Fabrication of ZnO Nanobrushes by H2-C2H2 Plasma Etching for H2 Sensing Applications.

Zinc oxide has widespread use in diverse applications due to its distinct properties. Many of these applications benefit from controlling the morphology on the nanoscale, where for example gas sensing is strongly enhanced for high surface-to-volume ratios. In this work the formation of novel ZnO nanobrushes by plasma etching treatment as a new approach is presented. The morphology and structure of the ZnO nanobrushes are studied in detail by transmission and scanning electron microscopy. It is revealed that ZnO nanobrush structures are fabricated by self-patterned preferential etching of ZnO microtetrapods in a hydrogen-acetylene plasma. The etching process was found to be most effective at 1% C2H2 admixture. Nanowire arrays are formed enabled by sidewall passivation due to a-C:H deposition. The nanobrush structures are further stabilized by simultaneous deposition of a SiOx layer from the opposite direction. Highly sensitive (gas response S = 148), selective, and fast (response time 15 s, recovery time 6 s) hydrogen sensors are fabricated from single nanobrushes. Single nanobrush sensors show enhanced sensing performance in increased gas response S of at least 10 times and improved response as well as recovery times when compared to nonporous single ZnO nanorod sensors due to the small diameters (≈50 nm) of the formed nanowires as well as the strongly enhanced surface-to-volume ratio of the nanobrushes by a factor of more than 10.

In vitro proinflammatory gene expression changes in human whole blood after contact with plasma-treated implant surfaces.

BACKGROUND: The aim of this in vitro study was to identify changes in gene expression of proinflammatory cytokines in human whole blood after contact with titanium implant surfaces after plasma treatment. MATERIALS AND METHODS: Grade 4 titanium dental implants were conditioned with low-pressure plasma (LPP) and atmospheric-pressure plasma (APP) and submerged in human whole blood in vitro. Unconditioned implants and blood samples without implants served as control and negative control groups, respectively. Sampling was performed at 1, 8, and 24 h. Changes in mRNA expression levels of interleukin 1-beta (IL1-ß) and tumor necrosis factor-alpha (TNF-α) were assessed using RT-qPCR. RESULTS: In the control group, significant increases in IL1-ß and TNF-α expression were observed. Significant decreases in the expression of IL1-ß and TNF-α were identified in blood with implants after plasma treatment. CONCLUSION: Differences in gene expression of proinflammatory cytokines after incubation of plasma-conditioned titanium implants can be assessed using human whole blood. The results of the present study indicate that plasma treatment (APP and LPP) of titanium dental implants leads to downregulation of proinflammatory cytokine gene expression, which might be beneficial in early osseointegration.

An optical trapping system for particle probes in plasma diagnostics.

We present one of the first experiments for optically trapping of single microparticles as probes for low temperature plasma diagnostics. Based on the dual laser beam, counter-propagating technique, SiO2 microparticles are optically trapped at very large distances in low-temperature, low-pressure rf plasma. External forces on the particle are measured by means of the displacement of the probe particle in the trap. Measurements can be performed during plasma operation as well as without plasma. The paper focuses on the optical setup and the verification of the system and its principle. Three examples for the particle behavior in the trapping system are presented: First, we measured the neutral gas damping as a verification of the technique. Second, an experiment without a plasma studies the changing particle charge by UV light radiation, and third, by moving the probe particle in the vertical direction into the sheath or into the plasma bulk, respectively, the acting forces on the probe particle are measured.

Shaping thin film growth and microstructure pathways via plasma and deposition energy: a detailed theoretical, computational and experimental analysis.

Understanding the science and engineering of thin films using plasma assisted deposition methods with controlled growth and microstructure is a key issue in modern nanotechnology, impacting both fundamental research and technological applications. Different plasma parameters like electrons, ions, radical species and neutrals play a critical role in nucleation and growth and the corresponding film microstructure as well as plasma-induced surface chemistry. The film microstructure is also closely associated with deposition energy which is controlled by electrons, ions, radical species and activated neutrals. The integrated studies on the fundamental physical properties that govern the plasmas seek to determine their structure and modification capabilities under specific experimental conditions. There is a requirement for identification, determination, and quantification of the surface activity of the species in the plasma. Here, we report a detailed study of hydrogenated amorphous and crystalline silicon (c-Si:H) processes to investigate the evolution of plasma parameters using a theoretical model. The deposition processes undertaken using a plasma enhanced chemical vapor deposition method are characterized by a reactive mixture of hydrogen and silane. Later, various contributions of energy fluxes on the substrate are considered and modeled to investigate their role in the growth of the microstructure of the deposited film. Numerous plasma diagnostic tools are used to compare the experimental data with the theoretical results. The film growth and microstructure are evaluated in light of deposition energy flux under different operating conditions.

Plasma engineering of silicon quantum dots and their properties through energy deposition and chemistry.

The characterization of plasma and atomic radical parameters along with the energy influx from plasma to the substrate during plasma enhanced chemical vapor deposition (PECVD) of Si quantum dot (QD) films is presented and discussed. In particular, relating to the Si QD process optimization and control of film growth, the necessity to control the deposition environment by inducing the effect of the energy of the key plasma species is realized. In this contribution, we report dual frequency PECVD processes for the low-temperature and high-rate deposition of Si QDs by chemistry and energy control of the key plasma species. The dual frequency plasmas can effectively produce a very high plasma density and atomic H and N densities, which are found to be crucial for the growth and nucleation of QDs. Apart from the study of plasma chemistry, the crucial role of the energy imparted due to these plasma activated species on the substrate is determined in light of QD formation. Various plasma diagnostics and film analysis methods are integrated to correlate the effect of plasma and energy flux on the properties of the deposited films prepared in the reactive mixtures of SiH4/NH3 at various pressures. The present results are highly relevant to the development of the next-generation plasma process for devices that rely on effective control of the QD size and film properties.

Effect of surface modifications on the bond strength of zirconia ceramic with resin cement resin.

OBJECTIVES: Purpose of this in vitro study was to evaluate the effect of surface modifications on the tensile bond strength between zirconia ceramic and resin. METHODS: Zirconia ceramic surfaces were treated with 150-µm abrasive alumina particles, 150-µm abrasive zirconia particles, argon-ion bombardment, gas plasma, and piranha solution (H2SO4:H2O2=3:1). In addition, slip casting surfaces were examined. Untreated surfaces were used as the control group. Tensile bond strengths (TBS) were measured after water storage for 3 days or 150 days with additional 37,500 thermal cycling for artificial aging. Statistical analyses were performed with 1-way and 3-way ANOVA, followed by comparison of means with the Tukey HSD test. RESULTS: After storage in distilled water for three days at 37 °C, the highest mean tensile bond strengths (TBS) were observed for zirconia ceramic surfaces abraded with 150-µm abrasive alumina particles (TBS(AAP)=37.3 MPa, TBS(CAAP)=40.4 MPa), and 150-µm abrasive zirconia particles (TBS(AZP)=34.8 MPa, TBS(CAZP)=35.8 MPa). Also a high TBS was observed for specimens treated with argon-ion bombardment (TBS(BAI)=37.8 MPa). After 150 days of storage, specimens abraded with 150-µm abrasive alumina particles and 150-µm abrasive zirconia particles revealed high TBS (TBS(AAP)=37.6 MPa, TBS(CAAP)=33.0 MPa, TBS(AZP)=22.1 MPa and TBS(CAZP)=22.8 MPa). A high TBS was observed also for specimens prepared with slip casting (TBS(SC)=30.0 MPa). A decrease of TBS was observed for control specimens (TBS(UNT)=12.5 MPa, TBS(CUNT)=9.0 MPa), specimens treated with argon-ion bombardment (TBS(BAI)=10.3 MPa) and gas plasma (TBS(GP)=11.0 MPa). A decrease of TBS was observed also for specimens treated with piranha solution (TBS(PS)=3.9 MPa, TBS(CPS)=4.1 MPa). A significant difference in TBS after three days storage was observed for specimens treated with different methods (p<0.001). Thermal cycling significantly reduced TBS for all groups (p<0.001) excluding groups: AAP(p>0.05), CAAP(p>0.05) and SC(p>0.05). However, the failure patterns of debonded specimens prepared with 150-µm abrasive zirconia particles were 96.7% cohesive. CONCLUSION: Treatment of zirconia ceramic surfaces with abrasive zirconia particles is a promising method to increase the tensile bond strength without significant damage of the ceramic surface itself. An alternative promising method is slip casting.

Effect of surface treatments on the properties and morphological change of dental zirconia.

STATEMENT OF PROBLEM: Creating a rough surface for bonding with airborne-particle abrasion with alumina may damage the surface of zirconia. Other treatment methods for creating a bonding surface without causing damage require investigation. PURPOSE: The purpose of this in vitro study was to find ways of treating the zirconia surface without causing flaws, debris, pits, microcracks, or tetragonal to monoclinic phase transformation. MATERIAL AND METHODS: Yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic surfaces were treated with gas plasma, argon-ion bombardment, 150-µm abrasive zirconia particles, and abrasive 150-µm alumina particles; untreated surfaces were used as the control group. X-ray diffraction (XRD) and confocal Raman spectroscopy were used to study the phase transformation. The roughness of specimens was measured with a confocal 3D laser scanning microscope. Modification of surface topography was analyzed with field emission scanning electron microscopy (FESEM), and the flexural strength was measured with a universal testing machine. Statistical analyses were performed with 1-way ANOVA, followed by comparison of means with the Tukey honest significant difference test. The standard deviation was calculated with descriptive statistics. RESULTS: The sintered Y-TZP ceramic used in this study showed 2 phases, tetragonal and cubic. Specimens abraded with 150-µm alumina particles showed a higher monoclinic volume fraction (VmXRD=8.68%) and roughness (Ra=0.91µm) than specimens abraded with 150-µm zirconia particles (VmXRD=1.22%, Ra=0.08µm). One-way ANOVA indicated a significance difference in roughness among groups (P<.01). No phase transformation was observed in specimens treated with argon-ion bombardment or plasma. According to the Raman results, the volume fraction of the monoclinic phase for the specimens treated with airborne-particle abrasion depended on the distance from the ceramic surfaces and decreased with the increase in this distance. A slightly higher flexural strength was observed for untreated specimens (1009 MPa), followed by specimens treated with gas plasma (1000 MPa) and those airborne-particle abraded with 150-µm zirconia particles (967 MPa). The flexural strength of other specimens was lower (940 MPa for specimens abraded with 150-µm alumina particles and 916 MPa for specimens subjected to argon-ion bombardment). One-way ANOVA analysis indicated no significant difference in flexural strengths among all groups (P>.2). FESEM measurements showed that airborne-particle abrading Y-TZP surfaces with 150-µm alumina particles caused more damage to this area than the other methods. CONCLUSIONS: Y-TZP ceramic surfaces treated with zirconia particles, argon-ion bombardment, and gas plasma were damaged less in comparison with surfaces abraded with alumina particles.

Copper-capped carbon nanocones on silicon: plasma-enabled growth control.

Controlled self-organized growth of vertically aligned carbon nanocone arrays in a radio frequency inductively coupled plasma-based process is studied. The experiments have demonstrated that the gaps between the nanocones, density of the nanocone array, and the shape of the nanocones can be effectively controlled by the process parameters such as gas composition (hydrogen content) and electrical bias applied to the substrate. Optical measurements have demonstrated lower reflectance of the nanocone array as compared with a bare Si wafer, thus evidencing their potential for the use in optical devices. The nanocone formation mechanism is explained in terms of redistribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array and passivation of carbon in narrow gaps where the access of plasma ions is hindered. Extensive numerical simulations were used to support the proposed growth mechanism.

A calorimetric probe for plasma diagnostics.

A calorimetric probe for plasma diagnostics is presented, which allows measurements of the power taken by a test substrate. The substrate can be biased and used as an electric probe in order to obtain information about the composition of the total heating power. A new calibration technique for calorimetric probes, which uses monoenergetic electrons at low pressure, has been developed for an improved accuracy. The use of the probe is exemplified with an experiment where both energetic neutral atoms and ions heat the test substrate.

An experiment for the investigation of forces on microparticles in ion beams.

A novel experiment for the study of forces on microparticles in ion beams is presented. A broad beam ion source provides a vertically upward directed beam wherein 100 microm hollow glass spheres are injected. The particles are illuminated by a diode laser and recorded with a charge-coupled device camera. From the trajectories the acceleration and the net force on the particles are determined. Information on energetic neutral atoms is achieved, which is not accessible by electrostatic methods.

Measuring the temperature of microparticles in plasmas.

Temperature sensitive features of particular phosphors were utilized for measuring the temperature T(p) of microparticles, confined in the sheath of a rf plasma. The experiments were performed under variation of argon pressure and rf power of the process plasma. T(p) has been determined by evaluation of characteristic fluorescent lines. The results for T(p) measurements are strongly dependent on rf power and gas pressure.

Microparticles in plasmas as diagnostic tools and substrates.

An interesting aspect in the research of complex (dusty) plasmas is the experimental study of the interaction of nano- and micro-particles with the surrounding plasma for diagnostic purpose. From the behaviour of the particles, local electric fields can be determined ("particles as electrostatic probes"), the energy fluxes towards the particles ("particles as thermal probes"), or reactive processes on surfaces ("particles as micro-substrates") can be studied. The behaviour of particles in front of an adaptive electrode, which allows for an efficient confinement and manipulation of the grains, has been experimentally studied in dependence on the discharge parameters and on different bias conditions of the electrode. The effect of the biased surface on the charged micro-particles has been investigated by novel particle falling experiments, which were observed by a fast camera. Furthermore, preliminary experiments on the excitation of whispering gallery modes of micro-particles trapped in a plasma sheath have been demonstrated for the first time.