of charge amplifiers allows for SPV measurements in dc and ac modes with the same electrode. Application example Figure 1 shows DCPD spectra of GaN, Al 0.25 Ga 0.75 N/GaN and 4h-SiC/GaN deposited onto sapphire wafers. Aside directions of charge separation and transition energies at band gaps, defect transitions can be distinguished. Signatures of slow processes can be discriminated in modulated SPV measurements (figure 2). References [1] Th. Dittrich, S. Fengler, “Surface photovoltage analysis of photoactive materials”, World Scientific, 2020. [2] Th. Dittrich, S. Fengler, N. Nickel, “Surface photovoltage spectroscopy over wide time domains for semiconductors with ultrawide bandgap: example of gallium oxide”, Phys. Stat. Sol. A 11 (2021) 2100176. Fig. 1: DCPD spectra of GaN (blue), Al0.26Ga0.74N / GaN (green) and 4h-SiC / GaN (red) epitaxial layers deposited on sapphire. Fig. 2: Modulated in-phase and phase-shifted by 90° SPV spectra of GaN (a), 4h-SiC / GaN (b) and Al0.26Ga0.74N / GaN (c). Related Solutions and Industries: Epitaxial Layers & Thin Films Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Application

Study and monitoring of photocatalytic materials (TiO2)

Study and monitoring of photocatalytic materials (TiO2) Aim Photocatalytic materials such as TiO 2 are of great interest, for example, for cleaning of industrial wastewater and for water splitting. The identification of directed charge transfer is important for deeper understanding of the role of defect states, defect bands and doping as well as for technology control. Solution SPV spectroscopy in the dc (Kelvin probe, measurement of the contact potential difference, DCPD) and ac (modulated) modes provides information about preferential directed charge separation [1] and allows the investigation of the influence doping on band bending, recombination losses and scavengers (entities accepting electrons or holes) at surfaces. Application example It was shown that TiO 2 can be doped n- and p-type by thermal treatment in reducing or oxidizing atmosphere (figure 1, more in [2]). Figure 2 shows the deposition temperature dependence of defect and band gap transitions in TiO 2 after deposition by cold gas spraying of TiO 2 powder (more in [3]). The evolution of defect bands in TiO 2 caused by incorporation, of nitrogen and their effect on charge transfer was studied in [4]. References [1] Th. Dittrich, S. Fengler, “Surface photovoltage analysis of photoactive materials”, World Scientific, 2020. [2] M. K. Nowotny, et al., „Observation of p-type semiconductivity in titanium dioxide at room temperature”, Materials Letters 64 (2010) 928. [3] I. Hermann-Geppert, et al., „Cold gas sprayed TiO 2 -based electrodes for the photo-induced water oxidation”, ECS Transactions 58 (2014) 21. [4] R. Beranek, et al., „Exploring the electronic structure of nitrogen-modified TiO 2 photocatalysts through photocurrent and surface photovoltage studies”, Chem. Phys. 339 (2007) 11. Fig. 1: 1st (thick) and 2nd (thin) DCPD spectra of reduced (red) and oxidized (blue) TiO2 (rutile). Band gap and defect states marked. Data partially after [2]. Fig. 2: Modulated SPV spectra of cold gas sprayed TiO2 for different temperatures. Data partially after [3]. Related Solutions and Industries: Epitaxial Layers & Thin Films Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Application

Investigation of photocatalytic materials (BiVO4)

Investigation of photocatalytic materials (BiVO4) Aim Photocatalytic materials such as BiVO 4 are of great interest, for example, for water splitting. Electronic defect states and surface passivation are important limiting factors. Photocatalytic materials can be applied as powders, porous layers or thin films what makes a simple and contactless photoelectric characterization of such materials still challenging. Solution SPV spectroscopy in the dc (Kelvin probe, measurement of the contact potential difference: DCPD) and ac (modulated) modes is a contactless and highly sensitive method allowing to detect very low SPV signals related to charge separation under excitation of defect states for powder, porous and thin film samples [1]. Application example Figure 1 shows spectra of the modulated SPV amplitude for a BiVO 4 thin film, porous layer and powder (see also [2]). The onset of the band gap of BiVO 4 (2.5 eV), the energy parameters of exponential tails and transitions related to defects can be well measured. Figure 2 shows DCPD spectra of porous BiVO 4 layers decorated with V 13 O 15 with and without a passivating cobalt phosphate (Co-Pi) cocatalyst (see also [3]). References [1] Th. Dittrich, S. Fengler, “Surface photovoltage analysis of photoactive materials”, World Scientific, 2020. [2] S. Fengler, et al., „Characterization of BiVO 4 powders and cold gas sprayed layers by surface photovoltage techniques“, Catalysis Today 321 (2019) 34. [3] H. Ren, et al., „Manipulation of charge transport by metallic V 13 O 16 decorated on bismuth vanadate photoelectrochemical catalyst“, Adv. Mater. (2019) 1807204. Fig. 1: Viewgraphs and spectra of the modulated SPV amplitudes for a BiVO4 thin film (black), porous layer (red) and powder (blue). Band gap is marked. Fig. 2: DCPD spectra of porous BiVO4 layers decorated with V13O15 with (red) and without (blue) a cobalt phosphate cocatalyst. Related Solutions and Industries: Epitaxial Layers & Thin Films Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com

Application

Silicon photovoltaic – Wafer check after diamond wire sawing

Silicon photovoltaic – Wafer check after diamond wire sawing Diamond wire sawing (DWS) is an established technology for wafering semiconductor ingots, as it has many advantages over other technologies, such as of slurry cutting. Some of these advantages include faster cutting speeds with higher cutting efficiency, production of thinner wafers with improved thickness uniformity, easier way to filter silicon debris for slurry recycling (if desired), and use of cutting wire for more than one cut. Diamond wire sawing uses a long (hundreds of kilometres) wire, impregnated with diamond flakes (grit) as a cutting medium. The cutting wire is made up of a stainless-steel core (80– 120 µm in diameter) that is coated with diamond flakes (8–25 µm in size) which are then bonded to the wire by a layer of electroplated Ni or a layer of a resin material. The as-sawn DWS wafer might look perfect to the naked eye, but the diamond wire and the strategy of moving the diamond wire through the ingot (speed and reciprocation), has a high impact on the quality of the as-sawn wafers as well as subsequent processes such as lapping, grinding or etching. For PV wafers in particular, there can be a huge difference in the sub surface damage over the as-sawn square wafer and this needs to be accounted for in the damage etch and texturing etch process step that proceeds the DWS process. SPV spectroscopy using the HR-SPS tool provides direct information about the quality of the as-sawn wafers – it can be used to find areas of wire snap-off, wire reciprocation and also provide a map with relation to subsurface damage depth. It is contactless and fast, allowing for an integration of the tool into a process line QC control of as-sawn wafers. Below is a shown an example for a 156 x 156 mm 2 pseudo square DWS PV wafer (n-type monocrystalline, 1-3 Ohm-cm). Figure 1 shows maps of the SPV height across the n-type PV wafer by illuminated with three different photons energies – the penetration depths of the photons into the wafer is approximately 0.1, 10 and 100 mm, respectively. Also shown are the relaxation time constant across the wafer – defined as the logarithmic SPV signal transient decay time after turning off the light. It is clear from the SPV maps (left side) that the wafer has varying degrees of subsurface damage across the wafer; the top part has more subsurface damage than the bottom part and the periphery also has more damage. This is to be expected because of the force of the wire is higher at the periphery of the ingot to be sawn. In the relaxation maps (right side), there is a distinct zone below the centre of the wafer towards the bottom. This distinct centre has a lower than expected relation time (-10%) and this probably marks the reciprocation process start. The SPV and relaxation maps complement each other and give a fingerprint of the state of the as-sawn PV wafer. Fig. 1. SPV maps (right) and relaxation time maps (left) for the same DWS wafer and illuminated with three different energies (wavelengths) Related Solutions and Industries: Epitaxial Layers & Thin Films Matching Products SPS/SPV series HR-SPSmap with fixed energy excitation sources High-Resolution and Sensitive Surface Photovoltage Measurement Solutions Learn more SPS/SPV series HR-SPSmap with variable energy excitation source with a variable energy excitation source Learn more Get in touch Do not hesitate to contact us – we are available to assist you with any inquiries or requests. Use our inquiry tool or reach out via email: sales @ freiberginstruments.com