Laser sintering of silver nanoparticle thin films: microstructure and optical properties

We present a method for the sintering of silver (Ag) nanoparticle thin films by millisecond pulsed laser irradiation. The microstructure of sintered thin films and sintering behaviors of nanoparticles were systematically investigated in this paper. Absorption spectra of sintered thin films showed blue-shifted surface plasmon resonances (SPR) from 500 nm to 480 nm and red-shifted from 480 nm to 550 nm when laser power was varied from 100 W to 140 W and from 140 W to 200 W, respectively. This indicates a new technique to control light absorption through joining nanoparticles with laser sintering. According to theoretical calculations based on a heat diffusion model, the melting temperature of these Ag nanoparticles was estimated to be 440 °C during laser irradiation.     

激光辐照对热退火金属/掺氟二氧化锡透明导电薄膜光电性能的影响

采用532 nm纳秒脉冲激光对热退火的铝(Al)/掺氟二氧化锡(FTO)、铜(Cu)/FTO和银(Ag)/FTO三种双层复合薄膜表面分别进行处理, 结果显示薄膜样品的光电性能都得到提高.其中, 热退火Ag/FTO薄膜的平均透光率(400–800 nm)增幅最大, 从72.6%提高到80.5%, 主要是由于其表面产生了具有减反增透作用的光栅结构.激光辐照后热退火Ag/FTO薄膜的导电性也略有提高, 其方块电阻从5.6 Ω/sq下降到5.3 Ω/sq, 原因主要是激光辐照的热效应造成的退火作用使薄膜的晶粒尺寸增大, 减少了晶界散射而使载流子迁移率提高.计算结果显示, 激光辐照后热退火Ag/FTO薄膜的品质因子从0.73×10^-2Ω^-1增大为2.16×10^-2Ω^-1, 表明其综合光电性能得到显著提高.激光辐照可同步实现薄膜表面光栅结构的制备和附加退火作用, 这为金属层复合透明导电薄膜光电性能的综合优化提供了新的思路.     

Study on the electrical and optical properties of Ag/Al-doped ZnO coatings deposited by electron beam evaporation

A layer of silver was deposited onto the surface of glass substrates, coated with AZO (Al-doped ZnO), to form Ag/AZO film structures, using e-beam evaporation techniques. The electrical and optical properties of AZO, Ag and Ag/AZO film structures were studied. The deposition of Ag layer on the surface of AZO films resulted in lowering the effective electrical resistivity with a slight reduction of their optical transmittance. Ag (11 nm)/AZO (25 nm) film structure, with an accuracy of ±0.5 nm for the thickness shows a sheet resistance as low as 5.6 ± 0.5 Ω/sq and a transmittance of about 66 ± 2%. A coating consisting of AZO (25 nm)/Ag (11 nm)/AZO (25 nm) trilayer structure, exhibits a resistance of 7.7 ± 0.5 Ω/sq and a high transmittance of 85 ± 2%. The coatings have satisfactory properties of low resistance, high transmittance and highest figure of merit for application in optoelectronics devices including flat displays, thin films transistors and solar cells as transparent conductive electrodes.     

Laser sintering of Cu paste film printed on polyimide substrate

We here show that highly conductive copper films are obtainable from Cu paste by laser sintering. The Cu paste synthesized using an organo-metallic compound was screen-printed onto polyimide substrate and the printed films were scanned by an ultraviolet laser beam at 355 nm under nitrogen atmosphere. Very compact microstructure was observed throughout the whole thickness and the sintered films were mechanically robust. Although Cu is known susceptible to oxidation, no Cu oxides were incorporated into the film during laser sintering. An electrical resistivity of 1.86 × 10⁻⁵ Ω cm was obtained. This resistivity is several orders of magnitude lower than those reported for the copper nanoparticle paste thermally sintered under N₂ or H₂ atmosphere.     

Synthesis and characterization of conductive silver ink for electrode printing on cellulose film

Silver nanoparticles with size less than 50 nm were synthesized from silver nitrate, polyvinylpyrrolidone (PVP) and ethylene glycol, where these chemicals acted as metal precursor, stabilizer and reducing agent, respectively. Then a conductive silver ink was prepared with a suitable solvent by adding a viscosifier, hydroxyethyl-cellulose (HEC), and a surfactant, diethylene glycol (DEG). The combined effect of both viscosifier and surfactant on the physical property of the silver ink was analyzed by measuring the contact angle of the silver ink on a cellulose film. Moreover, the influences of PVP molecular weight and reaction temperature on the size of the silver nanoparticles were analyzed. Then the silver ink was coated on the cellulose film by spin coating and the effects of different solvents, sintering temperatures and solid contents on its electrical resistivity were examined. It was found that, with 50 % co-solvent of deionized water and DEG and solid content of around 50 %, the silver ink exhibited the lowest resistivity. This ink can be used for inkjet printing of conductive patterns on cellulose films.     

Non-vacuum, single-step conductive transparent ZnO patterning by ultra-short pulsed laser annealing of solution-deposited nanoparticles

A solution-processable, high-concentration transparent ZnO nanoparticle (NP) solution was successfully synthesized in a new process. A highly transparent ZnO thin film was fabricated by spin coating without vacuum deposition. Subsequent ultra-short-pulsed laser annealing at room temperature was performed to change the film properties without using a blanket high temperature heating process. Although the as-deposited NP thin film was not electrically conductive, laser annealing imparted a large conductivity increase and furthermore enabled selective annealing to write conductive patterns directly on the NP thin film without a photolithographic process. Conductivity enhancement could be obtained by altering the laser annealing parameters. Parametric studies including the sheet resistance and optical transmittance of the annealed ZnO NP thin film were conducted for various laser powers, scanning speeds and background gas conditions. The lowest resistivity from laser-annealed ZnO thin film was about 4.75×10⁻² Ω cm, exhibiting a factor of 10⁵ higher conductivity than the previously reported furnace-annealed ZnO NP film and is even comparable to that of vacuum-deposited, impurity-doped ZnO films within a factor of 10. The process developed in this work was applied to the fabrication of a thin film transistor (TFT) device that showed enhanced performance compared with furnace-annealed devices. A ZnO TFT performance test revealed that by just changing the laser parameters, the solution-deposited ZnO thin film can also perform as a semiconductor, demonstrating that laser annealing offers tunability of ZnO thin film properties for both transparent conductors and semiconductors.     

Effects of metal doping on the physical properties of ZnTe thin films

Zinc telluride (ZnTe) thin films were sublimated on a glass substrate using closed space sublimation (CSS) technique. ZnTe thin films of same thickness were tailored with copper (Cu) & silver (Ag) doping, considered for comparative study. X-ray diffraction (XRD) patterns of as-deposited ZnTe thin film and doped ZnTe samples exhibited polycrystalline behavior. The preferred orientation of (111) having cubic phase was observed. XRD patterns indicated that the crystallite size had increased after silver and copper immersion in as-deposited ZnTe thin films. Scanning electron microscopy (SEM) was used to observe the change of as-deposited and doped sample's grains sizes. EDX confirmed the presence of Cu and Ag in the ZnTe thin films after doping respectively. The optical studies showed the decreasing trend in energy band gap after Cu and Ag-doping. Transmission also decreased after doping. Resistivity of as-deposited ZnTe thin film was about 10⁶ Ω cm. The resistivity was reduced to 68.97 Ω cm after Cu immersion, and 10⁴ Ω cm after Ag immersion. Raman spectra were used to check the crystallinity of as-deposited, Cu and Ag-doped ZnTe thin film samples.     

Infra-red assisted sintering of inkjet printed silver tracks on paper substrates

In this study, conductive silver features using inkjet printing have been successfully prepared and their sintering studied. Regarding conductivity, metallic inks are the most efficient available conductive inks, even if important drawbacks regarding the use of such inks in inkjet still exist. Indeed, the sintering step is an important limiting factor for the productivity and the substrate choice. An infrared (IR) drying method was experimented to optimize the sintering treatment time. Trials with glass and paper substrates were performed and proved that IR drying is interesting to optimize sintering. Indeed a similar level of resistance was obtained for conventional heating (200 °C, 5 min) and for IR radiations within a shorter treatment time (3 min). Moreover, the substrate temperature during the IR sintering treatment was controlled. The substrate appears to be a relevant parameter to optimize sintering because its thermal behaviour directly impacts on the treatment duration. And for the first time a sheet resistance of 1.9 Ω sq⁻¹ was obtained on paper substrate after only 2 min of IR treatment without any observation of substrate degradation. The evaluation of an electrical treatment on the sintering of a nanoparticle film was also performed using a corona pre-treatment. This lead appears to be interesting because the study proves that an electrical treatment can initiate the sintering of silver nanoparticles. The current flow generated by the corona electrodes certainly generates a local heating by dissipation of the conductive pattern. Finally, the solutions presented in this article allow reducing the sintering time of silver conductive inkjet inks. However mainly, it proves that using paper as substrate for such inks is now possible.     

A promising approach to conductive patterns with high efficiency for flexible electronics

A promising approach for conductive patterns with high efficiency for flexible electronics was developed by direct-writing, silver(I) solution (silver nitrate, acetate silver, etc.) with no solid particles as a conductive ink, conductive pen as a writing implement, and polyimide (PI) film as a substrate. The physical properties of the conductive ink were investigated by a dynamic contact angle system, ubbelohde viscometer and surface tension instrument. Conductive properties of silver ink film were investigated by 4-point probe, scanning electron microscope (SEM) and surface profilometer. It is demonstrated how the design of solvent composition in conductive ink affects surface morphology, and conductivity of silver ink films. It can be obtained that conductive patterns drawn on PI substrate not only have good mechanical/electrical fatigue properties, but also have low resistivity. Especially, when the sintering condition is 200 °C for 60 min, the resistivity can be down to 6.6 μΩ cm, 4.25 times the silver bulk resistivity.     

Synthesis of 10 nm Ag nanoparticle polymer composite pastes for low temperature production of high conductivity films

The conversion of silver nanoparticle (NP) paste films into highly conductive films at low sintering temperature is an important requirement for the developing areas of additive fabrication and printed electronics. Ag NPs with a diameter of ∼10 nm were prepared via an improved chemical process to produce viscous paste with a high wt%. The paste consisted of as-prepared Ag NP and an organic vehicle of ethylcellulose that was deposited on glass and Si substrates using a contact lithographic technique. The morphology and conductivity of the imprinted paste film were measured as a function of sintering temperature, sintering time and the percentage ratio of Ag NP and ethylcellulose. The morphology and conductivity were examined using scanning electron microscopy (SEM) and a two-point probe electrical conductivity measurement. The results show that the imprinted films were efficiently converted into conducting states when exposed to sintering temperature in the range of 200-240 °C, this temperature is lower than the previously reported values for Ag paste.     

Electrical properties of Sb-doped epitaxial SnO2 thin films prepared using excimer-laser-assisted metal–organic deposition

Excimer-laser-assisted metal–organic deposition (ELAMOD) was used to prepare Sb-doped epitaxial (001) SnO₂ thin films on (001) TiO₂ substrates at room temperature. The effects of laser fluence, the number of shots with the laser, and Sb content on the electrical properties such as resistivity, carrier concentration, and carrier mobility of the films were investigated. The resistivity of the Sb-doped epitaxial (001) SnO₂ thin film prepared using an ArF laser was lower than that of the film prepared using a KrF laser. The van der Pauw method was used to measure the resistivity, carrier concentration, and carrier mobility of the Sb-doped epitaxial (001) SnO₂ thin films in order to determine the effect of Sb content on the electrical resistivity of the films. The lowest resistivity obtained for the Sb-doped epitaxial (001) SnO₂ thin films prepared using ELAMOD with the ArF laser and 2 % Sb content was 2.5 × 10^?3 Ω cm. The difference between the optimal Sb concentrations and resistivities of the films produced using either ELAMOD or conventional thermal MOD was discussed.     

银纳米粒子自组装复合LB膜的结构与性质

纳米粒子的自组装和有序组装膜的结构与性质近年来受到了人们的广泛关注,纳米粒子的表面结构与性质对由其组装成的有序膜的结构与性质有直接的影响。文章报道了利用自组装技术制备的银纳米粒子与双亲有机分子的单层和多层复合LB膜,通过吸收光谱和表面增强拉曼光谱研究了银纳米粒子与吸附分子间的相互作用,探讨了复合膜的成膜特性及银纳米粒子的拉曼增强特性。十八胺/银粒子复合LB膜的吸收光谱及拉曼光谱显示,十八胺分子与银纳米粒子表面的活位通过NH₂中的氮原子以复合体的形式结合;同时,在激发光的作用下复合体可能存在光催化过程。根据银粒子复合LB膜的实验结果,十八胺和十八酸之间的反应产物在复合膜中起空间位阻作用,与银粒子表面的相互作用较弱。     

Transparent carbon nanotube coatings

Thin networks of carbon nanotubes (CNTs) are sprayed onto glass or plastic substrates in order to obtain conductive transparent coatings. Transparency and conductivity at room temperature of different CNT material are evaluated. CNT coatings maintain their properties under mechanical stress, even after folding the substrate. At a transparency of 90% for visible light we observe a surface resistivity of 1 kΩ/sq which is already a promising value for various applications.     

Deposition of ITO Nanopowder Layers on Flexible Substrate by Spin Coating Using Pulsed Nd-YAG Laser for Crystallization and Bonding

A transparent thin layer of indium–tin oxide (ITO) is coated on polyethylene terephthalate (PET) by a spin coating process. The surface is treated by a pulsed Nd-YAG laser. We investigate the effect of laser treatment on crystallization and bonding processes of the thin layer using atomic force microscope (AFM) and scanning electron microscope (SEM). The best results are obtained when the pulse frequency, duration, and energy were 1000 Hz, 0.2 to 20 ms, and 25 to 40 J, respectively. The results show that the ITO layer coated on a flexible PET substrate is conductive and transparent. The sheet resistance obtained is 0.6 kΩ, and the transparency of a 350-nm layer in the visible range is more than 83.6%. Using the Nd-YAG laser treatment, we increase the conductivity by a factor of 100 times, and higher bonding performances are achieved.     

氧氩比对SnO2/Ag/SnO2透明导电膜光电性能的影响

在室温及不同的氧氩比条件下,采用射频磁控溅射Ag层和直流磁控溅射SnO₂层,在载玻片衬底上制备出了SnO₂/Ag/SnO₂多层薄膜.用霍尔效应测试仪、四探针电阻测试仪和紫外-可见-近红外光谱仪等表征了薄膜的电学性质和光学性质.实验结果表明:当氧氩比为1:14时,所制得的薄膜的光电性质优良指数最大,为1.69×10^-2 Ω^-1;此时,薄膜的电阻率为9.8×10^-5 Ω·cm,方电阻为9.68 Ω/sq,在400~800 nm可见光区的平均光学透射率达85%;并且,在氧氩比为1:14时,利用射频磁控溅射Ag层和直流磁控溅射SnO₂层在PET柔性衬底上制备出了光电性质优良的柔性透明导电膜,其在可见光区的平均光学透过率达85%以上,电阻率为1.22×10^-4 Ωcm,方电阻为12.05 Ω/sq.     

Self-assembled silver nanoparticles: correlation between structural and surface plasmon resonance properties

We report a facile method for controllable fabrication of high-density silver nanoparticle films with a widely adjustable surface plasmon resonance (SPR) frequency, based on the gas phase cluster beam deposition. On the one hand, we can control the particle size by depositing clusters on silica substrate. Light extinction spectra of the self-assembled Ag nanoparticles with various particle sizes are characterized and show two SPRs, in which a SPR exhibits a redshift from less 400 nm to more than 570 nm with an increase in the particle size, whereas the other shows a slight position shifting. On the other hand, the inter-particle distance of the self-assembled Ag nanoparticles can also be controlled by depositing clusters on silica glass coated with Formvar film, and the SPR wavelength shows a redshift from <400 nm to more than 560 nm, which can be attributed to the increase of the fraction of closely spaced nanoparticle pairs that are near-field coupled with the deposition mass. The size and coverage-dependent SPR properties are also compared with the results from the discrete dipole approximation calculations. The present method of tailoring metallic microstructures could find important applications in plasmonics.     

Characteristic difference between ITO/ZrCu and ITO/Ag bi-layer films as transparent electrodes deposited on PET substrate

The metallic-glass film of ZrCu layer deposited by co-sputtering was utilized as the metallic layer in the bi-layer structure transparent conductive electrode of ITO/ZrCu (IZC) deposited on the PET substrate using magnetron sputtering at room temperature. In addition, the pure Ag metal layer was applied in the same structure of transparent conductive film, ITO/Ag, in comparison with the IZC film. The ZrCu layer could form a continuous and smooth film in thickness lower than 6 nm, compared with the island structure of pure Ag layer of the same thickness. The 30 nm ITO/3 nm ZrCu films could show the optical transmittance of 73% at 550 nm wavelength. The 30 nm ITO/12 nm ZrCu films could show the better sheet resistance of 20 Ω/sq, but it was still worse than that of the ITO/Ag films. It was suggested that an alloy system with lower resistivity and negative mixing heat between atoms might be another way to form a continuous layer in thickness lower than 6 nm for metal film.     

Effect of Al doping on structural,optical and electrical properties of SnO2 thin films synthesized by pulsed laser deposition

Aluminium-doped (Al = 0–5?wt.%) SnO₂ thin films with low-electrical resistivity and high optical transparency have been successfully synthesized by pulsed laser deposition technique at 500 °C. Structural, optical and electrical properties of the as-deposited and post-annealed thin films were investigated. X-ray diffraction patterns suggest that the films transform from crystalline to amorphous state with increasing aluminium content. The root mean square (R_q) surface roughness parameter, determined by atomic force microscopy decreases upon annealing of the as-deposited film. While resistivity of the film is the lowest (9.49 × 10^?4 Ω-cm) at a critical doping level of 1?wt.% Al, optical transparency is the highest (nearly 90%) in the as-deposited condition. Temperature dependence of the electrical resistivity suggests that the Mott’s variable range hopping process is the dominant carrier transport mechanism in the lower temperature range (40–135 K) for all the films whereas, thermally activated band conduction mechanism seems to account for conduction in the higher temperature region (200–300 K).     

Silver nanoparticles produced by PLD in vacuum: role of the laser wavelength used

In this work we report the results of investigation of silver (Ag) nanoparticles prepared on a silica substrate by laser ablation. Our attention was focused on the mean diameter, size distribution and optical absorption properties of nanoparticles prepared in vacuum by using different laser wavelengths. The fundamental wavelength and the second, third, and fourth harmonics of a nanosecond Nd:YAG laser were used for nanoparticles fabrication. The corresponding values of the laser fluence for each wavelength were: 0.6 J/cm² at 266 nm, 0.8 J/cm² at 355 nm, 2.8 J/cm² at 532 nm, and 2 J/cm² at 1064 nm. The Ag nanoparticles produced have mean diameters in the range from 2 nm to 12 nm as the nanoparticles’ size decreases with the decrease of the wavelength used. The presence of the Ag nanoparticles was also evidenced by the appearance of a strong optical absorption band in the measured UV-VIS spectra associated with surface plasmon resonance (SPR). A redshift and widening of the absorption peak were observed as the laser wavelength was increased. Some additional investigations were performed in order to clarify the structure of the Ag nanoparticles.     

Laser-induced synthesis of silver nanoparticles and their conjugation with protein

Partially oxidized spherical silver nanoparticles (AgNPs) of different size are prepared by pulsed laser ablation in water and directly conjugated to protein S-ovalbumin for the first time and characterized by various optical techniques. UV–Visible spectrum of AgNPs showed localized surface plasmon resonance (LSPR) peak at 396 nm which red shift after protein addition. Further the increased concentration of AgNPs resulted a decrease in intensity and broadening of S-ovalbumin peak (278 nm), which can be related to the formation of protein NPs complex caused by the partial adsorption of S-ovalbumin on the surface of AgNPs. The red shift in LSPR peak of AgNPs after mixing with S-ovalbumin and decrease in protein-characteristic peak with increased silver loading confirmed the formation of protein–AgNPs bioconjugates. The effect of laser fluence on the size of AgNPs and nanoparticle–protein conjugation in the size range 5–38 nm is systematically studied. Raman spectra reveal broken disulphide bonds in the conjugated protein and formation of Ag–S bonds on the nanoparticle surface. Fluorescence spectroscopy showed quenching in fluorescence emission intensity of tryptophan residue of S-ovalbumin due to energy transfer from tryptophan moieties of albumin to AgNPs. Besides this, small blue shift in emission peak is also noticed in presence of AgNPs, which might be due to complex formation between protein and nanoparticles. The binding constant (K) and the number of binding sites (n) between AgNPs and S-ovalbumin have been found to be 0.006 M^?1 and 7.11, respectively.