Sergey V. Baryshev

Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films

The highest efficiency solar cells based on copper zinc tin sulfide (CZTS), a promising photovoltaic material comprised of earth abundant elements, are built on soda lime glass (SLG), a substrate which contains many impurities, including Na and K. These impurities may diffuse into CZTS films during processing and affect film structure and properties. We have investigated the effects of these impurities on the microstructure of CZTS films synthesized by ex situ sulfidation of Cu–Zn–Sn alloy films co-sputtered on SLG, Pyrex, and quartz. CZTS films synthesized on SLG were found to have significantly larger grains than films grown on the other substrates. Furthermore, we show that by including a bare additional piece of SLG in the sulfidation ampoule, the grain size of films grown on nominally impurity-free quartz increases from 100s of nm to greater than 1 μm. This demonstrates conclusively that impurities in SLG volatilize in S-containing atmospheres and incorporate into nearby CZTS films synthesized on other substrates. Impurity concentrations in these CZTS films were examined using depth profiling with time-of-flight secondary ion mass spectrometry (TOF-SIMS). Of all the impurities present in SLG, the TOF-SIMS experiments implicated Na, K, and Ca as possible elements responsible for the enhanced grain growth. To investigate the effects of these impurities individually, we introduced very small and controllable amounts of Na, K, or Ca into the sulfidation ampoule during CZTS synthesis. Impurity amounts as low as 10−6 moles of Na or 10−7 moles of K resulted in a dramatic increase in grain size, from 100s of nm to several microns, for films deposited on quartz, while Ca loading had no visible effect on the final microstructure. Based on this vapor transport mechanism, we thus demonstrate an approach for delivering precisely controlled amounts of specific impurities into CZTS films on arbitrary substrates to facilitate large-grain growth.

Stabilizing Cu2S for photovoltaics one atomic layer at a time.

Stabilizing Cu2S in its ideal stoichiometric form, chalcocite, is a long-standing challenge that must be met prior to its practical use in thin-film photovoltaic (PV) devices. Significant copper deficiency, which results in degenerate p-type doping, might be avoided by limiting Cu diffusion into a readily formed surface oxide and other adjacent layers. Here, we examine the extent to which PV-relevant metal-oxide over- and underlayers may stabilize Cu2S thin films with desirable semiconducting properties. After only 15 nm of TiO2 coating, Hall measurements and UV-vis-NIR spectroscopy reveal a significant suppression of free charge-carrier addition that depends strongly on the choice of deposition chemistry. Remarkably, the insertion of a single atomic layer of Al2O3 between Cu2S and TiO2 further stabilizes the active layer for at least 2 weeks, even under ambient conditions. The mechanism of this remarkable enhancement is explored by in situ microbalance and conductivity measurements. Finally, photoluminescence quenching measurements point to the potential utility of these nanolaminate stacks in solar-energy harvesting applications.

High quantum efficiency ultrananocrystalline diamond photocathode for photoinjector applications

We report results of quantum efficiency (QE) measurements carried out on a 150 nm thick nitrogen-incorporated ultrananocrystalline diamond terminated with hydrogen; abbreviated as (N)UNCD:H. (N)UNCD:H demonstrated a remarkable QE of ∼10−3 (∼0.1%) at 254 nm. Moreover, (N)UNCD:H was sensitive in visible light with a QE of ∼5 × 10−8 at 405 nm and ∼5 × 10−9 at 436 nm. Importantly, after growth and prior to QE measurements, samples were exposed to air for about 2 h for transfer and loading. Such design takes advantage of a key combination: (1) H-termination proven to induce negative electron affinity on the (N)UNCD and to stabilize its surface against air exposure; and (2) N-incorporation inducing n-type conductivity in intrinsically insulating UNCD.

Planar ultrananocrystalline diamond field emitter in accelerator radio frequency electron injector: Performance metrics

A case performance study of a planar field emission cathode (FEC) based on nitrogen-incorporated ultrananocrystalline diamond, (N)UNCD, was carried out in an RF 1.3 GHz electron gun. The FEC was a 100 nm (N)UNCD film grown on a 20 mm diameter stainless steel disk with a Mo buffer layer. At surface gradients 45–65 MV/m, peak currents of 1–80 mA (equivalent to 0.3–25 mA/cm2) were achieved. Imaging with two YAG screens confirmed emission from the (N)UNCD surface with (1) the beam emittance of 1.5 mm × mrad/mm-rms and (2) longitudinal FWHM and rms widths of non-Gaussian energy spread of 0.7% and 11% at an electron energy of 2 MeV. Current stability was tested over the course of 36 × 103 RF pulses (equivalent to 288 × 106 GHz oscillations).

Single-crystal diamond refractive lens for focusing X-rays in two dimensions

The fabrication and performance evaluation of single-crystal diamond refractive X-ray lenses of which the surfaces are paraboloids of revolution for focusing X-rays in two dimensions simultaneously are reported. The lenses were manufactured using a femtosecond laser micromachining process and tested using X-ray synchrotron radiation. Such lenses were stacked together to form a standard compound refractive lens (CRL). Owing to the superior physical properties of the material, diamond CRLs could become indispensable wavefront-preserving primary focusing optics for X-ray free-electron lasers and the next-generation synchrotron storage rings. They can be used for highly efficient refocusing of the extremely bright X-ray sources for secondary optical schemes with limited aperture such as nanofocusing Fresnel zone plates and multilayer Laue lenses.

GHz laser-free time-resolved transmission electron microscopy: A stroboscopic high-duty-cycle method

A device and a method for producing ultrashort electron pulses with GHz repetition rates via pulsing an input direct current (dc) electron beam are provided. The device and the method are based on an electromagnetic-mechanical pulser (EMMP) that consists of a series of transverse deflecting cavities and magnetic quadrupoles. The EMMP modulates and chops the incoming dc electron beam and converts it into pico- and sub-pico-second electron pulse sequences (pulse trains) at >1GHz repetition rates, as well as controllably manipulates the resulting pulses. Ultimately, it leads to negligible electron pulse phase-space degradation compared to the incoming dc beam parameters. The temporal pulse length and repetition rate for the EMMP can be continuously tunable over wide ranges. Applying the EMMP to a transmission electron microscope (TEM) with any dc electron source (e.g. thermionic, Schottky, or field-emission source), a GHz stroboscopic high-duty-cycle TEM can be realized. Unlike in many recent developments in time-resolved TEM that rely on a sample pumping laser paired with a laser launching electrons from a photocathode to probe the sample, there is no laser in the presented experimental set-up. This is expected to be a significant relief for electron microscopists who are not familiar with laser systems. The EMMP and the sample are externally driven by a radiofrequency (RF) source synchronized through a delay line. With no laser pumping the sample, the problem of the pump laser induced residual heating/damaging the sample is eliminated. As many RF-driven processes can be cycled indefinitely, sampling rates of 1-50GHz become accessible. Such a GHz stroboscopic TEM would open up a new paradigm for in situ and in operando experiments to study samples externally driven electromagnetically. Complementary to the lower (MHz) repetition rates experiments enabled by laser photocathode TEM, new experiments in the multi-GHz regime will be enabled by the proposed RF design. Because TEM is also a platform for various analytical methods, there are infinite application opportunities in energy and electronics to resolve charge (electronic and ionic) transport, and magnetic, plasmonic and excitonic dynamics in advanced functional materials. In addition, because the beam duty-cycle can be as high as ~10(-1) (or 10%), detection can be accomplished by commercially available detectors. In this article, we report an optimal design of the EMMP. The optimal design was found using an analytical generalized matrix approach in the thin lens approximation along with detailed beam dynamics taking actual realistic dc beam parameters in a TEM operating at 200keV.

Efficient extraction of high power THz radiation generated by an ultra-relativistic electron beam in a dielectric loaded waveguide

We have measured an intense THz radiation produced by a sub-picosecond, relativistic electron bunch in a dielectric loaded waveguide. For efficient THz pulse extraction, the dielectric loaded waveguide end was cut at an angle. For an appropriate choice of angle cut, such antenna converts the TM01 mode excited in the waveguide into a free-space fundamental Gauss-Hermite mode propagating at an angle with respect to the electron beam trajectory. Simulations show that more than 95% of energy can be extracted using such a simple approach. More than 40 oscillations of about 170 ps long 0.48 THz signal were explicitly measured with an interferometer and 10 μJ of energy per pulse, as determined with a calorimetric energy meter, were delivered outside the electron beamline to an area suitable for THz experiments.

Observation of Field-Emission Dependence on Stored Energy

Field emission from a solid metal surface has been continuously studied for a century over macroscopic to atomic scales. It is general knowledge that, other than the surface properties, the emitted current is governed solely by the applied electric field. A pin cathode has been used to study the dependence of field emission on stored energy in an L-band rf gun. The stored energy was changed by adjusting the axial position (distance between the cathode base and the gun back surface) of the cathode while the applied electric field on the cathode tip is kept constant. A very strong correlation of the field-emission current with the stored energy has been observed. While eliminating all possible interfering sources, an enhancement of the current by a factor of 5 was obtained as the stored energy was increased by a factor of 3. It implies that under certain circumstances a localized field emission may be significantly altered by the global parameters in a system.

Locally Resolved Electron Emission Area and Unified View of Field Emission from Ultrananocrystalline Diamond Films

In this paper we study the effect of actual, locally resolved, field emission (FE) area on electron emission characteristics of uniform semimetallic nitrogen-incorporated ultrananocrystalline diamond ((N)UNCD) field emitters. To obtain the actual FE area, imaging experiments were carried out in a vacuum system in a parallel-plate configuration with a specialty anode phosphor screen. Electron emission micrographs were taken concurrently with I-V characteristics measurements. It was found that in uniform (N)UNCD films the field emitting site distribution is not uniform across the surface, and that the actual FE area depends on the applied electric field. To quantify the actual FE area dependence on the applied electric field, a novel automated image processing algorithm was developed. The algorithm processes extensive imaging datasets and calculates emission area per image. By doing so, it was determined that the emitting area was always significantly smaller than the FE cathode surface area of 0.152 cm available. Namely, the actual FE area would change from 5× 10 % to 1.5 % of the total cathode area with the applied electric field increased. We also found that (N)UNCD samples deposited on stainless steel with molybdenum and nickel buffer layers always had better emission properties with the turn-on electric field <5 V/μm and β-factor of about 1,000, as compared to those deposited directly onto tungsten having the turn-on field >10 V/μm and β-factor of about 200. It was concluded that rough or structured surface, either on the macroor microscale, is not a prerequisite for good FE properties. Raman spectroscopy suggested that increased amount of the graphitic sp phase, manifested as reduced D/G peak ratio, was responsible for improved emission characteristics. Finally and most importantly, it was shown that when I-E curves as measured in the experiment were normalized by the field-dependent emission area, the resulting j-E curves demonstrated a strong kink and significant deviation from Fowler-Nordheim (FN) law, and eventually saturated at a current density of ∼100 mA/cm. This value was nearly identical for all studied (N)UNCD films, regardless of the substrate.In this paper, we study the effect of the actual, locally resolved, field emission area on electron emission characteristics of uniform planar conductive nitrogen-incorporated ultrananocrystalline diamond ((N)UNCD) field emitters. High resolution imaging experiments were carried out in a field emission microscope with a specialty imaging anode screen such that electron emission micrographs were taken concurrently with measurements of I-V characteristics. An automated image processing algorithm was applied to process the extensive imaging data sets and calculate the emission area per image. It was routinely found that field emission from as-grown planar (N)UNCD films was always confined to a counted number of discrete emitting centers across the surface, which varied in size and electron emissivity. It was established that the actual field emission area critically depends on the applied electric field and that the field emission area and overall electron emissivity improve with the sp2-fraction present in the film, irrespective of the original substrate roughness or morphology. Most importantly, when as-measured I-E characteristics were normalized by the electric field-dependent emission area, the resulting j-E curves demonstrated a strong kink and departed from the Fowler-Nordheim law, finally saturating at a value on the order of 100 mA/cm2. This value was nearly identical for all studied films regardless of substrate. It was concluded that the saturation value is specific to the intrinsic fundamental properties of (N)UNCD.

Electron emission projection imager

A new projection type imaging system is presented. The system can directly image the field emission site distribution on a cathode surface by making use of anode screens in the standard parallel plate configuration. The lateral spatial resolution of the imager is on the order of 1-10 μm. The imaging sensitivity to the field emission current can be better than the current sensitivity of a typical electrometer, i.e., less than 1 nA.