Funding for this work was provided by Defense Threat Reduction Agency contracts HDTRA1-10-1-0073: HDTRA1-13-1-0001.

Caution: Please consult Material Safety Data Sheets (MSDS) when working with these chemicals, and be aware of the other hazards such as high voltage, mechanical motion of the deposition system, and high temperatures of the hotplate and furnaces utilized.
Note: Begin this protocol with bulk chalcogenide glass, which is prepared by well-known melt-quench techniques 2.
1. Preparation of ChG Solutions
Note: Two solutions are utilized in this study, Ge<su...

<ol>
	<li>Novak, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evolution+of+the+structure+and+properties+of+solution-based+Ge23Sb7S70+thin+films+during+heat+treatment.">Evolution of the structure and properties of solution-based Ge23Sb7S70 thin films during heat treatment.</a> Mat. Res. Bull. 48, 1250-1255 (2013).</li><li>Musgraves, J. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Comparison+of+the+optical,+thermal+and+structural+properties+of+Ge-Sb-S+thin+films+deposited+using+thermal+evaporation+and+pulsed+laser+deposition+techniques.">Comparison of the optical, thermal and structural properties of Ge-Sb-S thin films deposited using thermal evaporation and pulsed laser deposition techniques.</a> Acta Materiala. 59, 5032-5039 (2011).</li><li>Zha, Y., Waldmann, M., Arnold, C. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+review+on+solution+processing+of+chalcogenide+glasses+for+optical+components.">A review on solution processing of chalcogenide glasses for optical components.</a> Opt. Mat. Exp. 3 (9), 1259-1272 (2013).</li><li>Chiles, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Low-loss,+submicron+chalcogenide+integrated+photonics+with+chlorine+plasma+etching.">Low-loss, submicron chalcogenide integrated photonics with chlorine plasma etching.</a> Appl. Phys. Lett. 106, 11110 (2015).</li><li>Hu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Demonstration+of+chalcogenide+glass+racetrack+microresonators.">Demonstration of chalcogenide glass racetrack microresonators.</a> Opt. Lett. 38 (8), 761-763 (2008).</li><li>Singh, V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mid-infrared+materials+and+devices+on+a+Si+platform+for+optical+sensing.">Mid-infrared materials and devices on a Si platform for optical sensing.</a> Sci. Technol. Adv. Mater. 15, 014603 (2014).</li><li>Novak, S., Johnston, D. E., Li, C., Deng, W., Richardson, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Deposition+of+Ge23Sb7S70+chalcogenide+glass+films+by+electrospray.">Deposition of Ge23Sb7S70 chalcogenide glass films by electrospray.</a> Thin Solid Films. 588, 56-60 (2015).</li><li>Kovalenko, M. V., Schaller, R. D., Jarzab, D., Loi, M. A., Talapin, D. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Inorganically+functionalized+PbS-CdS+colloidal+nanocrystals:+integration+into+amorphous+chalcogenide+glass+and+luminescent+properties.">Inorganically functionalized PbS-CdS colloidal nanocrystals: integration into amorphous chalcogenide glass and luminescent properties.</a> J. Am. Chem. Soc. 134, 2457-2460 (2012).</li><li>Novak, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Incorporation+of+luminescent+CdSe/ZnS+core-shell+quantum+dots+and+PbS+quantum+dots+into+solution-derived+chalcogenide+glass+films.">Incorporation of luminescent CdSe/ZnS core-shell quantum dots and PbS quantum dots into solution-derived chalcogenide glass films.</a> Opt. Mat. Exp. 3 (6), 729-738 (2013).</li><li>Lu, C., Almeida, J. M. P., Yao, N., Arnold, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fabrication+of+uniformly+dispersed+nanoparticle-doped+chalcogenide+glass.">Fabrication of uniformly dispersed nanoparticle-doped chalcogenide glass.</a> Appl. Phys. Lett. 105, 261906 (2014).</li><li>Zhao, X. -. Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhancement+of+the+performance+of+organic+solar+cells+by+electrospray+deposition+with+optimal+solvent+system.">Enhancement of the performance of organic solar cells by electrospray deposition with optimal solvent system.</a> Sol. Energ. Mat. Sol. C. 121, 119-125 (2014).</li><li>Novak, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electrospray deposition of chalcogenide glass films for gradient refractive index and quantum dot incorporation [dissertation]. , (2015).</li><li>Tolansky, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=New+contributions+to+interferometry,+with+applications+to+crystal+studies.">New contributions to interferometry, with applications to crystal studies.</a> J. Sci. Instrum. 22 (9), 161-167 (1945).</li><li>Archer, R. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determination+of+the+properties+of+films+on+silicon+by+the+method+of+ellipsometry.">Determination of the properties of films on silicon by the method of ellipsometry.</a> J. Opt. Soc. Am. 52 (9), 970-977 (1962).</li><li>Hu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Optical+loss+reduction+in+high-index-contrast+chalcogenide+glass+waveguides+via+thermal+reflow.">Optical loss reduction in high-index-contrast chalcogenide glass waveguides via thermal reflow.</a> Opt. Exp. 18 (2), 1469-1478 (2010).</li><li>Hu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exploration+of+waveguide+fabrications+from+thermally+evaporated+Ge-Sb-S+glass+films.">Exploration of waveguide fabrications from thermally evaporated Ge-Sb-S glass films.</a> Opt. Mater. 30, 1560-1566 (2008).</li><li>Song, S., Dua, J., Arnold, C. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+annealing+conditions+on+the+optical+and+structural+properties+of+spin-coated+As2S3+chalcogenide+glass+thin+films.">Influence of annealing conditions on the optical and structural properties of spin-coated As2S3 chalcogenide glass thin films.</a> Opt. Exp. 18 (6), 5472-5480 (2010).</li><li>Deng, W., Klemic, J. F., Li, X., Reed, M. A., Gomez, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Increase+of+electrospray+throughput+using+multiplexed+microfabricated+sources+for+the+scalable+generation+of+monodisperse+droplets.">Increase of electrospray throughput using multiplexed microfabricated sources for the scalable generation of monodisperse droplets.</a> J. Aerosol. Sci. 37 (6), 696-714 (2006).</li></ol>

At the beginning of a uniform thickness film deposited with serpentine motion of the spray relative to the substrate, the film thickness profile is increasing. Once the distance travelled in the y-direction exceeds the diameter of the spray (upon arrival at the substrate), the flow rate becomes approximately equivalent for every point on the substrate, and thickness uniformity is achieved. To determine the appropriate deposition parameters of a uniform thickness electrosprayed film, theoretical film thickness, T, is util...

Chalcogenide glasses (ChGs) are well-known for their broad infrared transmission and amenability to uniform thickness, blanket film deposition 1-3. On-chip waveguides, resonators, and other optical components can then be formed from this film by lithography techniques, and then subsequent polymer coating to fabricate microphotonic devices 4-5. One key application that we seek to develop is small, inexpensive, highly sensitive chemical sensing devices operating in the mid-IR, where many organic species have optical signatures 6. Microphotonic chemical sensors can be deployed in harsh environments, such as near nuclear reactors, where exposure to radiation (gamma and alpha) is likely. Hence an extensive study of the modification of optical properties of the ChG electrospray materials is critical and will be reported in another paper. In this article, electrospray film deposition of ChGs is exhibited, as it is a method only recently applied to ChGs 7.
The existing film deposition methods can be categorized into two classes: vapor deposition techniques, such as thermal evaporation of bulk ChG targets, and solution-derived techniques, such as by spin-coating a solution of ChG dissolved in an amine solvent. Generally, solution-derived films tend to result in higher loss of the light signal due to the presence of residual solvent in the film matrix 3, but a unique advantage of solution-derived techniques over vapor deposition is the simple incorporation of nanoparticles (e.g., quantum dots or QDs) prior to spin-coating 8-10. However, aggregation of nanoparticles has been observed in spin-coated films 10. In addition, while vapor deposition and spin-coating approaches are well-suited to the formation of uniform thickness, blanket films, they do not lend themselves well to localized depositions, or engineered non-uniform thickness films. Furthermore, scale-up of spin-coating is difficult because of high material waste due to run-off from the substrate, and because it is not a continuous process 11.
In order to overcome some of the limitations of current ChG film deposition techniques, we have investigated the application of electrospray to the ChG materials system. In this process, an aerosol spray can be formed of the ChG solution by applying a high voltage electric field 7. Because it is a continuous process which is compatible with roll-to-roll processing, near 100% use of material is possible, which is an advantage over spin-coating. In addition, we have proposed that isolation of single QDs in the individual ChG aerosol droplets could lead to better QD dispersion, due to the charged droplets being spatially self-dispersing by Coulombic repulsion, combined with the quicker drying kinetics of the high surface area droplets that minimize the movement of QDs due to the increasing viscosity of the droplets while in-flight 7, 12. Finally, localized deposition is an advantage that can be utilized to fabricate GRIN coatings. Explorations of both QD incorporation and GRIN fabrication of ChG with electrospray are currently underway to be submitted as a future article.
In this publication, the flexibility of electrospray is demonstrated by both localized depositions and uniform thickness films. To investigate the suitability of the films for planar photonic applications, transmission Fourier transform infrared (FTIR) spectroscopy, surface quality, thickness, and refractive index measurements are utilized.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Ethanolamine</td>
			<td>Sigma-Aldrich</td>
			<td>411000-100ML</td>
			<td>99.5% purity</td>
		</tr>
		<tr>
			<td>Si wafer</td>
			<td>University Wafer</td>
			<td>1708</td>
			<td>Double side polished, undoped</td>
		</tr>
		<tr>
			<td>Syringe</td>
			<td>Sigma-Aldrich</td>
			<td>20788</td>
			<td>Hamilton 700 series, 50 microliter volume</td>
		</tr>
		<tr>
			<td>Syringe pump</td>
			<td>Chemyx</td>
			<td>Nanojet</td>
			<td></td>
		</tr>
		<tr>
			<td>CNC milling machine</td>
			<td>MIB instruments</td>
			<td>CNC 3020</td>
			<td></td>
		</tr>
		<tr>
			<td>Power supply</td>
			<td>Acopian</td>
			<td>P015HP4</td>
			<td>AC-DC power supply, 15 kV, 4 mA</td>
		</tr>
	</tbody>
</table>

electrospray deposition of uniform thickness ge23sb7s70 and as40s60 chalcogenide glass films

Solution-based electrospray film deposition, which is compatible with continuous, roll-to-roll processing, is applied to chalcogenide glasses. Two chalcogenide compositions are demonstrated: Ge23Sb7S70 and As40S60, which have both been studied extensively for planar mid-infrared (mid-IR) microphotonic devices. In this approach, uniform thickness films are fabricated through the use of computer numerical controlled (CNC) motion. Chalcogenide glass (ChG) is written over the substrate by a single nozzle along a serpentine path. Films were subjected to a series of heat treatments between 100 &#176;C and 200 &#176;C under vacuum to drive off residual solvent and densify the films. Based on transmission Fourier transform infrared (FTIR) spectroscopy and surface roughness measurements, both compositions were found to be suitable for the fabrication of planar devices operating in the mid-IR region. Residual solvent removal was found to be much quicker for the As40S60 film as compared to Ge23Sb7S70. Based on the advantages of electrospray, direct printing of a gradient refractive index (GRIN) mid-IR transparent coating is envisioned, given the difference in refractive index of the two compositions in this study.

A schematic representation of the serpentine path utilized to obtain uniform thickness films with single nozzle electrospray is shown in Figure 2. Figure 3 shows an example transmission FTIR spectrum of a partially-cured As40S60 film made with serpentine motion of the spray, as well as the spectrum of pure ethanolamine solvent. From the information that can be obtained from the FTIR spectra such as shown in Figure 3,...

Watch this Scientific Journal Video about Electrospray Deposition of Uniform Thickness Ge23Sb7S70 and As40S60 Chalcogenide Glass Films at JoVE.com

Electrospray Deposition of Uniform Thickness Ge23Sb7S70 and As40S60 Chalcogenide Glass Films

A method of uniform thickness solution-derived chalcogenide glass film deposition is demonstrated using computer numerical controlled motion of a single-nozzle electrospray.

Electrospray Deposition of Uniform Thickness Ge23Sb7S70 and As40S60 Chalcogenide Glass Films

Solution-based electrospray film deposition, which is compatible with continuous, roll-to-roll processing, is applied to chalcogenide glasses. Two ...

The overall goal of this investigation is to develop electrospray film deposition of chalcogenide glasses for mid-infrared photonic applications, and to explore the unique flexibility of this deposition method. The main advantages of this technique are that it allows localized deposition of material with the ability to fabricate an engineered film thickness profile. This makes it possible to create a spatially-varying compositional gradient.Due to these advantages electrospray can advance the field of chip-based mid-infrared chemical sensing devices by allowing more flexible device design. To set up the deposition process, first place the end of the needle into the chalcogenide glass. Draw the solution into the syringe by setting the syringe pump to Extract Mode at a slow rate, such as 150 microliters per hour to prevent the formation of bubbles.Set the working distance between the end of the nozzle and the top of the silicon substrate by using the computer numerical control in Manual Movement Mode. Place the silicon substrate on an aluminum plate connected to the power supply ground return. Then, dispense some liquid from the syringe, utilizing the syringe pump, to allow a small volume of liquid to coat the outside surface of the nozzle.Turn the hot plate on at a surface temperature of about 75 to 100 degrees Celsius. Wait for approximately two hours to allow a film of glass to dry on the nozzle surface. Connect the direct current or DC power supply to the syringe nozzle with an electrical clip.Set the flow rate at 10 micro-liters per hour and tune the DC voltage to form a stable Taylor cone. View the spray with a high magnification camera. Once the spray is stable, start computer numerical controlled motion of the spray over the substrate to deposit the film.Use a serpentine path for uniform thickness. Use passes with a distance longer than the width of the substrate, such that the spray moves completely off of the substrate before making the next pass. This ensures that the flow rate of liquid is the same at every point on the substrate.Alternatively, use one-dimensional passes for a linear thickness profile. Subject the deposited film to a series of heat treatments under vacuum as described in the text protocol. Take a transmission Fourier Transform InfraRed, or FTIR spectrum, periodically throughout the annealing conditions.To measure the same location on the sample each time, draw an outline of the substrate on the sample stage and place it within the south line each time a measurement is taken. In the FTIR software, click Experiment Setup and type in the number of scans as 64. Click to the Bench tab and type in the scan range as 7, 000 to 500 inverse centimeters.Take a background scan with just the sample stage in the instrument by clicking on Collect Background, then place the sample on the stage and click Collect Sample to take the spectrum of the sample. To track the removal of the solvent, estimate the size of the organic absorptions in the film matrix. In the FTIR software, draw a baseline in the spectral range of interest of approximately 2, 300 to 3, 600 inverse centimeters.The software calculates the area beneath the transmission spectrum of the sample relative to the baseline designated by the user. Scratch the film with fine point tweezers until the dark substrate becomes visible amongst the lighter colored film, which typically occurs in one scratching motion with light pressure. Remove debris caused by scratching with compressed nitrogen.Load the sample into a contact profilometer and measure the thickness of the blanket films to determine the step height from film to substrate. Open Measurement Setup and type in a scan rate of 0.1 millimeters per second and a scan length of 500 microns. Locate the scratch and rotate the sample, such that the scratch is oriented in the left to right direction.Move the state, such that the crosshairs are just below the scratch, and begin the surface scan by clicking Measurement. Once the scan is finished, drag the R and M cursors so that they are both on the film surface, and click Level Two Point Linear to level the surface profile. Move one cursor to the bottom of the scratch and write down the distance between each cursor position in the Y dimension.Measure the thickness as multiple locations to obtain an average thickness and variance in the data. Determine the thickness profiles of the non-uniform thickness films by scanning the profilometer across the entire film. Use this surface profile to create a graph of film thickness versus position.Scan across the entire film by entering an appropriate scan length greater than the width of the film, usually 10 to 20 millimeters, in Measurement Setup. Place the crosshairs on the uncoated substrate on one side of the film and click Measurement, allowing the profilometer to complete the scan on the uncoated substrate on the other side of the film. Right click on the surface profile and export as a csv file.Next, measure the surface roughness with a white-light interferometer. Adjust the focus and stage tilt to generate interference fringes over the entire measurement area using the 5X objective. Take five measurements across the uniform thickness film to determine the average roughness and variance of the data.Load the sample into an ellipsometer and measure the refractive index in the range of 600 to 1, 700 nanometers wavelength. In this case, use an angle of incidence of 60 degrees, and focus the beam to a spot size of 35 microns. Representative results of electrosprayed film properties are shown here.FTIR transmission spectra of pure ethanolamine solvent and a partially cured arsenic trisulfide film with residual ethanolamine showed the transparency of the films in mid-infrared and also the method by which the solvent peak absorption area is characterized. By characterizing the solvent peak absorption area, and film thickness throughout heat treatments, the evolution of solvent removal and film densification is demonstrated. Minimal residual solvent is achieved by vacuum annealing.Following deposition and heat treatment, electrosprayed films have a generally smooth appearance. On the left is a film with a uniform thickness region deposited with a serpentine path of the spray. On the right are films made with one-dimensional motion in order to achieve controlled non-uniform thickness profiles.One-dimensional motion allows linearly-sloped film thickness profiles with film thickness and coverage area controlled by the working distance of the spray. In conclusion, electrospray is the most treated as a method of infrared transparent chalcogenide glass fume deposition with the ability to make localized depositions with engineered non-uniform thickness profiles. Electrospray of chalcogenized glass is a new tool for the field of mid-infrared microphotonics, and it is envisioned that the additional flexibility allowed by this process will lead to novel device designs.

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8.4K visualizações.  Clemson University. The overall goal of this investigation is to develop electrospray film deposition of chalcogenide glasses for mid-infrared photonic applications, and to explore the unique flexibility of this deposition method. The main advantages of this technique are that it allows localized deposition of material with the ability to fabricate an engineered film thickness profile. This makes it possible to create a spatially-varying compositional gradient.Due to these advantages electrospray can adva...