The authors acknowledge the financial support from S&#227;o Paulo Research Foundation &#8211; FAPESP &#8211; Brazil (grants 19/05620-3, 19/08019-9, 19/01671-2, 16/03484-7 and 14/13904-8) and Research Collaboration Program Newton Fund from Royal Academy of Engineering. Authors also acknowledge the technical support from B. F. da Silva, J.P. Braga, J.B. Cantuaria, G.R. de Lima and G.A. de Lima Sobrinho and Prof. Marcelo de Carvalho Borba&#8217;s group (IGCE/UNESP) for providing the filming equipment.

The protocol described in the present work is separated into: i) preparation of the electrolytic solution for anodization; ii) substrate cleaning and preparation; iii) anodization process; iv) deposition of the TFT active layer and drain/source electrodes; v) TFT electrical characterization and analysis and vi) application of ANOVA to determine the significance of the manufacturing factors in the TFT mobility.
1. Preparation of the electrolytic solution for anodization
<ol>
	<li>Perform all the procedures of the protocol inside a cleanroom or a laminar flow cabinet, to avoid dust or contaminants during the sample preparation.</li>
	<li>Prepare two solutions of tartaric acid (0.1 M) in different water/ethylene glycol volume ratios (16% and 30%), which will be used as the anodization electrolytic solution. Use the water content in the electrolytic solution as fabrication parameter of the anodized layer.</li>
	<li>In a 150 mL beaker, dissolve 1.5 g of tartaric acid into 16 mL of deionized water and 84 mL of ethylene glycol to obtain a 16% water electrolyte stock solution. For a 30% water electrolyte stock solution, use 1.5 g of tartaric acid, 30 mL of deionized water and 70 mL of ethylene glycol. Stir both solutions using a magnetic bar for 30 min.</li>
	<li>Separate about 10-20 mL of ammonium hydroxide (NH4OH) solution (as purchased, 28 &#8211; 30% NH3 in volume) in a 20 mL beaker to make the rough adjustment of the pH of the electrolytic solution.</li>
	<li>Prepare 80 mL of a diluted solution (about 2% in volume) from the original NH4OH solution to make the fine control of the pH of the electrolytic solution.</li>
	<li>Separate the electrolyte solution into a 150 mL beaker to adjust the pH of the solution.</li>
	<li>Measure the pH of the electrolytic solution using a bench pH meter. Start pipetting the more concentrated NH4OH until the pH is close to the desired pH (5 or 6).</li>
	<li>Pipette the more diluted NH4OH solution into the electrolytic solution until the pH is set in the desired value. Prepare the electrolyte solutions at pH values of 5 and 6 to study the effect on the anodization process.</li>
</ol>
2. Substrate cleaning and preparation
<ol>
	<li>Use 20 mm x 25 mm glass slides (1.1 mm thick) as substrates.</li>
	<li>Sonicate the glass slides in a heated (60 &#176;C) alkaline detergent solution (5% in deionized water) for 15 min. Rinse abundantly in deionized water and dry in clean dry air (CDA) or nitrogen.</li>
	<li>Sonicate the glass slides in acetone (ACS reagent grade or superior) for 5 min. Dry the substrates in CDA or nitrogen.</li>
	<li>Sonicate the glass slides in isopropanol (ACS reagent grade or superior) for 5 min. Dry the substrates in CDA or nitrogen.</li>
	<li>Insert the substrates into the chamber of a plasma cleaner, close the lid and evacuate the chamber using a vacuum pump.</li>
	<li>When the vacuum is achieved, switch on the RF generator at medium power (10.5 W) for 5 min. After plasma cleaning, the substrates are ready for aluminum gate deposition.</li>
</ol>
3. Aluminum gate electrode evaporation
<ol>
	<li>Insert the glass slides into mechanical shadow masks to deposit an aluminum stripe of 25 x 3 mm. This aluminum stripe will be used as the TFT gate electrode and the aluminum oxide layer formed by anodization will be the TFT dielectric layer. Example of shadow mask design for the gate electrode is presented in the supplementary files.</li>
	<li>Place the substrates with the shadow mask inside the chamber of the thermal evaporating chamber for the aluminum layer deposition. Shut the chamber. Start the chamber evacuation procedure. Wait until the chamber pressure is below 2.0 x 10-6 mbar to start the thermal evaporation.</li>
	<li>Deposit the aluminum layer. Use two different thicknesses (60 nm and 200 nm) to evaluate the effect on the dielectric layer. Use two different evaporation rates 5 &#197;/s and 15 &#197;/s to study the influence of the Al evaporation rate.</li>
	<li>Remove the samples from the evaporation chamber after aluminum evaporation.</li>
	<li>Remove the glass slides with the aluminum stripe from the masks and check if the aluminum layer was properly deposited. The electrode is ready for the anodization process.</li>
</ol>
4. Anodization process of the aluminum layer
<ol>
	<li>Attach two alligator clip connectors in a plastic lid that fits on top of the beaker. This lid can be 3-D printed.</li>
	<li>Connect one of the clip connectors to the aluminum strip of a glass slide and the other to a gold-plated stainless-steel sheet (0.8 mm thick, 20 x 25 mm). Face both electrodes towards each other with a separating distance of about 2 cm.</li>
	<li>Use approximately 150 mL of the electrolytic solution (after pH adjustment) in a 150 mL beaker. Use a small magnetic bar to stir the solution during the anodization procedure.</li>
	<li>Place the beaker on top of a magnetic stirrer with heating. Adjust the temperature to the desired value (40 &#176;C and 60 &#176;C were used in the current paper).</li>
	<li>Immerse the electrodes in the electrolytic solution by covering the beaker with the plastic lid attached to the clip connectors.</li>
	<li>Connect the aluminum electrode to the positive output and the golden-plated stainless-steel electrode to the negative output of a current/voltage source and measuring unit (SMU).</li>
	<li>Calculate the submerged area of the aluminum electrode and apply a constant current equivalent to the desired current density (we used two values 0.45 mA/cm2 and 0.65 mA/cm2) and monitor the linear increase of the voltage until the pre-set final value (we used VF = 30 V and VF = 40 V).</li>
	<li>After the final voltage is achieved, switch the SMU from the current source to the voltage source and apply a constant voltage (equal to the final voltage) during a time long enough to the current decrease next to zero (about 5 min). Use a script in Python 2.7 to automatically control the SMU during anodization process. A copy of this script is available in the supplementary files section.</li>
	<li>Remove the electrodes from the electrolytic solution, rinse abundantly with deionized water, dry with CDA or nitrogen and store the Al/Al2O3 glass substrates until use.</li>
	<li>To observe the effect of annealing on the dielectric layer, anneal the substrates in an oven at 150 &#176;C for 1 h.</li>
</ol>
5. Deposition of the ZnO Active layer
<ol>
	<li>Insert the substrates with the anodized aluminum oxide layer in appropriate mechanical shadow masks for active layer deposition.</li>
	<li>Place the substrates with the masks inside the chamber of the sputtering system. Use a ZnO (99.9%) sputtering target. Close the chamber and start the evacuating procedure.</li>
	<li>Adjust the Ar pressure to 1.2 x 10-2 Torr and the RF power to 75 W and start the ZnO deposition. Control the deposition rate at 0.5 &#197;/s. Stop the ZnO deposition when the active layer thickness achieves 40 nm.</li>
	<li>Open the chamber and remove the samples.</li>
</ol>
6. Drain and source electrodes deposition
<ol>
	<li>Insert the samples with the sputtered ZnO layer in appropriate mechanical shadow masks for TFT source/drain electrodes deposition. An appropriate drain and source electrode spacing is 100 &#181;m, with a lateral overlapping of 5 mm. A template of the drain/source mask design is supplied with the supplementary files. In such a configuration, notice that both drain and source electrodes are identical and can be interchangeable without change on the device operation.</li>
	<li>Place the samples attached to the shadow masks inside the chamber of the thermal evaporating system and start the procedure for aluminum evaporation.</li>
	<li>Deposit a 100 nm Al layer at a deposition rate of 5 &#197;/s to obtain the drain/source electrodes on top of the active layer, finishing the TFT manufacture procedure.</li>
	<li>Remove the TFTs from the evaporation chamber, check the quality of the deposited electrodes and store them protected from light until use.</li>
</ol>
7. TFT electrical characterization
<ol>
	<li>Place the TFTs on a semiconductor probe station or custom sample holder. Connect the gate, drain and source electrodes using spring-probe connectors for electrical contacts.</li>
	<li>Connect the probes to a two-channel source-measuring unit (recommended Keithley 2612B or similar). Connect the gate electrode to the &#8220;high&#8221; output/input of channel 1 and the drain (or source) electrode to the &#8220;high&#8221; output/input of channel 2. Short the &#8220;low&#8221; output/input terminals of both channels and the source (or drain) electrode, which remained disconnected.</li>
	<li>Obtain characteristic TFT curves. Obtain the output curve by applying constant voltage bias at the gate (Vg) and sweeping the drain-source voltage (VDS) and recording the drain-source current (IDS). Obtain the transfer curve by recording the drain-source current (IDS) while sweeping the gate voltage (Vg) and maintaining the drain-source voltage (VDS) constant.</li>
	<li>Plot the square root of the drain current versus the gate voltage ((IDS)1/2 vs. Vg) and obtain the carrier mobility in the saturation regime (&#181;s) from the curve slope and the threshold voltage from the x-axis intercept of the linear portion of the curve.</li>
	<li>If wanted, determine other performance parameters from the transistors curves as described elsewhere18.</li>
</ol>
8. ANOVA and influence of design factors on device performance
<ol>
	<li>Use a software to set a design of experiment (DOE) based on a Placket-Burman matrix considering 8 fabrication factors. We used Chemoface, which is a free, user-friendly software developed by Federal University of Lavras (UFLA), Brazil30.</li>
	<li>Use as factors the anodization parameters: i) the thickness of the Al layer; ii) the Al evaporation rate; iii) the water content in the electrolytic solution; iv) the temperature of the electrolyte; v) the pH of the electrolytic solution; vi) the current density during anodization; vii) the annealing temperature and viii) the final voltage of anodization.</li>
	<li>For each factor, consider two levels, as given by Table 1.</li>
	<li>Assemble the Plackett-Burman design table aided by the DOE software as given by Table 2.</li>
	<li>Prepare the TFTs varying the fabrication parameter according to the 12 generated &#8220;runs&#8221; from Table 2. Each run provides a representative variation of the fabrication factors without the need to perform all 256 (28) possible combinations for a two-level, eight-parameters experiment.</li>
	<li>Feed the DOE table from the software with the performance data from TFT characterization (e.g., TFT mobility in saturation) following the manufacturing directions of each run.</li>
	<li>Add as many replicates from different devices using the same fabrication factors to increase the number of degrees of freedom for the analysis.</li>
	<li>Perform ANOVA from the data and analyze the output to determine which anodizing parameters influence most the TFT performance.</li>
</ol>

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The authors have nothing to disclose.

The anodization process used to obtain the dielectric has a strong influence on the performance of the TFTs fabricated, keeping constant all geometrical parameters and the fabrication parameters of the active. For the TFT mobility, which is one of the most important performance parameters for TFTs, it can vary more than 2 orders of magnitude by changing the manufacturing factors in the range given by Table I. Therefore, the careful control of the anodization parameters is of great importance when fabricating devices comp...

Flexible, printed and large area electronics represent an emerging market that is expected to attract billions of dollars in investments in upcoming years. To achieve the hardware requirements for the new generation of smartphones, flat panel displays and internet-of-things (IoT) devices, there is a huge demand for materials that are lightweight, flexible and with optical transmittance in the visible spectrum without sacrificing speed and high performance. A key point is to find alternatives to amorphous silicon (a-Si) as the active material of the thin-film transistors (TFTs) used in the drive circuits of most of the current active-matrix displays (AMDs). a-Si has low compatibility to flexible and transparent substrates, presents limitations to large-area processing, and has a carrier mobility of about 1 cm2&#8729;V-1&#8729;s-1, which cannot meet the needs of resolution and refresh rate for next generation displays. Semiconducting metal oxides (SMOs) such as zinc oxide (ZnO)1,2,3, indium zinc oxide (IZO)4,5 and indium gallium zinc oxide (IGZO)6,7 are good candidates to replace a-Si as the active layer of TFTs because they are highly transparent in the visible spectrum, are compatible to flexible substrates and large area deposition and can achieve mobilities as high as 80 cm2&#8729;V-1&#8729;s-1. Moreover, SMOs can be processed in a variety of methods: RF sputtering6 , pulsed laser deposition (PLD)8, chemical vapor deposition (CVD)9, atomic layer deposition (ALD)10, spin-coating11, ink-jet printing12 and spray-pyrolysis13.
However, few challenges such as the control of intrinsic defects, air/UV stimulated instabilities and formation of semiconductor/dielectric interface localized states still need to be overcome to enable the large-scale manufacturing of circuits comprising SMO-based TFTs. Among the desired characteristics of high performance TFTs, one can mention the low power consumption, low operation voltage, low gate leakage current, threshold voltage stability and wideband frequency operation, which are extremely dependent on the gate dielectrics (and the semiconductor/insulator interface as well). In this sense, high-&#954; dielectric materials14,15,16 are particularly interesting since they provide large values of capacitance per unit area and low leakage currents using relatively thin films. Aluminum oxide (Al2O3) is a promising material for the TFT dielectric layer since it presents a high dielectric constant (from 8 up to 12), high dielectric strength, high electrical resistivity, high thermal stability and can be processed as extremely thin and uniform films by several different deposition/growth techniques15,17,18,19,20,21. Additionally, aluminum is the third most abundant element in the Earth&#8217;s crust, what means that it is easily available and relatively cheap compared to other elements used to produce high-k dielectrics.
Although deposition/growth of Al2O3 thin (below 100 nm) films can be successfully attained by techniques such as RF magnetron sputtering, chemical vapor deposition (CVD), atomic layer deposition (ALD), the growth by anodization of a thin metallic Al layer17,18,21,22,23,24,25,26 is particularly interesting for flexible electronics owing to its simplicity, low cost, low temperature, and film thickness control in nanometric scale. Besides, anodization has a great potential for roll-to-roll (R2R) processing, which can be easily adapted from processing techniques already being used at industrial level, permitting quick manufacturing upscaling.
Al2O3 growth by anodization of metallic Al can be described by the following equations
2Al + 3 / 2 02 &#8594; Al2O3&#160; &#160; &#160; (1)
2Al + 3H2O &#8594; Al2O3 + 3H2&#160; &#160; &#160; (2)
where the oxygen is provided by the dissolved oxygen in the electrolyte solution or by the adsorbed molecules at the film surface, whereas the water molecules are promptly available from the electrolyte solution. The anodized film roughness (which affects the TFT mobility due to carrier scattering at the semiconductor/dielectric interface) and the density of localized states at the semiconductor/dielectric interface (which affects the TFT threshold voltage and electrical hysteresis) are strongly dependent on anodization process parameters, to name a few: the water content, the temperature and the pH of the electrolyte24,27. Other factors related to the Al layer deposition (like evaporation rate and metal thickness) or to post-anodization processes (like annealing) can also influence the electrical performance of fabricated TFTs. The effect of these multiple factors on response parameters can be studied by varying each factor individually while keeping all other factors constant, which is an extremely time-consuming and inefficient task. Design of experiments (DOE), on the other hand, is a statistical method based on the simultaneous variation of multiple parameters, which permits the identification of the most significant factors on a system/device performance response by using a relatively reduced number of experiments28.
Recently, we have used multivariate analysis based on a Plackett-Burman29 DOE to analyze the effects of Al2O3 anodization parameters on the performance of sputtered ZnO TFTs18. The results were used to find the most significant factors for several different response parameters and applied to the optimization of the device performance changing only parameters related to the anodization process of the dielectric layer.
The current work presents the whole protocol for manufacturing TFTs using anodized Al2O3 films as gate dielectrics, as well a detailed description for the study of the influence of the multiple anodization parameters on the device electrical performance by using a Plackett-Burman DOE. The significance of the effects on TFT response parameters such as the carrier mobility is determined by performing analysis of variance (ANOVA) to the results obtained from the experiments.

<table border="0" cellpadding="0" cellspacing="0" style="width:1393px;" width="1393">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="23">
			<td height="23" style="height:23px;width:299px;">Acetone</td>
			<td style="width:212px;">LabSynth</td>
			<td style="width:161px;">A1017</td>
			<td style="width:721px;">ACS reagent grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Aluminum (Al) Wire Evaporation</td>
			<td style="width:212px;">Kurt J. Lesker Company</td>
			<td style="width:161px;">EVMAL40060</td>
			<td>1.5 mm (0.060&#34;) Dia.; 1lb; 99.99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Ammonium hydroxide solution</td>
			<td style="width:212px;">Sigma Aldrich</td>
			<td style="width:161px;">338818</td>
			<td>ACS reagent, 28.0-30.0% NH3 basis</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:299px;">Chemoface - Software to set a design of experiment (DOE)</td>
			<td style="width:212px;">Federal University of Lavras (UFLA), Brazil</td>
			<td style="width:161px;"></td>
			<td>Free software developed by Federal University of Lavras (UFLA), Brazil - http://www.ufla.br/chemoface/</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Cleaning detergent</td>
			<td style="width:212px;">Sigma Aldrich</td>
			<td style="width:161px;">Alconox</td>
			<td>Alkaline detergent for substrate cleaning</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Ethylene glycol</td>
			<td style="width:212px;">Sigma Aldrich</td>
			<td style="width:161px;">102466</td>
			<td>ReagentPlus, &#8805;99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Isopropanol</td>
			<td style="width:212px;">LabSynth</td>
			<td style="width:161px;">A1078</td>
			<td>ACS reagent grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Glass substrates</td>
			<td style="width:212px;">Sigma Aldrich</td>
			<td style="width:161px;">CLS294775X50</td>
			<td>Corning microscope slides, plain</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">L-(+)-Tartaric acid</td>
			<td style="width:212px;">Sigma Aldrich</td>
			<td style="width:161px;">T109</td>
			<td>&#8805;99.5%</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:299px;">Mechanical shadow mask for deposition of the sputtered ZnO active layer</td>
			<td style="width:212px;">Lasertools, Brazil</td>
			<td style="width:161px;">custom mask</td>
			<td>10 mm x 10 mm square.</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:299px;">Mechanical shadow mask for TFT gate electrode</td>
			<td style="width:212px;">Lasertools, Brazil</td>
			<td style="width:161px;">custom mask</td>
			<td>25 mm long stripe, 3 mm wide.</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:299px;">Mechanical shadow mask for TFT source/drain electrodes</td>
			<td style="width:212px;">Lasertools, Brazil</td>
			<td style="width:161px;">custom mask</td>
			<td>100 &#181;m stripes, separated by 100 &#181;m gap, overlapping of 5 mm</td>
		</tr>
		<tr height="29">
			<td height="29" style="height:29px;width:299px;">Plasma cleaner</td>
			<td style="width:212px;">MTI</td>
			<td style="width:161px;">PDC-32G</td>
			<td>Campact plasma cleaner with vacuum pump</td>
		</tr>
		<tr height="51">
			<td height="51" style="height:51px;width:299px;">Sputter coating system</td>
			<td style="width:212px;">HHV</td>
			<td style="width:161px;">Auto 500</td>
			<td>RF sputtering system with thickness and deposition rate control</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Stiring plate</td>
			<td style="width:212px;">Sun Valley</td>
			<td style="width:161px;">MS300</td>
			<td>Stiring plate with heating control</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Thermal evaporator</td>
			<td style="width:212px;">HHV</td>
			<td style="width:161px;">Auto 306</td>
			<td>it has a high precision sensor for measure the thickness and rate of deposition of thin films</td>
		</tr>
		<tr height="30">
			<td height="30" style="height:30px;width:299px;">Two-channel source-measuring unit</td>
			<td style="width:212px;">Keithley</td>
			<td style="width:161px;">2410</td>
			<td>Keithley model 2410 or similar/for anodization process</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Two-channel source-measuring unit</td>
			<td style="width:212px;">Keithley</td>
			<td style="width:161px;">2612B</td>
			<td>Dual channel source-measure unit (SMU) for TFT measurements</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Ultrasonic bath</td>
			<td style="width:212px;">Soni-tech</td>
			<td style="width:161px;">Soni-top 402A</td>
			<td>Ultrasonic bath with heating control</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:299px;">Zinc Oxide (ZnO) Sputtering Targets</td>
			<td style="width:212px;">Kurt J. Lesker Company</td>
			<td style="width:161px;">EJTZNOX304A3</td>
			<td>3.0&#34; Dia. x 0.250&#34; Thick; 99.9%</td>
		</tr>
	</tbody>
</table>

the effect of anodization parameters on the aluminum oxide dielectric layer of thin-film transistors

Aluminum-oxide (Al2O3) is a low cost, easily processable and high dielectric constant insulating material that is particularly appropriate for use as the dielectric layer of thin-film transistors (TFTs). Growth of aluminum-oxide layers from anodization of metallic aluminum films is greatly advantageous when compared to sophisticated processes such as atomic layer deposition (ALD) or deposition methods that demand relatively high temperatures (above 300 &#176;C) such as aqueous combustion or spray-pyrolysis. However, the electrical properties of the transistors are highly dependent on the presence of defects and localized states at the semiconductor/dielectric interface, which are strongly affected by the manufacturing parameters of the anodized dielectric layer. To determine how several fabrication parameters influence the device performance without performing all possible combination of factors, we used a reduced factorial analysis based on a Plackett-Burman design of experiments (DOE). The choice of this DOE permits the use of only 12 experimental runs of combinations of factors (instead of all 256 possibilities) to obtain the optimized device performance. The ranking of the factors by the effect on device responses such as the TFT mobility is possible by applying analysis of variance (ANOVA) to the obtained results.

Eight different aluminum oxide layer manufacture parameters were used as the fabrication factors which we used to analyze the influence on the TFT performance. These factors are enumerated in Table 1, where the corresponding &#8220;low&#8221; (-1) and &#8220;high&#8221; (+1) values for the two-level factorial DOE are presented.
For simplicity, each manufacturing factor was named by a capital letter (A, B, C, etc.) and the corresponding &#8220;low&#8221; or &#8220;high&#8221; l...

Watch this Scientific Journal Video about The Effect of Anodization Parameters on the Aluminum Oxide Dielectric Layer of Thin-Film Transistors at JoVE.com

The Effect of Anodization Parameters on the Aluminum Oxide Dielectric Layer of Thin-Film Transistors

Anodization parameters for growth of the aluminum-oxide dielectric layer of zinc-oxide thin-film transistors (TFTs) are varied to determine the effects on the electrical parameter responses. Analysis of variance (ANOVA) is applied to a Plackett-Burman design of experiments (DOE) to determine the manufacturing conditions that result in optimized device performance.

Aluminum-oxide (Al2O3) is a low cost, easily processable and high dielectric constant insulating material that is particularly appropriate for use as the ...

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8.6K Views.  São Paulo State University - UNESP. Anodization parameters for growth of the aluminum-oxide dielectric layer of zinc-oxide thin-film transistors (TFTs) are varied to determine the effects on the electrical parameter responses. Analysis of variance (ANOVA) is applied to a Plackett-Burman design of experiments (DOE) to determine the manufacturing conditions that result in optimized device performance.

Video: The Effect of Anodization Parameters on the Aluminum Oxide Dielectric Layer of Thin-Film Transistors

Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide (CdSe@CdS) nanorod photocatalysts. Seeded rods are grown using a colloidal hot-injection method and then moved to an aqueous medium by ligand exchange. CdSe@CdS nanorods, an iridium precursor and other salts are mixed and illuminated. The deposition process is initiated by absorption of photons by the semiconductor particle, which results with formation of charge carriers that are used to promote redox reactions. To insure photochemical oxidative growth we used an electron scavenger. The photogenerated holes oxidize the iridium precursor, apparently in a mediated oxidative pathway. This results in the growth of high quality crystalline iridium oxide particles, ranging from 0.5 nm to about 3 nm, along the surface of the rod. Iridium oxide grown on CdSe@CdS heterostructures was studied by a variety of characterization methods, in order to evaluate its characteristics and quality. We explored means for control over particle size, crystallinity, deposition location on the CdS rod, and composition. Illumination time and excitation wavelength were found to be key parameters for such control. The influence of different growth conditions and the characterization of these heterostructures are described alongside a detailed description of their synthesis. Of significance is the fact that the addition of iridium oxide afforded the rods astounding photochemical stability under prolonged illumination in pure water (alleviating the requirement for hole scavengers).

A protocol for the photochemical oxidative growth of small crystalline iridium oxide nanoparticles on the surface of CdSe@CdS seeded rod nanoparticles is presented.

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

The Effect of Interfacial Chemical Bonding in TiO2-SiO2 Composites on Their Photocatalytic NOx Abatement Performance

The chemical bonding of particulate photocatalysts to supporting material surfaces is of great importance in engineering more efficient and practical photocatalytic structures. However, the influence of such chemical bonding on the optical and surface properties of the photocatalyst and thus its photocatalytic activity/reaction selectivity behavior has not been systematically studied. In this investigation, TiO2 has been supported on the surface of SiO2 by means of two different methods: (i) by the in situ formation of TiO2 in the presence of sand quartz via a sol-gel method employing tetrabutyl orthotitanium (TBOT); and (ii) by binding the commercial TiO2 powder to quartz on a surface silica gel layer formed from the reaction of quartz with tetraethylorthosilicate (TEOS). For comparison, TiO2 nanoparticles were also deposited on the surfaces of a more reactive SiO2 prepared by a hydrolysis-controlled sol-gel technique as well as through a sol-gel route from TiO2 and SiO2 precursors. The combination of TiO2 and SiO2, through interfacial Ti-O-Si bonds, was confirmed by FTIR spectroscopy and the photocatalytic activities of the obtained composites were tested for photocatalytic degradation of NO according to the ISO standard method (ISO 22197&#8722;1). The electron microscope images of the obtained materials showed that variable photocatalyst coverage of the support surface can successfully be achieved but the photocatalytic activity towards NO removal was found to be affected by the preparation method and the nitrate selectivity is adversely affected by Ti-O-Si bonding.

The Effect of Interfacial Chemical Bonding in TiO2-SiO2 Composites on Their Photocatalytic NOx Abatement Performance

The focus of the present work is to establish means to generate and quantify levels of Ti-O-Si linkages and to correlate these with the photocatalytic properties of the supported TiO2.

The chemical bonding of particulate photocatalysts to supporting material surfaces is of great importance in engineering more efficient and practical ...

Chemical Synthesis of Porous Barium Titanate Thin Film and Thermal Stabilization of Ferroelectric Phase by Porosity-Induced Strain

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its well-balanced ferroelectricity, piezoelectricity, and dielectric constant. In addition, BT does not contain any toxic elements. Therefore, it is considered to be an eco-friendly material, which has attracted considerable interest as a replacement for lead zirconate titanate (PZT). However, bulk BT loses its ferroelectricity at approximately 130 &#176;C, thus, it cannot be used at high temperatures. Because of the growing demand for high-temperature ferroelectric materials, it is important to enhance the thermal stability of ferroelectricity in BT. In previous studies, strain originating from the lattice mismatch at hetero-interfaces has been used. However, the sample preparation in this approach requires complicated and expensive physical processes, which are undesirable for practical applications.
In this study, we propose a chemical synthesis of a porous material as an alternative means of introducing strain. We synthesized a porous BT thin film using a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles were used as an organic template. Through a series of studies, we clarified that the introduction of pores had a similar effect on distorting the BT crystal lattice, to that of a hetero-interface, leading to the enhancement and stabilization of ferroelectricity. Owing to its simplicity and cost effectiveness, this fabrication process has considerable advantages over conventional methods.

Here, we present a protocol for the synthesis of porous barium titanate (BaTiO3) thin film by a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles are used as an organic template.

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its ...

The Effect of Charging and Discharging Lithium Iron Phosphate-graphite Cells at Different Temperatures on Degradation

The effect of charging and discharging lithium iron phosphate-graphite cells at different temperatures on their degradation is evaluated systematically. The degradation of the cells is assessed by using 10 charging and discharging temperature permutations ranging from -20 &#176;C to 30 &#176;C. This allows an analysis of the effect of charge and discharge temperatures on aging, and their associations. A total of 100 charge/discharge cycles were carried out. Every 25 cycles a reference cycle was performed to assess the reversible and irreversible capacity degradation. A multi-factor analysis of variance was used, and the experimental results were fitted showing: i) a quadratic relationship between the rate of degradation and the temperature of charge, ii) a linear relationship with the temperature of discharge, and iii) a correlation between the temperature of charge and discharge. It was found that the temperature combination for charging at +30 &#176;C and discharging at -5 &#176;C led to the highest rate of degradation. On the other hand, the cycling in a temperature range from -20 &#176;C to 15 &#176;C (with various combinations of temperatures of charge and discharge), led to a much lower degradation. Additionally, when the temperature of charge is 15 &#176;C, it was found that the degradation rate is nondependent on the temperature of discharge.

This article describes the effect of dissimilar charging/discharging temperatures on the degradation of lithium iron phosphate-graphite pouch cells, aiming at simulating close to real case scenarios. In total, 10 temperature combinations are investigated in the range -20 to 30 &#176;C in order to analyze the impact of temperature on degradation.

The effect of charging and discharging lithium iron phosphate-graphite cells at different temperatures on their degradation is evaluated systematically. ...

The Effect of Ultraviolet Radiation on the Chemical Bath Deposition of Bis(thiourea) Cadmium Chloride Crystals and the Subsequent CdS Obtention

In this work, the effects on the preparation of bis(thiourea) cadmium chloride crystals when illuminated with ultraviolet (UV) light at a wavelength of 367 nm using the chemical bath deposition technique are studied comparatively. Two experiments are performed to make a comparison: one without UV light and the other with the aid of UV light. Both experiments are performed under equal conditions, at a temperature of 343 K and with a pH of 3.2. The precursors used are cadmium chloride (CdCl2) and thiourea [CS(NH2)2], which are dissolved in 50 mL of deionized water with an acidic pH. In this experiment, the interaction of electromagnetic radiation is sought at the moment the chemical reaction is carried out. The results demonstrate the existence of an interaction between the crystals and the UV light; the UV light assistance causes crystal growths in an acicular shape. Also, the final product obtained is cadmium sulfide and shows no evident difference when synthesized with or without the use of UV light.

The Effect of Ultraviolet Radiation on the Chemical Bath Deposition of Bisthiourea Cadmium Chloride Crystals and the Subsequent CdS Obtention

This article presents a protocol for the synthesis of bis(thiourea) cadmium chloride crystals by chemical bath deposition. Two experiments are described: one aided by ultraviolet light compared to one without ultraviolet light.

In this work, the effects on the preparation of bis(thiourea) cadmium chloride crystals when illuminated with ultraviolet (UV) light at a wavelength of ...

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks are effective in gas storage and heterogeneous catalysis, but typical synthesis methods result in loose powders that are difficult to incorporate into smart materials. We demonstrate a method of first coating fabrics with ALD metal oxides, resulting in conformal films of MOF on the fabrics during solvothermal synthesis.

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic polymers, with the aim of photo-activating oxygen-evolving manganese oxide catalysts, which are important components in artificial photosynthesis. The cross-linking technique was applied to obtain a self-standing membrane with a high PW12O403- content. Incorporation and structure retention of PW12O403- within the polymer matrix were confirmed by FT-IR and micro-Raman spectroscopy, and optical characteristics were investigated by UV-Vis spectroscopy, which revealed successful construction of the metal-to-metal charge transfer (MMCT) unit. After deposition of MnOx oxygen evolving catalysts, photocurrent measurements under visible light irradiation verified the sequential charge transfer, Mn &#8594; MMCT unit &#8594; electrode, and&#160;the photocurrent intensity was consistent with the redox potential of the donor metal (Ce or Co). This method provides a new strategy for preparing integrated systems involving catalysts and photon-absorption parts for use with photo-functional materials.

Here, we present a protocol to prepare charge transfer chromophores based on a polyoxometalate/polymer composite membrane.

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...

Extraction of Lignin with High &#946;-O-4 Content by Mild Ethanol Extraction and Its Effect on the Depolymerization Yield

Lignin valorization strategies are a key factor for achieving more economically competitive biorefineries based on lignocellulosic biomass. Most of the emerging elegant procedures to obtain specific aromatic products rely on the lignin substrate having a high content of the readily cleavable &#946;-O-4 linkage as present in the native lignin structure. This provides a miss-match with typical technical lignins that are highly degraded and therefore are low in &#946;-O-4 linkages. Therefore, the extraction yields, and the quality of the obtained lignin are of utmost importance to access new lignin valorization pathways. In this manuscript, a simple protocol is presented to obtain lignins with high &#946;-O-4 content by relatively mild ethanol extraction that can be applied to different lignocellulose sources. Furthermore, analysis procedures to determine the quality of the lignins are presented together with a depolymerization protocol that yields specific phenolic 2-arylmethyl-1,3-dioxolanes, which can be used to evaluate the obtained lignins. The presented results demonstrate the link between lignin quality and potential for the lignins to be depolymerized into specific monomeric aromatic chemicals. Overall, the extraction and depolymerization demonstrates a trade-off between the lignin extraction yield and the retention of the native aryl-ether structure and thus the potential of the lignin to be used as the substrate for the production of chemicals for higher-value applications.

Extraction of Lignin with High &amp;#946;-O-4 Content by Mild Ethanol Extraction and Its Effect on the Depolymerization Yield

Here, we present a protocol to perform ethanol extraction of lignin from several biomass sources. The effect of the extraction conditions on the lignin yield and &#946;-O-4 content are presented. Selective depolymerization is performed on the obtained lignins to obtain high aromatic monomer products.

Lignin valorization strategies are a key factor for achieving more economically competitive biorefineries based on lignocellulosic biomass. Most of the ...

Electrochemical Roughening of Thin-Film Platinum Macro and Microelectrodes

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries of the metal. Using this method, a crack free, thin-film macroelectrode surface with up to 40 times increase in active surface area was obtained. The roughening is easy to do in a standard electrochemical characterization laboratory and incudes the application of voltage pulses followed by extended application of a reductive voltage in a perchloric acid solution. The protocol includes the chemical and electrochemical preparation of both a macroscale (1.2 mm diameter) and microscale (20 &#181;m diameter) platinum disc electrode surface, roughening the electrode surface and characterizing the effects of surface roughening on electrode active surface area. This electrochemical characterization includes cyclic voltammetry and impedance spectroscopy and is demonstrated for both the macroelectrodes and the microelectrodes. Roughening increases electrode active surface area, decreases electrode impedance, increases platinum charge injection limits to those of titanium nitride electrodes of same geometry and improves substrates for adhesion of electrochemically deposited films.

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries. The electrochemical techniques of cyclic voltammetry and impedance spectroscopy are demonstrated to characterize these electrode surfaces.

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries ...