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Ramanathan, Kannan

Publications and source records attributed to Ramanathan, Kannan.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Variations in the Chemical and Electronic Impact of Post-Deposition Treatments on Cu(In,Ga)(S,Se) 2 Absorbers

We present a comparative study that focuses on the variability of post-deposition treatments (NaF-PDT and KF-PDT) and their impact on the chemical and electronic structure of chalcopyrite thin film solar cell absorbers. For this purpose, two 'extreme' chalcopyrite absorber systems are studied: Cu(In,Ga)(S,Se)2 with industrial relevance (STION), and Cu(In,Ga)Se2 with 'research grade' properties (NREL). Samples were subjected to NaF-PDT and KF-PDT, and investigated using x-ray and ultra-violet photoelectron spectroscopy, Auger electron spectroscopy, as well as synchrotron-based soft x-ray emission spectroscopy. Considerably different alkali-induced effects are found for the two systems. In particular, we only detect a PDT-related Cu depletion on the NREL absorber surfaces (and only on those leading to high-efficiency devices). We also observe a reduction in the surface S/Se ratio for all alkali-treated STION absorbers, in addition to the presence of sulfates after the KF-PDT. After processing the PDT absorbers to fully operating cells, we find that the PDT temperature has a significant impact on the resulting device efficiencies - both the NREL and STION absorbers can result in high-efficiency and low-efficiency devices, depending on KF-PDT processing parameters. The absorbers of low-efficiency KF-PDT devices show the largest Cu surface content after PDT, causing the valence band maximum to be closer to the Fermi energy, thus possibly leading to less efficient charge-carrier separation and/or enhanced recombination at the interface. Finally, we find varying degrees of Na, K, and/or F residuals on the different absorber surfaces after PDT, indicating a potential 'hidden' parameter in employing PDTs for improved solar cell performance.

14 SOLAR ENERGY↗
DOE OSTI2019

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↗
DOE OSTI2018

Electrical properties of CdS/Cu(In,Ga)Se 2 interface

We present an experimental method to measure and extract the interface density of states and fixed charge at the CdS/Cu(In,Ga)Se 2 (CIGS) interface using the capacitance-voltage technique applied to a metal-insulator-semiconductor structure. The density of interface states is on the order of 10 10 to 10 13 cm -2 eV -1 . The effective fixed charge at the interface is (7.8 +/- 0.3) x 10 11 cm -2 and due to positive charges. These electrical properties make the CdS/CIGS interface well passivated and to some extent resemble the SiN x /p-Si interface. We also measure the inversion strength (i.e., Fermi level at the interface) and capture cross-section of interface states from admittance spectroscopy. Inputting the above extracted parameters into the extended Shockley-Read-Hall recombination formulation by Eades and Swanson [J. Appl. Phys. 58, 4267 (1985)], we calculate the surface recombination velocity of mid-to-high 10 3 cm•s –1 , which agrees reasonably with temperature-intensity dependent recombination analysis.

14 SOLAR ENERGY↗
DOE OSTI2018

Surface and bulk effects of K in highly efficient Cu 1-x K x InSe 2 solar cells

To advance knowledge of the beneficial effects of K in Cu(In,Ga)(Se,S) 2 (CIGS) photovoltaic (PV) absorbers, recent Cu-K-In-Se phase growth studies have been extended to PV performance. First, the effect of distributing K throughout bulk Cu 1-x K x InSe 2 absorbers at low K/(K+Cu) compositions (0 = x = 0.30) was studied. Efficiency, open-circuit voltage (VOC), and fill factor (FF) were greatly enhanced for x ~ 0.07, resulting in an officially-measured 15.0%-efficient solar cell, matching the world record CuInSe 2 efficiency. The improvements were a result of reduced interface and bulk recombination, relative to CuInSe 2 (x ~ 0). However, higher x compositions had reduced efficiency, short-circuit current density (J SC ), and FF due to greatly increased interface recombination, relative to the x ~ 0 baseline. Next, the effect of confining K at the absorber/buffer interface at high K/(K+Cu) compositions (0.30 = x = 0.92) was researched. Previous work showed that these surface layer growth conditions produced CuInSe 2 with a large phase fraction of KInSe 2 . After optimization (75 nm surface layer with x ~ 0.41), these KInSe 2 surface samples exhibited increased efficiency (officially 14.9%), VOC, and FF as a result of decreased interface recombination. The KInSe 2 surfaces had features similar to previous reports for KF post-deposition treatments (PDTs) used in world record CIGS solar cells - taken as indirect evidence that KInSe 2 can form during these PDTs. Both the bulk and surface growth processes greatly reduced interface recombination. However, the KInSe 2 surface had higher K levels near the surface, greater lifetimes, and increased inversion near the buffer interface, relative to the champion bulk Cu 1-x K x InSe 2 absorber. These characteristics demonstrate that K may benefit PV performance by different mechanisms at the surface and in the absorber bulk.

14 SOLAR ENERGY↗
DOE OSTI2018

Analysis of Back-Contact Interface Recombination in Thin-Film Solar Cells

The open-circuit voltage (VOC) in a generic TCO/buffer/absorber/back-contact thin-film solar cell device is a key parameter in the recombination analysis. In particular, VOC is sensitively influenced by the interface recombination at the buffer/absorber front interface and at the absorber/back-contact interface. This paper reports the temperature, excitation light intensity, and wavelength-dependent open-circuit voltage analysis to separate and quantify recombination rates in solar cells at the front and back interfaces, in the depletion regions, and in the quasi-neutral region. The wavelength-dependent VOC analysis is exploited to extract the absorber/back-contact recombination coefficient. The experimentally observed results are verified using SCAPS-1D (one dimensional-a solar cell capacitance simulator) simulation.

14 SOLAR ENERGY↗
DOE OSTI2017

Methods of forming CIGS films

Methods for forming CIGS films are provided. According to an aspect of the invention, a method of forming a CIGS film includes a precursor step, which includes simultaneously evaporating Cu, In, Ga, Se, and Sb onto a substrate. The Se is incident on the substrate at a rate of at least 20 .ANG./s. The method also includes a selenization step, which includes evaporating Se over the substrate after the precursor step.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electrical characterization and comparison of CIGS solar cells made with different structures and fabrication techniques

In a previous study, we reported on Cu(In,Ga)Se2-based (CIGS) solar cell samples collected from different research laboratories and industrial companies with the purpose of understanding the range of CIGS materials that can lead to high-quality and high-efficiency solar panels. Here, we report on electrical measurements of those same samples. Electron-beam induced current and time-resolved photoluminescence (TRPL) gave insights about the collection probability and the lifetime of carriers generated in each absorber. Capacitance and drive-level capacitance profiling revealed nonuniformity in carrier-density profiles. Admittance spectroscopy revealed small activation energies (= 0.03 eV) indicative of the inversion strength, larger activation energies (> 0.1 eV) reflective of thermal activation of absorber conductivity and a deeper defect level. Deep-level transient spectroscopy (DLTS) probed deep hole-trapping defects and showed that all samples in this study had a majority-carrier defect with activation energy between 0.3 eV and 0.9 eV. Optical-DLTS revealed deep electron-trapping defects in several of the CIGS samples. This work focused on revealing similarities and differences between high-quality CIGS solar cells made with various structures and fabrication techniques.

14 SOLAR ENERGY↗
DOE OSTI2017

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfaces reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.

14 SOLAR ENERGY↗
DOE OSTI2017

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effects of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.

14 SOLAR ENERGY↗
DOE OSTI2016

Investigation of Sb-Containing Precursors for Cu(In, Ga)Se2 Thin Films Through Design of Experiments

The Design of Experiments (DoE) module in JMP statistical software was used to determine the best parameters for Sb-containing CIGS precursors with a fixed selenization step. Solar cells were fabricated and measured for all completed films. The most important factor influencing the current-voltage device parameters was identified as the temperature and antimony flux interaction. The DoE prediction profiler and predictive contour plots provided guidance to further improve the device parameters. In one follow-up run, we increased device efficiency from 14.9% to 15.5% Additional gains in efficiency to 16.9% were realized by introducing an intentional Ga gradient and an antireflective coating.

14 SOLAR ENERGY↗
DOE OSTI2016

Photovoltaic Properties of Selenized CuGa/In Films with Varied Compositions

Thin CuGa/In films with varied compositions were deposited by co-evaporation and then selenized in situ with evaporated selenium. The selenized Cu(In, Ga)Se2 absorbers were used to fabricate 390 solar cells. Cu/(Ga+In) and Ga/(Ga+In) (Cu/III and Ga/III) were independently varied, and photovoltaic performance was optimal at Cu/III of 77-92% for all Ga/III compositions studied (Ga/III ~ 30, 50, and 70%). The best absorbers at each Ga/III composition were characterized with time-resolved photoluminescence, scanning electron microscopy, and secondary ion mass spectrometry, and devices were studied with temperature-dependent current density-voltage, light and electrical biased quantum efficiency, and capacitance-voltage. The best cells with Ga/III ~ 30, 50, and 70% had efficiencies of 14.5, 14.4, and 12.2% and maximum power temperature coefficients of -0.496, -0.452, and -0.413%/degrees C, respectively. This resulted in the Ga/III ~ 50% champion having the highest efficiency at temperatures greater than 40 degrees C, making it the optimal composition for practical purposes. This optimum is understood as a result of the absorber's band gap grading- where minimum band gap dominates short-circuit current density, maximum space charge region band gap dominates open-circuit voltage, and average absorber band gap dominates maximum power temperature coefficient.

14 SOLAR ENERGY↗
DOE OSTI2016

Soft x-ray spectroscopy of a complex heterojunction in high-efficiency thin-film photovoltaics: Intermixing and Zn speciation at the Zn(O,S)/Cu(In,Ga)Se 2 interface

In this study, the chemical structure of the Zn(O,S)/Cu(In,Ga)Se 2 interface in high-efficiency photovoltaic devices is investigated using X-ray photoelectron and Auger electron spectroscopy, as well as soft X-ray emission spectroscopy. We find that the Ga/(Ga+In) ratio at the absorber surface does not change with the formation of the Zn(O,S)/Cu(In,Ga)Se 2 interface. Furthermore, we find evidence for Zn in multiple bonding environments, including ZnS, ZnO, Zn(OH) 2 , and ZnSe. We also observe dehydrogenation of the Zn(O,S) buffer layer after Ar+ ion treatment. Similar to high-efficiency CdS/Cu(In,Ga)Se 2 devices, intermixing occurs at the interface, with diffusion of Se into the buffer, and the formation of S—In and/or S—Ga bonds at or close to the interface.

14 SOLAR ENERGY↗
DOE OSTI2016

Comparison of CIGS solar cells made with different structures and fabrication techniques

Cu(In, Ga)Se2 (CIGS)-based solar cells from six fabricators were characterized and compared. The devices had differing substrates, absorber deposition processes, buffer materials, and contact materials. The effective bandgaps of devices varied from 1.05 to 1.22 eV, with the lowest optical bandgaps occurring in those with metal-precursor absorber processes. Devices with Zn(O, S) or thin CdS buffers had quantum efficiencies above 90% down to 400 nm. Most voltages were 250-300 mV below the Shockley-Queisser limit for their bandgap. Electroluminescence intensity tracked well with the respective voltage deficits. Fill factor (FF) was as high as 95% of the maximum for each device's respective current and voltage, with higher FF corresponding to lower diode quality factors (~1.3). An in-depth analysis of FF losses determined that diode quality reflected in the quality factor, voltage-dependent photocurrent, and, to a lesser extent, the parasitic resistances are the limiting factors. As a result, different absorber processes and device structures led to a range of electrical and physical characteristics, yet this investigation showed that multiple fabrication pathways could lead to high-quality and high-efficiency solar cells.

14 SOLAR ENERGY↗
DOE OSTI2016

Low-Cd CIGS solar cells made with a hybrid CdS/Zn(O,S) buffer layer

In Cu(In,Ga)Se2 (CIGS) solar cells, CdS and Zn(O,S) buffer layers were compared with a hybrid buffer layer consisting of thin CdS followed Zn(O,S). We explore the physics of this hybrid layer that combines the standard (Cd) approach with the alternative (Zn) approach in the pursuit to unlock further potential for CIGS technology. CdS buffer development has shown optimal interface properties, whereas Zn(O,S) buffer development has shown increased photocurrent. Although a totally Cd-free solar module is more marketable, the retention of a small amount of Cd can be beneficial to achieve optimum junction properties. As long as the amount of Cd is reduced to less than 0.01% by weight, the presence of Cd does not violate the hazardous substance restrictions of the European Union (EU). We estimate the amount of Cd allowed in the EU for CIGS on both glass and stainless steel substrates, and we show that reducing Cd becomes increasingly important as substrate weights decrease. As a result, this hybrid buffer layer had reduced Cd content and a wider space charge region, while achieving equal or better solar cell performance than buffer layers of either CdS or Zn(O,S) alone.

14 SOLAR ENERGY↗
DOE OSTI2016

Properties of Cu 1–x K x InSe 2 alloys

Adding potassium to Cu(In,Ga)Se 2 absorbers has been shown to enhance photovoltaic power conversion efficiency. To illuminate possible mechanisms for this enhancement and limits to beneficial K incorporation, the properties of Cu 1-x K x InSe 2 (CKIS) thin-film alloys have been studied. Films with K/(K + Cu), or x, from 0 to 1 were grown by co-evaporation, and probed by XRF, EPMA, SEM, XRD, UV-Visible spectroscopy, current-voltage, and TRPL measurements. Composition from in situ quartz crystal and EIES monitoring was well correlated with final film composition. Crystal lattice parameters showed linear dependence on x, indicating complete K incorporation and coherent structural character at all compositions in the <100> and <010> lattice directions, despite the different symmetries of CuInSe 2 and KInSe 2 . The band gap energy showed pronounced bowing with x composition, in excellent agreement with experimental reports and semiconductor theory. Films of Mo/CKIS/Ni were non-ohmic, and increasing x from 0 to 0.58 decreased the apparent CKIS resistivity. Further evidence of decreased CKIS resistivity was observed with photoluminescence response, which increased by about half a decade for x > 0, and indicates increased majority carrier concentration. Minority carrier lifetimes increased by about an order of magnitude for films grown at x = 0.07 and 0.14, relative to CuInSe 2 and x ≥ 0.30. As a result, this is the first report of a Cu-K-In-Se film with >1 at.% K, and the observed property changes at increased x (wider band gap; lower resistivity; increased lifetime) comprise valuable photovoltaic performance-enhancement strategies, suggesting that CKIS alloys have a role to play in future engineering advances.

(Cu,K)InSe2↗
DOE OSTI2016

Electronic structure of the Zn(O,S)/Cu(In,Ga)Se 2 thin-film solar cell interface

The electronic band alignment of the Zn(O,S)/Cu(In,Ga)Se2 interface in high-efficiency thin-film solar cells was derived using X-ray photoelectron spectroscopy, ultra-violet photoelectron spectroscopy, and inverse photoemission spectroscopy. Similar to the CdS/Cu(In,Ga)Se2 system, we find an essentially flat (small-spike) conduction band alignment (here: a conduction band offset of (0.09 +/- 0.20) eV), allowing for largely unimpeded electron transfer and forming a likely basis for the success of high-efficiency Zn(O,S)-based chalcopyrite devices. Furthermore, we find evidence for multiple bonding environments of Zn and O in the Zn(O,S) film, including ZnO, ZnS, Zn(OH)2, and possibly ZnSe.

14 SOLAR ENERGY↗