Kathleen B. Reuter

High-Efficiency Solar Cell with Earth-Abundant Liquid-Processed Absorber

2010 WILEY-VCH Verlag Gmb Chalcogenide-based solar cells provide a critical pathway to cost parity between photovoltaic (PV) and conventional energy sources. Currently, only Cu(In,Ga)(S,Se)2 (CIGS) and CdTe technologies have reached commercial module production with stable power conversion efficiencies of over 9 percent. Despite the promise of these technologies, restrictions on heavy metal usage for Cd and limitations in supply for In and Te are projected to restrict the production capacity of the existing chalcogen-based technologies to <100GWp per year, a small fraction of our growing energy needs, which are expected to double to 27 TW by 2050. Earth-abundant copper-zinc-tin-chalcogenide kesterites, Cu2ZnSnS4 and Cu2ZnSnSe4, have been examined as potential alternatives for the two leading technologies, reaching promising but not yet marketable efficiencies of 6.7% and 3.2%, respectively, by multilayer vacuum deposition. Here we show a non-vacuum, slurry-based coating method that combines advantages of both solution processing and particlebased deposition, enabling fabrication of Cu2ZnSn(Se,S)4 devices with over 9.6% efficiency—a factor of five performance improvement relative to previous attempts to use highthroughput ink-based approaches and >40% higher than previous record devices prepared using vacuum-based methods. To address the issue of cost, non-vacuum ‘‘ink’’-based approaches—both from solutions and suspensions—are being developed for chalcogenide-based absorber layer deposition to replace potentially more expensive vacuum-based techniques. True solutions allow intermixing of the constituents at a molecular level and the formation of smooth homogeneous films, as demonstrated with spin-coated CIGS absorber layers from hydrazine (N2H4) solutions. [11–13] The chemically reducing character of hydrazine stabilizes solutions of anions with direct metal-chalcogen bonding for select elements (e.g. Cu, In, Ga, Sn), without the necessity to introduce typical impurities (e.g., C, O, Cl). Suspension approaches employ solid particles designed to be deposited on a substrate and reacted or fused with each other, to form a desired crystalline phase and grain structure. Normally insoluble components can be deposited by this approach using typical liquid-based deposition (e.g., printing, spin coating, slit casting, spraying). Although high-quality large-grained absorber layers can be formed for selected systems using either solutionor particlebased deposition, numerous challenges confront each approach for more general deposition needs. Solution processing is limited by the solubility of many materials of interest (e.g., ZnSe1–xSx in hydrazine solvents—relevant for the deposition of Cu2ZnSnS4 or Cu2ZnSnSe4). In addition, volume contraction upon drying of solution-deposited layers creates stress in the film that may cause crack formation in thicker films. In suspension approaches, a common difficulty is achieving single-phase crystallization among the solid particles. Particle-based approaches (as well as some solution methods) typically require the addition of organic agents to improve wetting and particle dispersion, and to avoid film cracks and delamination. Most of these non-volatile organic additives introduce carbon contamination in the final layer. Because of these challenges, vacuum-based techniques have historically shown superior performance to liquid coating. In the case of the earth-abundant Cu2ZnSn(S,Se)4 materials, ink-based approaches have to date yielded at most <1.6% efficiency devices. Here we demonstrate an hybrid solution-particle approach, using the earth-abundant Cu2ZnSn(S,Se)4 system as an example, which enables fabrication of PV devices with over 9.6% power conversion efficiency. The slurry (or ink) employed for deposition comprises a Cu–Sn chalcogenide (S or S–Se) solution in hydrazine (see Experimental section), with the in situ formation of readily dispersible particle-based Zn-chalcogenide precursors, ZnSe(N2H4) (Figure 1a,d) or ZnS(N2H4) (Figure 1b). Thermogravimetric analysis (TGA) of the isolated selenide particle precursor shows decomposition at approximately 200 8C, with mass loss of about 20%, close to the theoretical value expected upon transition to pure ZnSe (Figure 1c,d). Deposition using this hybrid slurry successfully combines the advantages of solution and suspension deposition routes by use of solutions containing solid particles, wherein both components (i.e., solution and particle) contain metal and chalcogen elements that integrate into the final film. Using the hybrid slurry method (i) solubility limitations are resolved, as virtually any materials system can be constituted by a combination of solid and dissolved components; (ii) the dissolved components can be engineered as an efficient binding media for the particles, eliminating the need of separate organic binders; (iii) solid particles act as stress-relief and crack-deflection centers allowing the deposition of thicker layers than pure solution processes; and (iv) the intimate contact between the two phases allows rapid reaction and homogeneous phase formation. Complete conversion of all constituents of the spin-coated hybrid precursor films into a single-phase, highly crystalline Cu2ZnSn(S,Se)4 is achieved by annealing at 540 8C on a hot plate. Three main types of samples were targeted – high selenium content (A), intermediate sulfoselenide (B) and pure sulfide (C) –

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu–Sn–S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

Principle of direct van der Waals epitaxy of single-crystalline films on epitaxial graphene

There are numerous studies on the growth of planar films on sp(2)-bonded two-dimensional (2D) layered materials. However, it has been challenging to grow single-crystalline films on 2D materials due to the extremely low surface energy. Recently, buffer-assisted growth of crystalline films on 2D layered materials has been introduced, but the crystalline quality is not comparable with the films grown on sp(3)-bonded three-dimensional materials. Here we demonstrate direct van der Waals epitaxy of high-quality single-crystalline GaN films on epitaxial graphene with low defectivity and surface roughness comparable with that grown on conventional SiC or sapphire substrates. The GaN film is released and transferred onto arbitrary substrates. The post-released graphene/SiC substrate is reused for multiple growth and transfer cycles of GaN films. We demonstrate fully functional blue light-emitting diodes (LEDs) by growing LED stacks on reused graphene/SiC substrates followed by transfer onto plastic tapes.

Evidence for segregation of Te in Ge2Sb2Te5 films: Effect on the “phase-change” stress

The authors present direct evidence for Te segregation to the grain boundaries in chalcogenide Ge2Sb2Te5 films by using transmission electron microscopy scans with a 0.5nm diameter focused probe. This finding is consistent with the observed impeded grain growth and with the post-transition relief of a “spikelike” stress, fully to the pretransition level. Te motion shows up in void formation below 200°C, a pileup of Te at the surface and its loss at higher (above 400°C) temperatures. Tuning the driving force for this segregation may be key for the optimal phase-change material design.

Electrodeposition of Indium on Copper for CIS and CIGS Solar Cell Applications

The electrodeposition of indium on copper substrates is studied in an acid sulfate solution for applications in CuInS 2 (CIS) and Cu(InGa)Se 2 (CIGS) solar cells. The study is focused on the film morphology and thickness uniformity on the nanometer scale. A two-step film growth behavior was observed, a conformal smooth film growth followed by a three-dimensional island growth. A hypothesis involving the Cu-In alloy formation and the Cu-In interdiffusion is proposed. While the room temperature alloy formation promotes the conformal deposition of a few monolayers of alloy, the fast interdiffusion between Cu and In further extends this alloy formation to a thicker layer and delays the typical island formation-growth phenomenon.

Fixed-Gap Tunnel Junction for Reading DNA Nucleotides

Previous measurements of the electronic conductance of DNA nucleotides or amino acids have used tunnel junctions in which the gap is mechanically adjusted, such as scanning tunneling microscopes or mechanically controllable break junctions. Fixed-junction devices have, at best, detected the passage of whole DNA molecules without yielding chemical information. Here, we report on a layered tunnel junction in which the tunnel gap is defined by a dielectric layer, deposited by atomic layer deposition. Reactive ion etching is used to drill a hole through the layers so that the tunnel junction can be exposed to molecules in solution. When the metal electrodes are functionalized with recognition molecules that capture DNA nucleotides via hydrogen bonds, the identities of the individual nucleotides are revealed by characteristic features of the fluctuating tunnel current associated with single-molecule binding events.

Torwards marketable efficiency solution-processed kesterite and chalcopyrite photovoltaic devices

Although CuIn1−xGaxSe2−ySy (CIGS) chalcopyrite and Cu2ZnSn(S,Se)4 (CZTSSe) kesterite-related films offer significant potential for low-cost high-efficiency photovoltaic (PV) devices, the complicated multi-element nature of these materials generally leads to the requirement of more complex and costly deposition processes. This talk focuses on employing the unique solvent properties of hydrazine to solution-deposit CIGS and CZTSSe films for high-performance solar cells. CIGS films are deposited by completely dissolving all elements in hydrazine, solution-depositing a molecular precursor film, and heat treating in an inert atmosphere, to yield a single-phase chalcopyrite film (no post-deposition selenization required). Trace additions of Sb improve grain structure in the resulting film and enhance device performance. Devices based on a glass/Mo/spin-coated CIGS/CdS/i-ZnO/ITO structure yield power conversion efficiencies of as high as 13.6% (AM1.5 illumination; NREL certified). Analogous CZTSSe absorber layers have been processed using a hybrid hydrazine-based slurry approach, enabling liquid-based deposition of kesterite-type films and resulting device efficiencies of as high as 9.6% (AM1.5 illumination; NREL certified)—exceeding the previous kesterite performance record by ∼40%. The combination of improved efficiency, In-free absorber and solution-based processing opens opportunities for development of a low-cost and pervasive technology.

Vertical thinking in blue light emitting diodes: GaN-on-graphene technology

In this work, we show that a 2D cleave layer (such as epitaxial graphene on SiC) can be used for precise release of GaNbased light emitting diodes (LEDs) from the LED-substrate interface. We demonstrate the thinnest GaN-based blue LED and report on the initial electrical and optical characteristics. Our LED device employs vertical architecture: promising excellent current spreading, improved heat dissipation, and high light extraction with respect to the lateral one. Compared to conventional LED layer release techniques used for forming vertical LEDs (such as laser-liftoff and chemical lift-off techniques), our process distinguishes itself with being wafer-scalable (large area devices are possible) and substrate reuse opportunity.

High efficiency Cu 2 ZnSn(S x Se 1−x ) 4 thin film solar cells by thermal co-evaporation

We report on the device results of thermally evaporated high efficiency Cu2ZnSn(SxSe1−x)4 (CZTSSe) thin film solar cells with power conversion efficiencies of 7.1% (x=1.0) and 7.5% (x=0.34). We have carried out extensive electrical and structural characterization of CZTSSe solar cells to identify major factors that limit the efficiency. Bias-dependent quantum efficiency measurements revealed ineffective collection of charge carriers photo-generated deep in the absorber layer suggesting a short minority carrier diffusion length, which was confirmed by time-resolved photoluminescence measurements. Temperature-dependence of the series resistance of the devices is consistent with the presence of a Schottky-type barrier in the back contact, likely caused by secondary phases near the CZTS/Mo interface and/or an interfacial MoSx layer.