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At least 595 records · Page 33

Nanoshell quantum dots: Quantum confinement beyond the exciton Bohr radius

Nanoshell quantum dots (QDs) represent a novel class of colloidal semiconductor nanocrystals (NCs), which supports tunable optoelectronic properties over the extended range of particle sizes. Traditionally, the ability to control the bandgap of colloidal semiconductor NCs is limited to small-size nanostructures, where photoinduced charges are confined by Coulomb interactions. A notorious drawback of such a restricted size range concerns the fact that assemblies of smaller nanoparticles tend to exhibit a greater density of interfacial and surface defects. This presents a potential problem for device applications of semiconductor NCs where the charge transport across nanoparticle films is important, as in the case of solar cells, field-effect transistors, and photoelectrochemical devices. Furthermore, the morphology of nanoshell QDs addresses this issue by enabling the quantum-confinement in the shell layer, where two-dimensional excitons can exist, regardless of the total particle size. Such a geometry exhibits one of the lowest surface-to-volume ratios among existing QD architectures and, therefore, could potentially lead to improved charge-transport and multi-exciton characteristics. The expected benefits of the nanoshell architecture were recently demonstrated by a number of reports on the CdS bulk /CdSe nanoshell model system, showing an improved photoconductivity of solids and increased lifetime of multi-exciton populations. Along these lines, this perspective will summarize the recent work on CdS bulk /CdSe nanoshell colloids and discuss the possibility of employing other nanoshell semiconductor combinations in light-harvesting and lasing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable random lasing in CdSSe micropowders

The random lasing in CdS micropowder in the green region (near 520 nm) at room temperature under optical pumping by pulsed Nd{sup 3+} : YAG and N{sub 2} lasers at wavelengths of 355 and 337 nm, respectively, is studied. The influence of fluctuations of pump pulse output energy on the random lasing action in CdS micropowder is determined. It is shown that the use of a pump laser with highly stable output power and high spatial beam uniformity (in particular, an N{sub 2} laser) provides stable random lasing in CdSSe micropowders. The lasing is characterised by the presence of a clear structure of narrow lines in the spectrum and stability of their position during pulsed operation at a repetition rate of 700 Hz at wavelengths of 525, 570, 600, and 650 nm with thresholds in the range of 1100 – 1600 kW cm{sup −2}. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Spectroscopic elucidation of energy transfer in hybrid inorganic–biological organisms for solar-to-chemical production

We present that the rise of inorganic–biological hybrid organisms for solar-to-chemical production has spurred mechanistic investigations into the dynamics of the biotic–abiotic interface to drive the development of next-generation systems. The model system, Moorella thermoacetica–cadmium sulfide (CdS), combines an inorganic semiconductor nanoparticle light harvester with an acetogenic bacterium to drive the photosynthetic reduction of CO 2 to acetic acid with high efficiency. In this work, we report insights into this unique electrotrophic behavior and propose a charge-transfer mechanism from CdS to M. thermoacetica. Transient absorption (TA) spectroscopy revealed that photoexcited electron transfer rates increase with increasing hydrogenase (H 2 ase) enzyme activity. On the same time scale as the TA spectroscopy, time-resolved infrared (TRIR) spectroscopy showed spectral changes in the 1,700–1,900-cm -1 spectral region. The quantum efficiency of this system for photosynthetic acetic acid generation also increased with increasing H 2 ase activity and shorter carrier lifetimes when averaged over the first 24 h of photosynthesis. However, within the initial 3 h of photosynthesis, the rate followed an opposite trend: The bacteria with the lowest H 2 ase activity photosynthesized acetic acid the fastest. These results suggest a two-pathway mechanism: a high quantum efficiency charge-transfer pathway to H 2 ase generating H 2 as a molecular intermediate that dominates at long time scales (24 h), and a direct energy-transducing enzymatic pathway responsible for acetic acid production at short time scales (3 h). Lastly, this work represents a promising platform to utilize conventional spectroscopic methodology to extract insights from more complex biotic–abiotic hybrid systems.

14 SOLAR ENERGY↗

Current enhancement of CdTe-based solar cells

We report on the realization of CdTe solar cell photocurrent enhancement using an n-type CdSe heterojunction partner sputtered on commercial SnO 2 /SnO 2 :F coated soda-lime glass substrates. With high-temperature close-space sublimation CdTe deposition followed by CdCl 2 activation, this thin-film stack allows for substantial interdiffusion at the CdSe/CdTe interface facilitating a CdSe x Te 1-x alloy formation. The bowing effect causes a reduced optical bandgap of the alloyed absorber layer and, therefore, leads to current enhancement in the long-wavelength region and a decrease in open-circuit voltage (V OC ). To overcome the V OC loss and maintain a high short-circuit current (J SC ), the CdTe cell configuration has been modified using combined CdS:O/CdSe window layers. The new device structure has demonstrated enhanced collection from both short-and long-wavelength regions as well as a V OC improvement. With an optimized synthesis process, a small-area cell using CdS:O/CdSe window layer showed an efficiency of 15.2% with a V OC of 831 mV, a J SC of 26.3 mA/cm 2 , and a fill factor of 69.5%, measured under an AM1.5 illumination without antireflection coating. Furthermore, the results provide new directions for further improvement of CdTe-based solar cells.

14 SOLAR ENERGY↗

Transmission Electron Microscopy Study on Microstructure of Degraded CdTe Mini-Modules

In this paper, we employ transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (EDS) to study the structure and chemistry of cadmium telluride (CdTe) thin-film solar cells with different extents of degradation. The studied regions originate from the same photovoltaic mini-module, which was subjected to one-sun light exposure at a temperature of 100 degrees C for 400 h to induce light and heat degradation. EDS maps reveal a discontinuous CdS layer and particles rich in O and S but Te-depleted within the CdTe absorber layer after the light and heat stress. These features could act as enhanced recombination centers, resulting in decreased photovoltaic conversion efficiency. Additionally, the most degraded CdTe sample shows a strong accumulation of Na precisely localized in the discontinuous part of the CdS layer. The local Na concentration is determined to be ~16 at.%. In addition, appreciable Na accumulation is observed at the soda-lime glass/transparent conductive oxide interface in both degraded CdTe solar cells. The microstructure of the baseline CdTe mini-module with no stress was also investigated to demonstrate that the structure difference was caused by the light- and heat-induced degradation, instead of module fabrication. These results highlight the need to control the distribution of Na in fielded CdTe modules to sustain long-term high-power output.

14 SOLAR ENERGY↗

Decoupling Thin Film CdTe Growth from Packaging: Toward Record Specific Power in Low Cost Polycrystalline PV

There are critical material and scientific barriers to producing high efficiency, flexible, lightweight solar cells that maximize specific power in a cost-effective manner. III-V solar cells have produced the highest specific power of any photovoltaic technology due to their extremely high efficiency, however, they are also among the most expensive to produce. This work explores a novel lift-off approach with thin-film solar cells, particularly CdTe, to achieve high specific power at low costs. Thin-film devices can be delaminated from their heavy, glass growth substrates post-growth by exploiting a mismatch in coefficient of thermal expansion between the two. This allows thin-film PV to be decoupled from high temperature growth requirements and repackaged using lightweight materials. In this work we evaluate different materials and approaches for achieving large area delamination of CdTe films from their glass superstrates. It is found that epoxy bonded to a rigid handle provides robust and reproducible delamination at the TCO/CdS interface upon submersion in liquid nitrogen. Following delamination, a transparent front contact is re-deposited and selectively etched to expose the back contact to produce a functioning device. Effects of delamination and contributions to device functionality from CdCl 2 and CdS layers are discussed. Reproducible delamination of high efficiency, thin-film solar cells over large areas will enable work to further improve device efficiency through passivation and reconstruction of the previously buried interface between the transparent contact and CdS.

14 SOLAR ENERGY↗

Alloy Loss Mitigation Through Use of Barrier Layers During CdCl2Processing of Cd0.60Zn0.4Te and Cd0.87Mg0.13Te

The main obstacle to realizing the use of polycrystalline wide bandgap alloys of CdTe with Mg and Zn in PV is the CdCl 2 processing step. This step, essential to CdTe device performance, removes Zn and Mg from the alloy films while producing less of the benefits seen from the process with CdTe. In this study, the use of Al 2 O 3 CdS, and MgZnO films at the free surface of the alloys to prevent loss of Mg or Zn is investigated. It is found that Al 2 O 3 is the most effective at reducing loss of Mg and Zn, followed by CdS and then MgZnO. A new method of evaluating the transition to CdTe from the as deposited alloy is proposed to account for differences in transition behaviors.

14 SOLAR ENERGY↗

Comparative operando XPS studies of quasi-Fermi level splitting and open-circuit voltage in CZTSe/CdS and CIGS/CdS junctions and device structures

This contribution describes operando x-ray photoelectron spectroscopy (opXPS) studies of Cu(In,Ga)Se 2 (CIGS) and Cu 2 ZnSnSe 4 (CZTSe) absorber layers and device structures. X-ray-excited valence-band and core-level spectra were acquired on bare absorber surfaces and after CdS and ZnO:Al depositions in standard absorber/CdS/ZnO/ZnO:Al device stacks. OpXPS data sets were acquired at various x-ray fluxes, with and without white-light illumination. From these measurements, quasi-Fermi level splitting (ΔE F ) values in the absorber/CdS junctions were measured directly as a function of excitation conditions. For both CIGS and CZTSe, results show that ..delta..EF proportional to the full open-circuit voltage (V OC ) of the completed devices is present after the deposition of the CdS layer - i.e., E F = qV OC - demonstrating that the so-called V OC deficit in CZTSe solar cells is also present at this stage of processing. The authors find that photoexcitation due to x-rays or stray visible light during XPS or similar measurements can produce measurable photovoltages in materials, absorber/CdS junctions, and finished devices. In situ current density versus voltage measurements on a typical CIGS device reveal that x-ray-induced photoexcitation associated with typical XPS measurement conditions is equivalent to ~3 x 10 -3 suns, which in this study produced V OC = 440 mV. These findings demonstrate that accounting for photoexcitation conditions during XPS or similar measurements can improve band-offset determinations and produce more reliable values for the junction built-in voltage. The implications of the study findings on the CZTSe V OC deficit and device performance are discussed.

36 MATERIALS SCIENCE↗

Optical properties of alloys based on II-S and II-Te chalcogenides

Spectroscopic studies of binary and multicomponent semiconductors of the CdS-CdTe, CdS-ZnTe, and ZnS-CdTe systems are performed. They result in confirmation of the formation of substitutional alloys in these systems (in addition to the results of X-ray diffractometry studies), and the chemical composition of the surface as well as the most important characteristic of semiconductors, theelectron work function, the frequencies of strongest luminescence (impurity and band-to band), the emission maxima, and the possibilities of predicting luminescence properties are determined. Recommendations concerning the use of fabricated materials of definite composition as phosphors are given.

36 MATERIALS SCIENCE↗

Surface-barrier photoconverters with graded-gap layers in the space-charge region

A novel possibility of controlling the parameters of p-Cu{sub 1.8}S-n-II-VI surface-barrier structures by embedding a thin graded-gap layer into a photoconverter space-charge region (SCR) is implemented. The feature of quasi-electric fields built in the SCR, i.e., the fact that an increase in the drift field for minority carriers can be accompanied by a decrease in the potential barrier for majority carriers, is considered. The proper choice of the parameters of the Cd{sub x}Zn{sub 1−x}S graded-gap layer embedded in the Cu{sub 1.8}S-ZnS structure SCR made it possible to double the quantum efficiency in the ultraviolet spectral region. For Cu{sub 1.8}S-CdS photoconverters with a (CdS){sub x}(ZnSe){sub 1−x} intermediate layer, dark diode currents are decreased by three orders of magnitude while retaining a high quantum efficiency.

36 MATERIALS SCIENCE↗

Quantitative analysis of optical and recombination losses in Cu(In,Ga)Se{sub 2} thin-film solar cells

Optical and recombination losses in a Cu(In,Ga)Se{sub 2} thin-film solar cell with a band gap of 1.36–1.38 eV are theoretically analyzed. The optical transmittance of the ZnO and CdS layers through which the radiation penetrates into the absorbing layer is determined. Using optical constants, the optical loss caused by reflection at the interfaces (7.5%) and absorption in the ZnO and CdS layers (10.2%) are found. To calculate the recombination loss, the spectral distribution of the quantum efficiency of CdS/CuIn{sub 1–x}Ga{sub x}Se{sub 2} is investigated. It is demonstrated that, taking the drift and diffusion components of recombination at the front and rear surfaces of the absorber into account, the quantum efficiency spectra of the investigated solar cell can be analytically described in detail. The real parameters of the solar cell are determined by comparing the calculated results and experimental data. In addition, the losses caused by the recombination of photogenerated carriers at the front and rear surfaces of the absorbing layer (1.8% and <0.1%, respectively), at its neutral part (7.6%), and in the space-charge region of the p–n heterojunction (1.0%) are determined. A correction to the parameters of Cu(In,Ga)Se{sub 2} is proposed, which enhances the charge-accumulation efficiency.

36 MATERIALS SCIENCE↗

Localization of the Wannier–Mott Exciton on a Langmuir-Film/CdS Organic Semiconductor Interface

The low-temperature (T = 2 K) light reflectance spectra of organic semiconductor structures produced by depositing Langmuir–Blodgett films on a cadmium sulfide (CdS) crystal surface are studied. The spectra were studied in the region of the resonant frequency of the exciton state A{sub n} {sub = 1} in CdS. The spectra were analyzed within a multilayer medium model with allowance for the spatial dispersion and an exciton-free “dead” layer near the crystal surface contacting with the film. A conclusion is made that, as a result of the deposition of an organic film on a semiconductor crystal surface, the Wanier–Mott exciton is spatially localized near the film–crystal interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantitative study on the chemical solution deposition of zinc oxysulfide

Zinc Oxysulfide (ZnOS) has demonstrated potential in the last decade to replace CdS as a buffer layer material since it is a wide-band-gap semiconductor with performance advantages over CdS (E g = 2.4 eV) in the near UV-range for solar energy conversion. However, questions remain on the growth mechanisms of chemical bath deposited ZnOS. In this study, a detailed model is employed to calculate solubility diagrams that describe simple conditions for complex speciation control using only ammonium hydroxide without additional base. For these conditions, ZnOS is deposited via aqueous solution deposition on a quartz crystal microbalance in a continuous flow cell. Data is used to analyze the growth rate dependence on temperature and also to elucidate the effects of dimethylsulfoxide (DMSO) when used as a co-solvent. Activation energies (EA) of ZnOS are calculated for different flow rates and solution compositions. As a result, the measured EA relationships are affected by changes in the primary growth mechanism when DMSO is included.

14 SOLAR ENERGY↗

Molecular level control of nanoscale composition and morphology: Toward photocatalytic nanocomposites for solar-to-chemical energy conversion of biomass

Understanding the factors influencing nanocrystal formation is a challenge yet to be realized. In comparison to the large number of studies on nanocrystal synthesis and their applications, the number of studies on the effect of the precursor chemistry on nanocrystal composition and shape remains low. Although photochemical fabrication of metalsemiconductor nano-heterostructures is reported in literature, control over the free particle formation and the site of metal deposition have not been achieved. Moreover, utilization of metal- semiconductor nano-heterostructures in photocatalytic reactions other than water splitting is hardly explored. In this thesis, we studied the effect of chalcogenide precursor reactivity on the composition, morphology and the axial anisotropy of cadmiumchalcogenide nanocrystals. We also investigated the influence of the irradiation wavelength in synthesizing metal-semiconductor nano-heterostructures. Finally, we showed that metal semiconductor nano-heterostructures can be used as a photocatalyst for alcohol dehydrogenation reactions. We explored the pathways for the formation of Pt and Pd nanoparticles on CdS and CdS{sub 0.4}Se{sub 0.6} nanorods. This study revealed that the wavelength of irradiation is critical to control free-standing vs. bound metal (Pt and Pd) nanoparticles to semiconductor. Additionally, we observed that metal photodeposition occurs on specific segments of axially anisotropic, compositionally graded CdS0.4Se0.6 nanorods due to the band-gap differential between their nano-domains. We used semiconductor-metal heterostructures for sunlightdriven dehydrogenation and hydrogenolysis of benzyl alcohol. Heterostructure composition dictates activity (turnovers) and product distribution. A few metal (Pt, Pd) islands on the semiconductor surface significantly enhance activity and selectivity and also greatly stabilize the semiconductor against photoinduced etching and degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Asymmetric Semiconductor Nanorod/Oxide Nanoparticle Hybrid Materials: Model Nanomaterials for Light-Activated Formation of Fuels from Sunlight. Formal Progress Report -- Award DE-FG02-05ER15753

Executive Summary on Project Accomplishments: We focused our efforts for this project on the synthesis and characterization of semiconductor nanomaterials composed of semiconductor nanorods (NRs - e.g., CdSe, CdSe@CdS, CdS) with metal (Au, Pt, Co) or metal oxide (CoxOy) nanoparticle (NP) “tips.” These systems are attractive model systems where control of spatial, energetic and compositional features of both NRs and NP tips potentially enhances the efficiency of photogeneration and directional transport of charges, and photoelectrochemical conversion of sunlight to fuels. Synthetic methods to control material dimensions (20-200 nm in length), topology (one vs. two NP tips) and NR/NP tip compositions have been developed in the current project period (Pyun). We also achieved, for the first time in heterostructured nanorod materials, estimates of both valence band energies (E VB ) and conduction band energies (E CB ), using unique combinations of in vacuuo ultraviolet photoelectron spectroscopy (UPS, Armstrong), and waveguide spectroelectrochemistry (Saavedra), respectively. The spectroelectrochemical measurements in particular provide a unique path to estimation of E CB , and the distribution in E CB brought about by modification of NR composition. The combination of both approaches promises to be universally applicable to the characterization of energetics in nanomaterials of interest both for photovoltaic and sunlight-to-fuel photoelectrochemical assemblies.

14 SOLAR ENERGY↗

Manufacturing and Reliability Science for CIGS Photovoltaics

The purpose of this program was to overcome the largest challenges to investor confidence and long product lifetime in CuIn x Ga 1-x Se 2 (CIGS)-based photovoltaic products: metastability, shading-induced hot spots, and potential-induced degradation. Key findings were made in each of these areas by studying CIGS reliability at the cell level, which very few groups are currently doing. Metastability was thought to be a function of the CIGS absorber. We have challenged the state-of-the-art by showing that the metastability seen in commercial products is likely to be caused by the buffer layer. SCAPS device modeling confirmed that the buffer layer has a significant influence on metastability in CIGS devices, and also led to a processing change - the introduction of CdS islands to Zn(O,S) buffer layers - that dramatically reduced metastability in CIGS solar cells. In the reverse-bias shading task, modeling showed us that 19% solar cells are possible with thin CIGS layers of 0.5 µm. We were able to fabricate 15.2% solar cells in this project, which is the highest reported efficiency of devices in the ultra-thin class. We also discovered that the best way to dissipate less power in reverse bias was to eliminate the intrinsic ZnO layer that is often used in CIGS devices. Lower power dissipation led to devices that allowed two times the maximum power point current density in reverse without damage. Potential-induced degradation (PID) is caused by the drift of Na+ ions from the back glass to the CIGS/Mo interface, followed by diffusion into the solar cells and to the CdS region. We found that PID can be slowed by using low-conductivity borosilicate glass that contains higher K and lower Na than soda-lime glass. Based on significant progress in each of the three reliability challenges, the CIGS cell-level reliability project was very successful. We have also proved that module-level degradation mechanisms can be tested and solved at the cell level.

14 SOLAR ENERGY↗

Advanced Thin Film Core Technology: CIGS Final Technical Report (FTR)

Cu(In,Ga)Se 2 (CIGS) thin-film photovoltaics are a high-efficiency and reliable technology. This project completed research in two important areas and was designed to work collaboratively with industrial partners. Task 1: Alkali Science focused on alkali post-deposition treatments (PDT). PDTs have been instrumental in the dramatic voltage improvements that have moved CIGS device efficiencies from 20% to 23.35% [1]. Based on a survey of CIGS companies at the beginning of the project, the single biggest breakthrough for the CIGS community would be a mechanistic understanding of the role of alkalis in the material system. Significant accomplishments of Task 1: Alkali Science: 1) KF post-deposition treatments were shown to improve lifetime, open-circuit voltage (VOC), and efficiency of industrial partner samples, even when done as a later step, separate from the original CIGS deposition. 2) KF boosted efficiency when incorporated at the end of the third stage of NREL CIGS growth. 3) XPS characterization of CIGS surfaces with and without PDTs led to a proposed mechanism whereby K drives structural transformation at 350 degrees C that is locked in at room temperature even after K is rinsed away. 4) Published recipes for KF and RbF PDTs. Literature to date did not provide enough detail to quickly reproduce experimental results. 5) Identified most important parameters (RbF cell temperature and lamp setpoint temperature) and set boundaries for successful RbF PDTs. The purpose of Task 2: Cell-level Reliability was to overcome the largest challenges to investor confidence and long product lifetime in CIGS-based photovoltaic products: metastability, shading-induced hot spots, and potential-induced degradation (PID). Key findings were made in each of these areas by studying CIGS reliability at the cell level: 1) Published NREL's cell-level reliability testing procedures along with challenges that were encountered while developing them. These were also distributed to the community through an MRS conference presentation. 2) Decreased metastability by adding a CdS hole-injection layer between the CIGS and Zn(O,S) in the device stack. It also improved device performance. Materials other than CdS can be used for the same purpose. 3) Reduced front-glass PID by replacing soda-lime glass with low-Na borosilicate glass. 4) Found that PID depends on leakage current and light/electrical bias. This will help labs avoid test-specific degradation. 5) Discovered that CIGS can suffer from two different types of PID with different mechanisms. Front is slower and leads to shunting ZnO. Back is faster and degrades the p-n junction. 6) Holding cells at open circuit slows PID compared to short circuit. This affects testing protocols for glass/glass modules.

14 SOLAR ENERGY↗

Metal-Tipped and Electrochemically Wired Semiconductor Nanocrystals: Modular Constructs for Directed Charge Transfer

In our 2017 proposal to the Solar Photochemistry division of DOE/BES/Office of Science we targeted the creation, characterization and integratation of new II-IV semiconductor heterostructured nanomaterials into ultra-thin film (tethered) nanocrystalline arrays on transparent metal oxide (TCO) supports. Materials were to include CdSe quantum dots (QDs), asymmetric CdSe@CdS tetrapods (TPs) and CdSe@CdS nanorods (NRs), into unique photoelectrochemical platforms. The ultimate goal was to tether these new nanomaterials to either electron- or hole-selective oxide interlayers that would afford vectoral photo-induced charge transfer and ultimately formation of molecular products such as H 2 . This was an ambitious set of goals but integrated well with our previous work in this general area.

14 SOLAR ENERGY↗