AJP was funded by the EPSRC Soft Nanotechnology platform grant EP/E046215/1. The neutron experiments were supported by the STFC via the allocation of experimental time to use OffSpec (RB 1110285).

1. Sample Preparation
<ol>
	<li>Clean the silicon substrates by placing 2 in&#160;silicon wafers that are 4 mm thick in oxygen plasma for 10 min.</li>
	<li>Spincoat the first layer on the substrates
	<ol>
		<li>Filter the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) through a 0.45 &#181;m PTFE filter (PALL).</li>
		<li>Use approximately 0.5 ml for each sample to spin coat a PEDOT:PSS thin film onto the two clean substrates at 5,000 rpm spinning for 60 sec.</li>
		<li>Dry each substrate for 10 min in an oven at 70 &#176;C.</li>
	</ol>
	</li>
	<li>Prepare the blend solution for the second layer
	<ol>
		<li>Dissolve some poly(3-hexylthiophene-2,5-diyl) (P3HT) in chlorobenzene at a concentration of 50 mg/ml.</li>
		<li>Prepare a solution of PCBM also in chlorobenzene at a concentration of 50 mg/ml.</li>
		<li>Mix the two solutions in a proportion of 1:0.7 P3HT:PCBM.</li>
		<li>Filter the mixed solution through a 0.45 &#181;m PTFE filter.</li>
	</ol>
	</li>
	<li>Spincoat second layer by depositing approximately 100 &#181;l of the P3HT:PCBM solution onto the PEDOT:PSS coated substrates and then spin at 2,000 rpm for 30 sec to form the second layer.</li>
	<li>Leave one sample as cast and thermally anneal the other for 1 hr at 150 &#176;C in an oven. This results in the growth of the large PCBM crystallites on the thin film surface.</li>
</ol>
2. Sample Characterization by Microscopy
<ol>
	<li>Optical microscopy
	<ol>
		<li>Take an optical microscopy image of both samples using a 40X microscope objective on an optical microscope operating in reflection mode, capturing the images using a CCD camera.</li>
		<li>Record a calibration image of a sample of known length at the same magnification used for the step 2.1.1</li>
		<li>Calculate the pixel size in microns for the images by determining the number of pixels for the sample of known size.</li>
		<li>Use this know pixel size to calibrate the images using any readily available microscopy software. An example of a calibrated optical microscopy image is shown in Figure 1.</li>
	</ol>
	</li>
	<li>Atomic Force Microscopy
	<ol>
		<li>Take an atomic force microscope (AFM) image of the two samples.</li>
		<li>Analyze the data using any readily available scanning probe software to generate line profile figures like those presented in Figure 1.</li>
	</ol>
	</li>
</ol>
3. SERGIS Experiment
<ol>
	<li>Select a suitable reference sample to provide the reference polarization P0, which enables the data acquired from the sample of interest data to be normalized.</li>
	<li>Align the sample and reference sample
	<ol>
		<li>Place all three samples on a positioning table; this can be translated across the neutron beam so each sample can be placed in the beam in turn.</li>
		<li>Position the P0 reference sample in the beam by translating the sample table.</li>
		<li>Align the P0 reference sample to an angular accuracy of &#60;0.005&#176; using standard reflection alignment methods.</li>
		<li>Place the sample of interest in the neutron beam by translating the sample table.</li>
		<li>Align both the sample of interest to an angular accuracy of &#60;0.005&#176; using standard reflection alignment methods.</li>
		<li>Repeat this alignment process for all samples of interest to be measured.</li>
	</ol>
	</li>
	<li>Tune the SERGIS instrument so it is in echo mode
	<ol>
		<li>Set up the dedicated off-specular reflectometer OffSpec at the ISIS Pulsed Neutron and Muon Source (Oxfordshire, UK) to produce wavelengths from 2-14 &#197;. Further details of the set up used can be found here10.</li>
		<li>Tune the instrument to balance the total number of neutron precessions in each arm of the instrument by scanning the current in part of the guide field arrangement. This is achieved by setting the strength and inclination of the magnetic fields within the encoding arms of the instrument, which are defined by the distance between the RF spin flippers.</li>
	</ol>
	</li>
	<li>Set the angle of grazing incidence by tilting the sample table so the neutron beam is incident upon the P0 sample (for this experiment at an angle of 0.3&#176;).</li>
	<li>Block the directly transmitted neutron beam from reaching the detector in order to prevent saturation problems.</li>
	<li>Measure the samples
	<ol>
		<li>Move the sample translation stage so the reference sample is once again in the neutron beam and measure the scattered neutron intensity as a function of position on a vertically oriented linear scintillator detector for the reference sample. Measure both spin up and spin down orientations by flipping the spin of the scattered beam immediately before the analyzer. Typically this is done for a period of about 1 hr. This enables the polarization to be determined as well as the scattered intensity for both settings.</li>
		<li>Translate the sample stage so as to measure the first of the samples of interest, again recording both spin up and spin down orientations as a function of position using a vertically oriented linear scintillator detector for a period of about 1 hr.</li>
		<li>Repeat steps 3.6.1 and 3.6.2 until sufficiently good counting statistics for this measurement have been obtained. Typically this is about 8 hr/sample in total.</li>
		<li>Repeat steps 3.6.1-3.6.3 for any further samples that need to be measured.</li>
	</ol>
	</li>
	<li>The collected data consists of both spin up and spin down 2D intensity maps for each sample. Calculate the polarization for each pixel in the 2D data sets by using the formula 
	<img alt="" height="51" src="/files/ftp_upload/51129/51129_3.7_equation.png" width="103" /> 
	where P is the polarization and Iup&#160;and Idown&#160;are the measured spin up and spin down intensities respectively.</li>
	<li>Normalize the data sets acquired for the samples of interest using the P0 reference sample data collected to produce a normalized polarization intensity map according to the formula 
	<img alt="" height="49" src="/files/ftp_upload/51129/51129_3.8_equation.png" width="116" /> 
	where PNormalized&#160;is the determined polarization calculated and PSample is the sample polarization value and P0 is the polarization measured using the P0 reference sample.</li>
	<li>Integrate the SERGIS data over a suitable range
	<ol>
		<li>Select the area (i.e. the pixel range in the normalized polarization plot) for the SERGIS data integration. This area should be selected so as to avoid swamping the desired SERGIS signal by any potential polarization inhomogeneities resulting from imperfections in the field line-integrals. The available Q space that the SERGIS signal may be integrated over is effectively limited to a series of discrete Q values at any given spin-echo length configuration, where Q is the momentum transfer vector i.e. the change in momentum of a neutron after interacting with the sample</li>
		<li>Reduce the 2D data by integrating the normalized polarization to get the SERGIS correlation function G(y) which has been defined previously5. Strictly G(y) should be integrated to infinity over both Q vectors perpendicular to y, however, for experimental reasons the integration area is limited to selected detected intensity above the sample horizon.</li>
	</ol>
	</li>
	<li>Compensate for different scattering length densities at different wavelengths by treating the data in a similar manner to spin echo small angle neutron scattering data by plotting the data in the form: 
	<img alt="" height="65" src="/files/ftp_upload/51129/51129_3.10_equation.png" width="127" /> 
	where &#955; is the spin echo length in nm and may be readily calculated using y = &#945;&#955;2 , where &#945; is a constant determined using calibrated constants for the given instrument setup11.</li>
</ol>

<ol>
	<li>Mezei, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Neutron+spin+echo:+A+new+concept+in+polarized+thermal+neutron+techniques.">Neutron spin echo: A new concept in polarized thermal neutron techniques.</a> Zeitschriftf&#252;r Physik A Hadrons Nuclei. 255, 146-160 (1972).</li><li>Falus, P., Vorobiev, A., Krist, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Test+of+a+two-dimensional+neutron+spin+analyzer.">Test of a two-dimensional neutron spin analyzer.</a> Physica B Condens. Matter. Mater. Phys. , 385-386 (2006).</li><li>Ashkar, R., 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=Dynamical+theory+calculations+of+spin-echo+resolved+grazing-incidence+scattering+from+a+diffraction+grating.">Dynamical theory calculations of spin-echo resolved grazing-incidence scattering from a diffraction grating.</a> J. Appl. Crystallogr. 43 (3), 455-465 (2010).</li><li>Ashkar, R., 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=Dynamical+theory:+Application+to+spin-echo+resolved+grazing+incidence+scattering+from+periodic+structures.">Dynamical theory: Application to spin-echo resolved grazing incidence scattering from periodic structures.</a> J. Appl. Phys. 110 (10), (2011).</li><li>Pynn, R., Ashkar, R., Stonaha, P., Washington, <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A.L.,Some+recent+results+using+spin+echo+resolved+grazing+incidence+scattering.">A.L.,Some recent results using spin echo resolved grazing incidence scattering.</a> SERGIS). hysica B Condens. Matter. Mater. Phys. 406 (12), 2350-2353 (2011).</li><li>Ashkar, R., 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=Spin-Echo+Resolved+Grazing+Incidence+Scattering+(SERGIS)+at+Pulsed+and+CW+Neutron+Sources.">Spin-Echo Resolved Grazing Incidence Scattering (SERGIS) at Pulsed and CW Neutron Sources.</a> J. Phy. Conf. Ser. 251 (1), (2010).</li><li>Vorobiev, A., 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=Phase+and+microphase+separation+of+polymer+thin+films+dewetted+from+Silicon-A+spin-echo+resolved+grazing+incidence+neutron+scattering+study.">Phase and microphase separation of polymer thin films dewetted from Silicon-A spin-echo resolved grazing incidence neutron scattering study.</a> J. Phys. Chem. B. 115 (19), 5754-5765 (2011).</li><li>Major, 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=A+spin-echo+resolved+grazing+incidence+scattering+setup+for+the+neutron+interrogation+of+buried+nanostructures.">A spin-echo resolved grazing incidence scattering setup for the neutron interrogation of buried nanostructures.</a> Rev. Sci. Instrum. 80 (12), (2009).</li><li>Parnell, A. J., Dalgliesh, R. M., Jones, R. A. L., Dunbar, A. D. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+neutron+spin+echo+resolved+grazing+incidence+scattering+study+of+crystallites+in+organic+photovoltaic+thin+films.">A neutron spin echo resolved grazing incidence scattering study of crystallites in organic photovoltaic thin films.</a> Appl. Phys. Lett. 102, (2013).</li><li>Dalgliesh, R. M., Langridge, S., Plomp, J., De Haan, V. O., Van Well, A. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Offspec,+the+ISIS+spin-echo+reflectometer.+hysica+B+Condens..">Offspec, the ISIS spin-echo reflectometer. hysica B Condens..</a> Matter. Mater. Phys. 406 (12), 2346-2349 (2011).</li><li>Krouglov, T., de Schepper, I. M., Bouwman, W. G., Rekveldt, M. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Real-space+interpretation+of+spin-echo+small-angle+neutron+scattering.">Real-space interpretation of spin-echo small-angle neutron scattering.</a> J. Appl. Crystallogr. 36, 117-124 (2003).</li><li>Brady, M. A., Su, G. M., Chabinyc, M. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+progress+in+the+morphology+of+bulk+heterojunctionphotovoltaics.">Recent progress in the morphology of bulk heterojunctionphotovoltaics.</a> Soft Matter. 7 (23), 11065-11077 (2011).</li><li>Huang, Y. -. C., 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=Study+of+the+effect+of+annealing+process+on+the+performance+of+P3HT/PCBM+photovoltaic+devices+using+scanning-probe+microscopy..">Study of the effect of annealing process on the performance of P3HT/PCBM photovoltaic devices using scanning-probe microscopy..</a> Solar Energy Mater. Solar Cells. 93 (6-7), 888-892 (2009).</li><li>Parnell, A. 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=Depletion+of+PCBM+at+the+Cathode+Interface+in+P3HT/PCBM+Thin+Films+as+Quantified+via+Neutron+Reflectivity+Measurements.">Depletion of PCBM at the Cathode Interface in P3HT/PCBM Thin Films as Quantified via Neutron Reflectivity Measurements.</a> Adv. Mater. 22 (22), 2444-2447 (2010).</li></ol>

The author Robert Dalgliesh is an employee of the ISIS Pulsed Neutron and Muon Source that hosts the instrument used in this experiment.

The microscopy data in Figure 1 clearly shows that before annealing the P3HT:PCBM thin film is flat and smooth and after thermal annealing there are many large irregular PCBM crystallites present on the surface with lateral dimensions ranging between about 1-10 &#181;m. This is attributed to PCBM migration towards the top surface of the film and subsequent aggregation to form large crystallites. A strong SERGIS signal associated with scattering from PCBM crystallites in the annealed sample is seen in <st...

The SERGIS technique aims to be able to yield unique structural information not accessible using other scattering or microscopy techniques from thin film samples. Microscopy techniques are typically surface limited or require significant alteration/sample preparation to view internal structures. Conventional scattering techniques such as reflectivity can provide detailed information about buried sample structures as a function of depth within the thin film but cannot probe structure in the plane of the thin film easily. Ultimately it is hoped that SERGIS will enable this lateral structure to be probed even when buried within the thin film sample. The representative results presented here demonstrate that it is possible to observe a SERGIS signal from irregular sample features and that the measured signal can be correlated with a characteristic length scale associated with the features present in the sample, as confirmed by conventional microscopy techniques.
Inelastic spin echo techniques were developed by Mezei&#160;et al.1&#160;in the 1970s. Since then the SERGIS technique (which is an extension of the ideas of Mezei&#160;et al.) has been successfully demonstrated experimentally using a variety of samples such as highly regular diffraction gratings2-6 and circular de-wetted polymer droplets7. A dynamical theory has been developed by Pynn and coworkers to model the strong scattering from highly regular samples3-6,8. This work has highlighted many practical aspects to be considered when performing this type of measurement and has led to a constant dialogue within a small multinational community.
Good results from SERGIS experiments will most likely be obtained if the sample being measured consists of a thin film on a flat substrate and contains scattering features with a high density of moderately sized features (30 nm to 5 &#181;m) that scatter neutrons strongly, as demonstrated by the authors9. Unlike other established reflectivity techniques that probe the sample as a function of depth, the SERGIS technique has the advantage that it can probe structures in the plane of the sample surface. Furthermore, the use of spin-echo removes the requirement to tightly collimate the neutron beam in order to obtain either high spatial or energy resolution, consequently significant flux gains can be achieved. This is particularly relevant for grazing incidence geometries that are significantly flux limited because of the need to collimate the beam strongly in one direction. Using the OffSpec instrument it should therefore be possible to probe length scales from 30 nm to 5 &#181;m in both bulk and surface structures.

<table border="0" cellpadding="0" cellspacing="0" width="605">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Silicon 2 in silicon substrates</td>
			<td style="width:103px;">Prolog</td>
			<td style="width:119px;"></td>
			<td style="width:167px;">4 mm thick polished one side</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Oxygen plasma</td>
			<td style="width:103px;">Diener</td>
			<td style="width:119px;"></td>
			<td>Oxygen plasma cleaning system to clean substrates prior to coating</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)</td>
			<td style="width:103px;">Ossila</td>
			<td style="width:119px;"></td>
			<td>PEDOT:PSS conductive polymer layer for organic photovoltaic samples</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">0.45 &#956;m PTFE filter</td>
			<td style="width:103px;">Sigma Aldrich</td>
			<td style="width:119px;"></td>
			<td>Filer to remove aggregates from PEDOT:PSS and P3HT solutions</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Chlorobenzene</td>
			<td style="width:103px;">Sigma Aldrich</td>
			<td style="width:119px;"></td>
			<td>Solvent for P3HT</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Poly(3-hexylthiophene-2,5-diyl)</td>
			<td style="width:103px;">Ossila</td>
			<td style="width:119px;"></td>
			<td>P3HT - polymer used in polymer photovoltaics</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Spin Coater</td>
			<td style="width:103px;">Laurell</td>
			<td style="width:119px;"></td>
			<td>Deposition system for making flat thin polymer films</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Vacuum Oven</td>
			<td style="width:103px;">Binder</td>
			<td style="width:119px;"></td>
			<td>Oven fro annealing samples after preparation</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Nikon Eclipse E600 optical microscope</td>
			<td style="width:103px;">Nikon</td>
			<td style="width:119px;"></td>
			<td>Microscope</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Veeco Dimension 3100 AFM</td>
			<td style="width:103px;">Veeco</td>
			<td style="width:119px;"></td>
			<td>AFM</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Tapping mode tips (~275 kHz)</td>
			<td style="width:103px;">Olympus</td>
			<td style="width:119px;"></td>
			<td>AFM tips</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Quartz Disc</td>
			<td style="width:103px;"></td>
			<td style="width:119px;"></td>
			<td>Refrence samples for SERGIS measurement</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Spin Echo off-specular reflectometer</td>
			<td colspan="2">OffSpec at the ISIS Pulsed Neutron and Muon Source (Oxfordshire, UK)</td>
			<td>Produces pulsed neutrons 2-14 &#197;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Neutron Detector</td>
			<td style="width:103px;">Offspec</td>
			<td style="width:119px;"></td>
			<td>vertically oriented linear scintillator detector</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">RF spin flippers</td>
			<td style="width:103px;">Offspec</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Magnetic Field Guides</td>
			<td style="width:103px;">Offspec</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Data Manipulation Software</td>
			<td style="width:103px;">Mantid</td>
			<td style="width:119px;"></td>
			<td><a href="http://www.mantidproject.org/Main_Page">http://www.mantidproject.org/Main_Page</a></td>
		</tr>
	</tbody>
</table>

using neutron spin echo resolved grazing incidence scattering to investigate organic solar cell materials

The spin echo resolved grazing incidence scattering (SERGIS) technique has been used to probe the length-scales associated with irregularly shaped crystallites. Neutrons are passed through two well defined regions of magnetic field; one before and one after the sample. The two magnetic field regions have opposite polarity and are tuned such that neutrons travelling through both regions, without being perturbed, will undergo the same number of precessions in opposing directions. In this case the neutron precession in the second arm is said to &#34;echo&#34; the first, and the original polarization of the beam is preserved. If the neutron interacts with a sample and scatters elastically the path through the second arm is not the same as the first and the original polarization is not recovered. Depolarization of the neutron beam is a highly sensitive probe at very small angles (&#60;50&#160;&#956;rad) but still allows a high intensity, divergent beam to be used. The decrease in polarization of the beam reflected from the sample as compared to that from the reference sample can be directly related to structure within the sample.
In comparison to scattering observed in neutron reflection measurements the SERGIS signals are often weak and are unlikely to be observed if the in-plane structures within the sample under investigation are dilute, disordered, small in size and polydisperse or the neutron scattering contrast is low. Therefore, good results will most likely be obtained using the SERGIS technique if the sample being measured consist of thin films on a flat substrate and contain scattering features that contains a high density of moderately sized features (30 nm to 5 &#181;m) which scatter neutrons strongly or the features are arranged on a lattice. An advantage of the SERGIS technique is that it can probe structures in the plane of the sample.

The representative results from samples of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and poly(3-hexylthiophene-2,5-diyl) (P3HT) presented here are of significant interest because of their widespread application as bulk hetero-junction materials in organic photovoltaic cells12,13. Typically during the fabrication of an organic photovoltaic device, a P3HT:PCBM blend solution is spin-cast from a blend solution to form a thin film on a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) coa...

Watch this Scientific Journal Video about Using Neutron Spin Echo Resolved Grazing Incidence Scattering to Investigate Organic Solar Cell Materials at JoVE.com

Using Neutron Spin Echo Resolved Grazing Incidence Scattering to Investigate Organic Solar Cell Materials

Progress has been made in utilizing spin echo resolved grazing incidence scattering (SERGIS) as a neutron scattering technique to probe the length-scales in irregular samples. Crystallites of [6,6]-phenyl-C61-butyric acid methyl ester have been probed using the SERGIS technique and the results confirmed by optical and atomic force microscopy.

The spin echo resolved grazing incidence scattering (SERGIS) technique has been used to probe the length-scales associated with irregularly shaped ...

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6.8K 次观看.  University of Sheffield. 利用自旋回声解决放牧发生率散射（SERGIS）作为中子散射技术，探测不规则样品的长度尺度方面取得了进展。使用SERGIS技术对[6，6]-苯-C61-丁酸甲基酯的晶体进行了探测，结果经光学和原子力显微镜确认。

视频: Using Neutron Spin Echo Resolved Grazing Incidence Scattering to Investigate Organic Solar Cell Materials

Angle-resolved Photoemission Spectroscopy At Ultra-low Temperatures

The physical properties of a material are defined by its electronic structure. Electrons in solids are characterized by energy (&omega;) and momentum (k) and the probability to find them in a particular state with given &omega; and k is described by the spectral function A(k, &omega;). This function can be directly measured in an experiment based on the well-known photoelectric effect, for the explanation of which Albert Einstein received the Nobel Prize back in 1921. In the photoelectric effect the light shone on a surface ejects electrons from the material. According to Einstein, energy conservation allows one to determine the energy of an electron inside the sample, provided the energy of the light photon and kinetic energy of the outgoing photoelectron are known. Momentum conservation makes it also possible to estimate k relating it to the momentum of the photoelectron by measuring the angle at which the photoelectron left the surface. The modern version of this technique is called Angle-Resolved Photoemission Spectroscopy (ARPES) and exploits both conservation laws in order to determine the electronic structure, i.e. energy and momentum of electrons inside the solid. In order to resolve the details crucial for understanding the topical problems of condensed matter physics, three quantities need to be minimized: uncertainty* in photon energy, uncertainty in kinetic energy of photoelectrons and temperature of the sample.
In our approach we combine three recent achievements in the field of synchrotron radiation, surface science and cryogenics. We use synchrotron radiation with tunable photon energy contributing an uncertainty of the order of 1 meV, an electron energy analyzer which detects the kinetic energies with a precision of the order of 1 meV and a He3 cryostat which allows us to keep the temperature of the sample below 1 K. We discuss the exemplary results obtained on single crystals of Sr2RuO4 and some other materials. The electronic structure of this material can be determined with an unprecedented clarity.

The overall goal of this method is to determine the low-energy electronic structure of solids at ultra-low temperatures using Angle-Resolved Photoemission Spectroscopy with synchrotron radiation.

The physical properties of a material are defined by its  electronic structure. Electrons in solids are characterized by energy (&omega;)  and momentum ...

Concurrent Quantitative Conductivity and Mechanical Properties Measurements of Organic Photovoltaic Materials using AFM

Organic photovoltaic (OPV) materials are inherently inhomogeneous at the nanometer scale. Nanoscale inhomogeneity of OPV materials affects performance of photovoltaic devices. Thus, understanding of spatial variations in composition as well as electrical properties of OPV materials is of paramount importance for moving PV technology forward.1,2 In this paper, we describe a protocol for quantitative measurements of electrical and mechanical properties of OPV materials with sub-100 nm resolution. Currently, materials properties measurements performed using commercially available AFM-based techniques (PeakForce, conductive AFM) generally provide only qualitative information. The values for resistance as well as Young's modulus measured using our method on the prototypical ITO/PEDOT:PSS/P3HT:PC61BM system correspond well with literature data. The P3HT:PC61BM blend separates onto PC61BM-rich and P3HT-rich domains. Mechanical properties of PC61BM-rich and P3HT-rich domains are different, which allows for domain attribution on the surface of the film. Importantly, combining mechanical and electrical data allows for correlation of the domain structure on the surface of the film with electrical properties variation measured through the thickness of the film.

Organic photovoltaic (OPV) materials are inherently inhomogeneous at the nanometer scale. Nanoscale inhomogeneity of OPV materials affects performance of photovoltaic devices. In this paper, we describe a protocol for quantitative measurements of electrical and mechanical properties of OPV materials with sub-100 nm resolution.

Organic photovoltaic  (OPV) materials are inherently inhomogeneous at the nanometer scale. Nanoscale  inhomogeneity of OPV materials affects performance ...

Measuring Material Microstructure Under Flow Using 1-2 Plane Flow-Small Angle Neutron Scattering

A new small-angle neutron scattering (SANS) sample environment optimized for studying the microstructure of complex fluids under simple shear flow is presented. The SANS shear cell consists of a concentric cylinder Couette geometry that is sealed and rotating about a horizontal axis so that the vorticity direction of the flow field is aligned with the neutron beam enabling scattering from the 1-2 plane of shear (velocity-velocity gradient, respectively). This approach is an advance over previous shear cell sample environments as there is a strong coupling between the bulk rheology and microstructural features in the 1-2 plane of shear. Flow-instabilities, such as shear banding, can also be studied by spatially resolved measurements. This is accomplished in this sample environment by using a narrow aperture for the neutron beam and scanning along the velocity gradient direction. Time resolved experiments, such as flow start-ups and large amplitude oscillatory shear flow are also possible by synchronization of the shear motion and time-resolved detection of scattered neutrons. Representative results using the methods outlined here demonstrate the useful nature of spatial resolution for measuring the microstructure of a wormlike micelle solution that exhibits shear banding, a phenomenon that can only be investigated by resolving the structure along the velocity gradient direction. Finally, potential improvements to the current design are discussed along with suggestions for supplementary experiments as motivation for future experiments on a broad range of complex fluids in a variety of shear motions.

A shear cell is developed for small-angle neutron scattering measurements in the velocity-velocity gradient plane of shear and is used to characterize complex fluids. Spatially resolved measurements in the velocity gradient direction are possible for studying shear-banding materials. Applications include investigations of colloidal dispersions, polymer solutions, and self-assembled structures.

A new small-angle neutron scattering (SANS) sample environment optimized for studying the microstructure of complex fluids under simple shear flow is ...

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric vehicles.1,2 However, many challenges, such as energy density and battery lifetimes, need to be overcome before this particular battery technology can be widely implemented in such applications.3 This research is challenging, and we outline a method to address these challenges using in situ NPD to probe the crystal structure of electrodes undergoing electrochemical cycling (charge/discharge) in a battery. NPD data help determine the underlying structural mechanism responsible for a range of electrode properties, and this information can direct the development of better electrodes and batteries.
We briefly review six types of battery designs custom-made for NPD experiments and detail the method to construct the &#8216;roll-over&#8217; cell that we have successfully used on the high-intensity NPD instrument, WOMBAT, at the Australian Nuclear Science and Technology Organisation (ANSTO). The design considerations and materials used for cell construction are discussed in conjunction with aspects of the actual in situ NPD experiment and initial directions are presented on how to analyze such complex in situ data.

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

We describe the design and construction of an electrochemical cell for the examination of electrode materials using in situ neutron powder diffraction (NPD). We briefly comment on alternate in situ NPD cell designs and discuss methods for the analysis of the corresponding in situ NPD data produced using this cell.

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric ...

Using Synchrotron Radiation Microtomography to Investigate Multi-scale Three-dimensional Microelectronic Packages

Synchrotron radiation micro-tomography (SR&#181;T) is a non-destructive three-dimensional (3D) imaging technique that offers high flux for fast data acquisition times with high spatial resolution. In the electronics industry there is serious interest in performing failure analysis on 3D microelectronic packages, many which contain multiple levels of high-density interconnections. Often in tomography there is a trade-off between image resolution and the volume of a sample that can be imaged. This inverse relationship limits the usefulness of conventional computed tomography (CT) systems since a microelectronic package is often large in cross sectional area 100-3,600 mm2, but has important features on the micron scale. The micro-tomography beamline at the Advanced Light Source (ALS), in Berkeley, CA USA, has a setup which is adaptable and can be tailored to a sample&#39;s properties, i.e., density, thickness, etc., with a maximum allowable cross-section of 36 x 36 mm. This setup also has the option of being either monochromatic in the energy range ~7-43 keV or operating with maximum flux in white light mode using a polychromatic beam. Presented here are details of the experimental steps taken to image an entire 16 x 16 mm system within a package, in order to obtain 3D images of the system with a spatial resolution of 8.7 &#181;m all within a scan time of less than 3 min. Also shown are results from packages scanned in different orientations and a sectioned package for higher resolution imaging. In contrast a conventional CT system would take hours to record data with potentially poorer resolution. Indeed, the ratio of field-of-view to throughput time is much higher when using the synchrotron radiation tomography setup. The description below of the experimental setup can be implemented and adapted for use with many other multi-materials.

For this study synchrotron radiation micro-tomography, a non-destructive three-dimensional imaging technique, is employed to investigate an entire microelectronic package with a cross-sectional area of 16 x 16 mm. Due to the synchrotron&#39;s high flux and brightness the sample was imaged in just 3 min&#160;with an 8.7 &#181;m spatial resolution.

Synchrotron radiation micro-tomography (SR&#181;T) is a non-destructive three-dimensional (3D) imaging technique that offers high flux for fast data ...

Recombination Dynamics in Thin-film Photovoltaic Materials via Time-resolved Microwave Conductivity

A method for investigating recombination dynamics of photo-induced charge carriers in thin film semiconductors, specifically in photovoltaic materials such as organo-lead halide perovskites is presented. The perovskite film thickness and absorption coefficient are initially characterized by profilometry and UV-VIS absorption spectroscopy. Calibration of both laser power and cavity sensitivity is described in detail. A protocol for performing Flash-photolysis Time Resolved Microwave Conductivity (TRMC) experiments, a non-contact method of determining the conductivity of a material, is presented. A process for identifying the real and imaginary components of the complex conductivity by performing TRMC as a function of microwave frequency is given. Charge carrier dynamics are determined under different excitation regimes (including both power and wavelength). Techniques for distinguishing between direct and trap-mediated decay processes are presented and discussed. Results are modelled and interpreted with reference to a general kinetic model of photoinduced charge carriers in a semiconductor. The techniques described are applicable to a wide range of optoelectronic materials, including organic and inorganic photovoltaic materials, nanoparticles, and conducting/semiconducting thin films.

A Time Resolved Microwave Conductivity technique for investigating direct and trap-mediated recombination dynamics and determining carrier mobilities of thin film semiconductors is presented here.

A method for investigating recombination dynamics of photo-induced charge carriers in thin film semiconductors, specifically in photovoltaic materials ...

Electrospinning of Photocatalytic Electrodes for Dye-sensitized Solar Cells

This work demonstrates a protocol to fabricate a fiber-based photoanode for dye-sensitized solar cells, consisting of a light-scattering layer made of electrospun titanium dioxide nanofibers (TiO2-NFs) on top of a blocking layer made of commercially available titanium dioxide nanoparticles (TiO2-NPs). This is achieved by first electrospinning a solution of titanium (IV) butoxide, polyvinylpyrrolidone (PVP), and glacial acetic acid in ethanol to obtain composite PVP/TiO2 nanofibers. These are then calcined at 500 &#176;C to remove the PVP and to obtain pure anatase-phase titania nanofibers. This material is characterized using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). The photoanode is prepared by first creating a blocking layer through the deposition of a TiO2-NPs/terpineol slurry on a fluorine-doped tin oxide (FTO) glass slide using doctor blading techniques. A subsequent thermal treatment is performed at 500 &#176;C. Then, the light-scattering layer is formed by depositing a TiO2-NFs/terpineol slurry on the same slide, using the same technique, and calcinating again at 500 &#176;C. The performance of the photoanode is tested by fabricating a dye-sensitized solar cell and measuring its efficiency through J-V curves under a range of incident light densities, from 0.25-1 Sun.

The overall goal of this project was to use electrospinning to fabricate a photoanode with improved performance for dye-sensitized solar cells.

This work demonstrates a protocol to fabricate a fiber-based photoanode for dye-sensitized solar cells, consisting of a light-scattering layer made of ...

Dielectric RheoSANS &#8212; Simultaneous Interrogation of Impedance, Rheology and Small Angle Neutron Scattering of Complex Fluids

A procedure for the operation of a new dielectric RheoSANS instrument capable of simultaneous interrogation of the electrical, mechanical and microstructural properties of complex fluids is presented. The instrument consists of a Couette geometry contained within a modified forced convection oven mounted on a commercial rheometer. This instrument is available for use on the small angle neutron scattering (SANS) beamlines at the National Institute of Standards and Technology (NIST) Center for Neutron Research (NCNR). The Couette geometry is machined to be transparent to neutrons and provides for measurement of the electrical properties and microstructural properties of a sample confined between titanium cylinders while the sample undergoes arbitrary deformation. Synchronization of these measurements is enabled through the use of a customizable program that monitors and controls the execution of predetermined experimental protocols. Described here is a protocol to perform a flow sweep experiment where the shear rate is logarithmically stepped from a maximum value to a minimum value holding at each step for a specified period of time while frequency dependent dielectric measurements are made. Representative results are shown from a sample consisting of a gel composed of carbon black aggregates dispersed in propylene carbonate. As the gel undergoes steady shear, the carbon black network is mechanically deformed, which causes an initial decrease in conductivity associated with the breaking of bonds comprising the carbon black network. However, at higher shear rates, the conductivity recovers associated with the onset of shear thickening. Overall, these results demonstrate the utility of the simultaneous measurement of the rheo-electro-microstructural properties of these suspensions using the dielectric RheoSANS geometry.

Dielectric RheoSANS &amp;#8212; Simultaneous Interrogation of Impedance, Rheology and Small Angle Neutron Scattering of Complex Fluids

Here, we present a procedure for the measurement of simultaneous impedance, rheology and neutron scattering from soft matter materials under shear flow.

A procedure for the operation of a new dielectric RheoSANS instrument capable of simultaneous interrogation of the electrical, mechanical and ...

Simultaneous Multi-surface Anodizations and Stair-like Reverse Biases Detachment of Anodic Aluminum Oxides in Sulfuric and Oxalic Acid Electrolyte

After reporting on the two-step anodization, nanoporous anodic aluminum oxides (AAOs) have been widely utilized in the versatile fields of fundamental sciences and industrial applications owing to their periodic arrangement of nanopores with relatively high aspect ratio. However, the techniques reported so far, which could be only valid for mono-surface anodization, show critical disadvantages, i.e., time-consuming as well as complicated procedures, requiring toxic chemicals, and wasting valuable natural resources. In this paper, we demonstrate a facile, efficient, and environmentally clean method to fabricate nanoporous AAOs in sulfuric and oxalic acid electrolytes, which can overcome the limitations that result from conventional AAO fabricating methods. First, plural AAOs are produced at one time through simultaneous multi-surfaces anodization (SMSA), indicating mass-producibility of the AAOs with comparable qualities. Second, those AAOs can be separated from the aluminum (Al) substrate by applying stair-like reverse biases (SRBs) in the same electrolyte used for the SMSAs, implying simplicity and green technological characteristics. Finally, a unit sequence consisting of the SMSAs sequentially combined with SRBs-based detachment can be applied repeatedly to the same Al substrate, which reinforces the advantages of this strategy and also guarantees the efficient usage of natural resources.

A protocol for fabricating nanoporous anodic aluminum oxides via simultaneous multi-surfaces anodization followed by stair-like reverse biases detachments is presented. It can be applied repeatedly to the same aluminum substrate, exhibiting a facile, high-yield, and environmentally clean strategy.

After reporting on the two-step anodization, nanoporous anodic aluminum oxides (AAOs) have been widely utilized in the versatile fields of fundamental ...

Experimental Methods for Spin- and Angle-Resolved Photoemission Spectroscopy Combined with Polarization-Variable Laser

The goal of this protocol is to present how to perform spin- and angle-resolved photoemission spectroscopy combined with polarization-variable 7-eV laser (laser-SARPES), and demonstrate a power of this technique for studying solid state physics. Laser-SARPES achieves two great capabilities. Firstly, by examining orbital selection rule of linearly polarized lasers, orbital selective excitation can be carried out in SAPRES experiment. Secondly, the technique can show full information of a variation of the spin quantum axis as a function of the light polarization. To demonstrate the power of the collaboration of these capabilities in laser-SARPES, we apply this technique for the investigations of spin-orbit coupled surface states of Bi2Se3. This technique affords to decompose spin and orbital components from the spin-orbit coupled wavefunctions. Moreover, as a representative advantage of using the direct spin detection collaborated with the polarization-variable laser, the technique unambiguously visualizes the light polarization dependence of the spin quantum axis in three-dimension. Laser-SARPES dramatically increases a capability of photoemission technique.

Here, we combine polarization-variable 7-eV laser with spin- and angle-resolved photoemission technique to visualize the spin-orbital coupling effect in solid states.

The goal of this protocol is to present how to perform spin- and angle-resolved photoemission spectroscopy combined with polarization-variable 7-eV laser ...