Maikel F. A. M. van Hest

rf magnetron sputter deposition of transparent conducting Nb-doped TiO2 films on SrTiO3

rf magnetron sputtering, an established and scalable large area deposition process, is used to deposit Nb:TiO2 and Ta:TiO2 films onto (100) SrTiO3 substrates at temperatures TS ranging from room temperature to 400°C. Optical, electrical, and structural properties similar to those reported for pulsed laser deposition grown films were obtained. In particular, the most conducting Ti0.85Nb0.15O2 films, grown at TS≈375°C, are epitaxially oriented anatase films with conductivity of 3000Scm−1, carrier concentration of 2.4×1021cm−3, Hall mobility of 7.6cm2V−1s−1, and optical transparency T>80% from 400to900nm. The conductivity is strongly correlated with the intensity of the anatase (004) x-ray diffraction peak.

The electrical, optical and structural properties of InxZn1−xOy (0 ⩽ x ⩽ 1) thin films by combinatorial techniques

Indium–zinc-oxide (IZO) compositional libraries were deposited with dc magnetron sputtering onto glass substrates at 100 °C and analysed with high throughput, combinatorial techniques. The composition range from 4 to 95 at% In for Zn was explored. A peak in conductivity with σ > 3000 (Ω cm)−1 was observed at an indium content of ~70%. The mobility exceeded 30 cm2 (V s)−1 and the carrier concentrations were greater than 8 × 1020 cm−3. Crystalline phases were observed for In concentrations less than 45% and greater than 80% with an intermediate amorphous region. The low indium content films have a zinc oxide type structure with a ZnO (002) spacing ranging from ~2.61 to 2.85 A for 4% In and 45% In, respectively. For indium contents between 82% and 95%, the In2O3 (222) spacing varied from 2.98 to 2.99 A. Regardless of the composition or the degree of crystallinity, all films showed high optical transparency with the transmission >80% across the visible spectrum.

Thermal engineering of FAPbI3 perovskite material via radiative thermal annealing and in situ XRD

Lead halide perovskites have emerged as successful optoelectronic materials with high photovoltaic power conversion efficiencies and low material cost. However, substantial challenges remain in the scalability, stability and fundamental understanding of the materials. Here we present the application of radiative thermal annealing, an easily scalable processing method for synthesizing formamidinium lead iodide (FAPbI3) perovskite solar absorbers. Devices fabricated from films formed via radiative thermal annealing have equivalent efficiencies to those annealed using a conventional hotplate. By coupling results from in situ X-ray diffraction using a radiative thermal annealing system with device performances, we mapped the processing phase space of FAPbI3 and corresponding device efficiencies. Our map of processing-structure-performance space suggests the commonly used FAPbI3 annealing time, 10 min at 170 °C, can be significantly reduced to 40 s at 170 °C without affecting the photovoltaic performance. The Johnson-Mehl-Avrami model was used to determine the activation energy for decomposition of FAPbI3 into PbI2.

Carbon- and Oxygen-Free Cu(InGa)(SSe)2 Solar Cell with a 4.63% Conversion Efficiency by Electrostatic Spray Deposition

We have demonstrated the first example of carbon- and oxygen-free Cu(In,Ga)(SSe)2 (CIGSSe) absorber layers prepared by electrospraying a CuInGa (CIG) precursor followed by annealing, sulfurization, and selenization at elevated temperature. X-ray diffraction and scanning electron microscopy showed that the amorphous as-deposited (CIG) precursor film was converted into polycrystalline CIGSSe with a flat-grained morphology after post-treatment. The optimal post-treatment temperature was 300 °C for annealing and 500 °C for both sulfurization and selenization, with a ramp rate of 5 °C/min. The carbon impurities in the precursor film were removed by air annealing, and oxide that was formed during annealing was removed by sulfurization. The fabricated CIGSSe solar cell showed a conversion efficiency of 4.63% for a 0.44 cm(2) area, with Voc = 0.4 V, Jsc = 21 mA/cm(2), and FF = 0.53.

Hydrazine-Free Solution-Deposited CuIn(S,Se)2 Solar Cells by Spray Deposition of Metal Chalcogenides

Solution processing of semiconductors, such as CuInSe2 and its alloys (CIGS), can significantly reduce the manufacturing costs of thin film solar cells. Despite the recent success of solution deposition approaches for CIGS, toxic reagents such as hydrazine are usually involved, which introduce health and safety concerns. Here, we present a simple and safer methodology for the preparation of high-quality CuIn(S, Se)2 absorbers from metal sulfide solutions in a diamine/dithiol mixture. The solutions are sprayed in air, using a chromatography atomizer, followed by a postdeposition selenization step. Two different selenization methods are explored resulting in power conversion efficiencies of up to 8%.

Radio-frequency superimposed direct current magnetron sputtered Ga:ZnO transparent conducting thin films

The utilization of radio-frequency (RF) superimposed direct-current (DC) magnetron sputtering deposition on the properties of gallium doped ZnO (GZO) based transparent conducting oxides has been examined. The GZO films were deposited using 76.2 mm diameter ZnO:Ga2O3 (5 at. % Ga vs. Zn) ceramic oxide target on heated non-alkaline glass substrates by varying total power from 60 W to 120 W in steps of 20 W and at various power ratios of RF to DC changing from 0 to 1 in steps of 0.25. The GZO thin films grown with pure DC, mixed approach, and pure RF resulted in conductivities of 2200 ± 200 S/cm, 3920 ± 600 S/cm, and 3610 ± 400 S/cm, respectively. X-ray diffraction showed all films have wurtzite ZnO structure with the c-axis oriented perpendicular to the substrate. The films grown with increasing RF portion of the total power resulted in the improvement of crystallographic texture with smaller full-width half maximum in χ and broadening of optical gap with increased carrier concentration via more efficient do...

Direct write metallization for photovoltaic cells and scaling thereof

Atmospheric solution processing can help toward a significant cost reduction of photovoltaics. We investigate the use of direct write deposition approaches for deposition of metallization for a variety of solar cell materials. We are studying inkjet printing and aerosol spraying of metal contacts for Si, CIS/CIGS and organic photovoltaics. We have developed metal organic decomposition inks for metals such as: silver, nickel, copper and aluminum. All of these can be deposited in lines with 30–40 µm width and conductivities close to that of bulk metals. For silicon photovoltaics materials have been developed to facilitate Ohmic contact formation through an anti reflection coating. Initial research has been focusing on small cells, but in order to transfer the technology to production it has to be demonstrated on large area cells as well. For this the Atmospheric Processing Platform (APP) was developed at NREL. This platform allows us to scale the deposition of the developed inks and processing to large area (Up to 157 mm × 157 mm) and prototype contact patterns. The APP consists of several deposition, processing and characterization units, most located in a controlled environment. The atmospheric deposition tools in the APP are: inkjet printing, aerosol spraying and ultrasonic spraying. A rapid thermal processing unit is integrated for thermal processing. XRF and XRD can be accessed without leaving the controlled environment to determine the composition and structure of the deposited material. Sputter deposition and evaporation are also part of the APP, even though these techniques are not atmospheric. Details of the individual platforms in the APP will be given together with results of direct write contacts on large area cells.

High-Performance Flexible Perovskite Solar Cells on Ultrathin Glass: Implications of the TCO

For halide perovskite solar cells (PSCs) to fulfill their vast potential for combining low-cost, high efficiency, and high throughput production they must be scaled using a truly transformative method, such as roll-to-roll processing. Bringing this reality closer to fruition, the present work demonstrates flexible perovskite solar cells with 18.1% power conversion efficiency on flexible Willow Glass substrates. We highlight the importance of the transparent conductive oxide (TCO) layers on device performance by studying various TCOs. While tin-doped indium oxide (ITO) and indium zinc oxide (IZO) based PSC devices demonstrate high photovoltaic performances, aluminum-doped zinc oxide (AZO) based devices underperformed in all device parameters. Analysis of X-ray photoemission spectroscopy data shows that the stoichiometry of the perovskite film surface changes dramatically when it is fabricated on AZO, demonstrating the importance of the substrate in perovskite film formation.

Combinatorial chemical bath deposition of CdS contacts for chalcogenide photovoltaics

Contact layers play an important role in thin film solar cells, but new material development and optimization of its thickness is usually a long and tedious process. A high-throughput experimental approach has been used to accelerate the rate of research in photovoltaic (PV) light absorbers and transparent conductive electrodes, however the combinatorial research on contact layers is less common. Here, we report on the chemical bath deposition (CBD) of CdS thin films by combinatorial dip coating technique and apply these contact layers to Cu(In,Ga)Se2 (CIGSe) and Cu2ZnSnSe4 (CZTSe) light absorbers in PV devices. Combinatorial thickness steps of CdS thin films were achieved by removal of the substrate from the chemical bath, at regular intervals of time, and in equal distance increments. The trends in the photoconversion efficiency and in the spectral response of the PV devices as a function of thickness of CdS contacts were explained with the help of optical and morphological characterization of the CdS thin films. The maximum PV efficiency achieved for the combinatorial dip-coating CBD was similar to that for the PV devices processed using conventional CBD. The results of this study lead to the conclusion that combinatorial dip-coating can be used to accelerate the optimization of PV device performance of CdS and other candidate contact layers for a wide range of emerging absorbers.

Rapid thermal processing chamber for in-situ x-ray diffraction

Rapid thermal processing (RTP) is widely used for processing a variety of materials, including electronics and photovoltaics. Presently, optimization of RTP is done primarily based on ex-situ studies. As a consequence, the precise reaction pathways and phase progression during the RTP remain unclear. More awareness of the reaction pathways would better enable process optimization and foster increased adoption of RTP, which offers numerous advantages for synthesis of a broad range of materials systems. To achieve this, we have designed and developed a RTP instrument that enables real-time collection of X-ray diffraction data with intervals as short as 100 ms, while heating with ramp rates up to 100 °Cs(-1), and with a maximum operating temperature of 1200 °C. The system is portable and can be installed on a synchrotron beamline. The unique capabilities of this instrument are demonstrated with in-situ characterization of a Bi2O3-SiO2 glass frit obtained during heating with ramp rates 5 °C s(-1) and 100 °C s(-1), revealing numerous phase changes.