This work is founded by the German Research Foundation (DFG) (Contract CH 943/2-1). The authors would like to thank Wolfgang Dittus, and Stefan Paetel from Zentrum f&uuml;r Sonnenenergie- und Wasserstoff-Forschung Baden-W&uuml;rttemberg for preparing the CIGS absorber layer for this work.

1. CIGS Layer Deposition
<ol>
 <li>Sputter-deposit 500 nm of molybdenum (back contact layer) onto a 3 mm thick soda lime glass substrate (SLG).</li>
 <li>Co-evaporate 2 &mu;m of CIGS in an inline multistage CIGS process 24. The obtained CIGS layer deposited on Mo back contact is shown in Figure 1.</li>
 <li>Measure the integral composition of CIGS layer by X-ray fluorescence spectrometry (XRF). The obtained CIGS composition is shown in Table 1.</li>
</ol>
2. Site-specific Samples Fabrication for APT Analysis
<ol>
 <li>Cut a TEM Mo grid into two halves in order to obtain a row of several pins, being the support for the later specimens. Mount the TEM half-grid onto a holder and taper the ends of the pins by electropolishing in 5 wt. % NaOH down to a tip diameter &lt;2 &mu;m. The process can be reasonable controlled using a stereoscope. Then mount the electropolished grid onto another holder that is optimized for sequential FIB, TEM, EBSD, and APT characterization.</li>
 <li>Mill two trenches into the CIGS thin-film using FIB to get an undercut (Figure 2a). Make a first free-cut on the left side of the chunk.</li>
 <li>Attach the micromanipulator to the chunk by depositing a Pt weld by ion-beam induced chemical vapor deposition. Then, make the final free-cut on the opposite site and lift-out the free-standing chunk (Figure 2b).</li>
 <li>Cut now the sharp pins of the TEM Mo half-grid to a wedge (2-3 &mu;m in diameter) having a good joint for the extracted chunk. Mount the chunk on the pins using Pt deposition (Figure 2c). Make a free-cut to finally obtain only a small part of the chunk (around 2 &mu;m) on the top of the Mo pin. Afterwards mount the grid holder upside down and fill the gap between the Mo pin and the mounted piece with Pt. Pursue the same procedure with the remaining chunk. For more details about the lift-out procedure, the reader may consult the following references 18,25.</li>
 <li>Place the grid upright and clean the cross-section of the chunk (choose the site with thinner Pt weld) by using a low accelerating voltage and beam current (5 kV and &lt;50 pA) in the FIB. Thus one gets a smooth surface and less contamination due to Ga+ implantation, which is required for EBSD measurements.</li>
 <li>From the EBSD measurement performed on the cross-section choose a GB of interest. The orientation of the GB is preferable to be perpendicular with respect to the analysis direction in the atom probe (z-axis) to reduce the local magnification effect 26, which is described more in detail in discussion part. An appropriate area with a GB is highlighted in Figure 2d.</li>
 <li>Perform an annular milling in the area of the GB selected in step 2.6) to form a sharp tip. The radius of curvature should be small enough (&lt;100 nm) for further TEM investigations. To reach this goal, reduce the inner diameter of the annular milling pattern step by step (Figure 2e) and concomitantly visualize the tip shaping by secondary electron (SE). Thus one can correct beam shifts or adjust the milling pattern to remove irregularities on the tip like ripple or redeposition of material originating from different sputter yields, shadowing effects etc.</li>
 <li>Localize the precise position of the GBs with respect to the apex of the tip by using the TEM tool (see Figure 2f), knowing that compared with other materials (like superalloys) the CIGS GBs are not visible in SEM.</li>
 <li>Knowing precisely where the GB is located within the APT tip, transfer the specimen back to the FIB and continue to mill the sample to situate the GB at maximum 200 nm below the apex of the tip. At this stage, the milling is done at very low kV (5 kV) and low current (&lt;50 pA). Indeed, the goal is not only to localize the GB closer to the apex of the tip, but also to minimize the Ga+ damage of the APT tip during this procedure. Concomitantly to the low-kV milling, visualize the shape of the APT tip in SEM and control the amount of the material which should be removed from the apex of the tip (Figure 2g).</li>
 <li>Transfer again the specimen to the TEM and check the position of the GB with respect to the apex of the tip. Make an overview image of the specimen (Figure 2h) to obtain precise knowledge about the GB position, the evolution of the specimen diameter and the half shank-angle. This is necessary to achieve an optimal reconstruction of the APT data. Furthermore, use low magnifications and reduced exposure times to minimize electron-beam induced damages and C contamination which can lead to a higher failure rate in the APT measurements.</li>
</ol>
3. APT Analysis in a CAMECA LEAP 3000X HR System
<ol>
 <li>Mount the specimen in the APT holder. Then, mount the specimen puck in one of the four carousels available.</li>
 <li>Insert the carousel containing the specimen puck inside the load lock and start pumping the load lock. When the vacuum inside the load lock is ~ 10-7 Torr, insert the carousel inside the buffer chamber.</li>
 <li>After waiting ca. 1 hr to restore the vacuum in the buffer chamber (~7x10-9 Torr), transfer the specimen from the buffer chamber to the main analysis chamber. This is done with a horizontal transfer rod, which is a manually operated device.</li>
 <li>Before starting the measurement inside the APT, cool down the temperature to 60 K. This low temperature will avoid the diffusion of the atoms at the surface of the specimen during the analysis. We note here that 60 K is the set temperature and not the real temperature measured on the APT tip, which should be higher due to the laser heat of the specimen. As proposed by Kellog et al. 27, this temperature can be estimated by taking into account the relative charge-state-ratio. Unfortunately, in this work the real temperature of the tips couldn't be calculated mainly because the field evaporation of the CIGS material is unknown.</li>
 <li>APT experiments are carried out in laser mode using a green laser with a wavelength of about 532 nm and 12 psec pulse length.</li>
</ol>
4. Reconstruction of APT Data
<ol>
 <li>Open the RHIT file (raw data directly obtained after APT measurements) with CAMECA's Integrated Visualization and Analysis Software (IVAS 3.6.2) 28 generally used to reconstruct the 3D map.</li>
 <li>Perform the reconstruction of the 3D map using the following eight steps 28:
 <ol>
 <li>Step 1- setup which is a read-only pane giving all the details about the nature and the content of the selected study.</li>
 <li>Step 2- select ion sequence range. This step defines the ion-sequence range relative to specimen-voltage to be selected in the reconstructing data.</li>
 <li>Step 3- select detector ROI. This step gives the opportunity to remove the ions located outside the detector ROI (black ellipse on the detector event histogram).</li>
 <li>Step 4- TOF corrections. This step computes the voltage, the time-of-flight (TOF), and the planarity of the detector ('bowl correction') corrections for the analysis.</li>
 <li>Step 5- Mass calibration. The measured peak position in the analyzed mass spectrum is calibrated with known isotope/charge states.</li>
 <li>Step 6- Ranged ion assignment. In this step the peaks in the mass spectrum are assigned to element isotope ranges.</li>
 <li>Step 7- Reconstruction. This step applies one of three reconstruction methods to the data acquired: voltage method, shank-angle method or tip-profile method. The last one is used in current study to reconstruct our 3D-map. This method requires an SEM or TEM image of the tip, as shown in Figure 2g and Figure 2h. The tip radius at any point in the reconstruction is defined by a linear interpolation between a series of points defined in the SEM image.</li>
 <li>Step 8- Confirmation. In this step, the preview created in the reconstruction tab is converted to a saved analysis.</li>
 </ol>
 </li>
</ol>

<ol>
	<li>Stanbery, B. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper+indium+selenides+and+related+materials+for+photovoltaic+devices.">Copper indium selenides and related materials for photovoltaic devices.</a> Crit. Rev. Solid State. 27, 73-117 (2002).</li><li>Kemell, M., Ritala, M., Leskel&#228;, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thin+film+deposition+methods+for+CuInSe2+solar+cells.">Thin film deposition methods for CuInSe2 solar cells.</a> Crit. Rev. Solid State. 30, 1-31 (2005).</li><li>Kazmerski, L. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solar+photovoltaics+R&amp;D+at+the+tipping+point:+a+2005+technology+overview.">Solar photovoltaics R&amp;D at the tipping point: a 2005 technology overview.</a> J. Electron Spectrosc. 150 (2-3), 105-135 (2006).</li><li>Sadewasser, S., Glatzel, T., Schuler, S., Nishiwaki, S., Kaigawa, R., Lux-Steiner, M. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kelvin+probe+force+microscopy+for+the+nano+scale+characterization+of+chalcopyrite+solar+cell+materials+and+devices.">Kelvin probe force microscopy for the nano scale characterization of chalcopyrite solar cell materials and devices.</a> Thin Solid Films. 431-432, 257-261 (2003).</li><li>Jiang, C. S., Noufi, R., AbuShama, J. A., Ramanathan, K., Moutinho, H. R., Pankow, J., Al-Jassim, M. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Local+built-in+potential+on+grain+boundary+of+Cu(In,Ga)Se2+thin-films.">Local built-in potential on grain boundary of Cu(In,Ga)Se2 thin-films.</a> Appl. Phys. Lett. 84, 3477-1-3477-3 (2004).</li><li>Abou-Ras, D., Koch, C. T., K&#252;stner, V., van Aken, P. A., Jahn, U., Contreras, M. A., Caballero, R., Kaufmann, C. A., Scheer, R., Unold, T., Schock, H. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Grain-boundary+types+in+chalcopyrite-type+thin+films+and+their+correlations+with+film+texture+and+electrical+properties.">Grain-boundary types in chalcopyrite-type thin films and their correlations with film texture and electrical properties.</a> Thin Solid Films. 517, 2545-2549 (2009).</li><li>Nichterwitz, M., Abou-Ras, D., Sakurai, K., Bundesmann, J., Unold, T., Scheer, R., Schock, H. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+grain+boundaries+on+current+collection+in+Cu(In,Ga)Se2+thin-film+solar+cells.">Influence of grain boundaries on current collection in Cu(In,Ga)Se2 thin-film solar cells.</a> Thin Solid Films. 517, 2554-2557 (2009).</li><li>Abou-Ras, D., Schorr, S., Schock, H. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Grain+sizes+and+grain+boundaries+in+chalcopyrite-type+thin+films.">Grain sizes and grain boundaries in chalcopyrite-type thin films.</a> J. Appl. Cryst. 40, 841-848 (2007).</li><li>Niles, D. W., Al-Jassim, M., Ramanathan, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+observation+of+Na+and+O+impurities+at+grain+surfaces+of+CuInSe2+thin+films.">Direct observation of Na and O impurities at grain surfaces of CuInSe2 thin films.</a> J. Vac. Sci. Technol. A. 17, 291-296 (1998).</li><li>Rockett, A., Granath, K., Asher, S., Al Jassim, M. M., Hasoon, F., Matson, R., Basol, B., Kapur, V., Britt, J. S., Gillespie, T., Marshall, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Na+incorporation+in+Mo+and+CuInSe2+from+production+processes.">Na incorporation in Mo and CuInSe2 from production processes.</a> Sol. Energy. 59, 255-264 (1999).</li><li>Heske, C., Eich, D., Fink, R., Umbach, E., Kakar, S., van Buuren, T., Bostedt, C., Terminello, L. J., Grush, M. M., Callcott, T. A., Himpsel, F. J., Ederer, D. L., Perera, R. C. C., Riedl, W., Karg, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Localization+of+Na+impurities+at+the+buried+CdS/Cu(In,+Ga)Se2+heterojunction.">Localization of Na impurities at the buried CdS/Cu(In, Ga)Se2 heterojunction.</a> Appl. Phys. Lett. 75, 2082-2084 (1999).</li><li>Braunger, D., Hariskos, D., Bilger, G., Rau, U., Schock, H. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+Na+on+the+growth+of+polycrystalline+Cu(In,Ga)Se2+thin+films.">Influence of Na on the growth of polycrystalline Cu(In,Ga)Se2 thin films.</a> Thin Solid Films. 361, 161-166 (2000).</li><li>Cerezo, A., Godfrey, T. J., Sijbrandij, S. J., Smith, G. D. W., Warren, P. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Performance+of+an+energy-compensated+three-dimensional+atom+probe.">Performance of an energy-compensated three-dimensional atom probe.</a> Rev. Sci. Instrum. 69, 49-58 .</li><li>Blavette, D., Bostel, A., Sarrau, J. M., Deconihout, B., Menand, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+atom-probe+for+three+dimensional+tomography.">An atom-probe for three dimensional tomography.</a> Nature. 363, 432-435 (1993).</li><li>Gault, B., Vurpillot, F., Vella, A., Gilbert, M., Menand, A., Blavette, D., Deconihout, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+of+a+femtosecond+laser+assisted+tomographic+atom+probe.">Design of a femtosecond laser assisted tomographic atom probe.</a> Rev. Sci. Instrum. 77, 043705-1-043705-8 (2006).</li><li>Kelly, T. F., Miller, M. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atom+probe+tomography.">Atom probe tomography.</a> Rev. Sci. Instrum. 78, 031101-1-031101-20 (2007).</li><li>Thompson, K., Lawrence, D., Larson, D. J., Olson, J. D., Kelly, T. F., Gorman, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+site-specific+specimen+preparation+for+atom+probe+tomography.">In situ site-specific specimen preparation for atom probe tomography.</a> Ultramicroscopy. 107 (2-3), 131-139 (2007).</li><li>Cadel, E., Barreau, N., Kessler, J., Pareige, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atom+probe+study+of+sodium+distribution+in+polycristalline+Cu(In,Ga)Se2+thin+film.">Atom probe study of sodium distribution in polycristalline Cu(In,Ga)Se2 thin film.</a> Acta Material. 58, 2634-2637 (2010).</li><li>Schlesiger, R., Oberdorfer, C., W&#252;rz, R., Greiwe, G., Stender, P., Artmeier, M., Pelka, P., Spaleck, F., Schmitz, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+of+a+laser-assisted+tomographic+atom+probe+at+M&#252;nster+University.">Design of a laser-assisted tomographic atom probe at M&#252;nster University.</a> Rev. Sci. Instr. 81, 043703 (2010).</li><li>Cojocaru-Mir&#233;din, O., Choi, P., Abou-Ras, D., Schmidt, S. S., Caballero, R., Raabe, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+grain+boundaries+in+Cu(In,Ga)Se2+films+using+atom-probe+tomography.">Characterization of grain boundaries in Cu(In,Ga)Se2 films using atom-probe tomography.</a> IEEE J. Photovolt. 1 (2), 207-212 (2011).</li><li>Cojocaru-Mir&#233;din, O., Choi, P., Wuerz, R., Raabe, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atomic-scale+characterization+of+the+CdS/CuInSe2+interface+in+thin-film+solar+cells.">Atomic-scale characterization of the CdS/CuInSe2 interface in thin-film solar cells.</a> Appl. Phys. Lett. 98, 103504-1-103504-3 (2011).</li><li>Couzinie-Devy, F., Cadel, E., Barreau, N., Arzel, L., Pareige, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atom+probe+study+of+Cu-poor+to+Cu-rich+transition+during+Cu(In,Ga)Se2+growth.">Atom probe study of Cu-poor to Cu-rich transition during Cu(In,Ga)Se2 growth.</a> Appl. Phys. Lett. 99, 232108-1-232108-3 (2011).</li><li>Voorwinden, G., Jackson, P., Kniese, R., Powalla, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-line+Cu(In,Ga)Se2+co-evaporation+process+on+30+cm+x+30+cm+substrates+with+multiple+deposition+stages.">In-line Cu(In,Ga)Se2 co-evaporation process on 30 cm x 30 cm substrates with multiple deposition stages.</a> , 2115-2118 (2007).</li><li>Miller, M. K., Russell, K. F., Thompson, K., Alvis, R., Larson, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Review+of+atom+probe+FIB-based+specimen+preparation+methods.">Review of atom probe FIB-based specimen preparation methods.</a> Microscopy Microanal. 13 (6), 428-436 (2007).</li><li>J, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modeling+image+distortions+in+3DAP.">Modeling image distortions in 3DAP.</a> Microscopy and Microanalysis. 10 (3), 384-390 (2008).</li><li>Kellog, G. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determining+the+field+emitter+temperature+during+laser+irradiation+in+the+pulsed+laser+atom+probe.">Determining the field emitter temperature during laser irradiation in the pulsed laser atom probe.</a> J. Appl. Phys. 52, 5320 (1981).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> IVASTM 3.6.2 User Guide 2012. , (2012).</li><li>Persson, C., Zunger, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Compositionally+induced+valence-band+offset+at+the+grain+boundary+of+polycrystalline+chalcopyrites+creates+a+hole+barrier.">Compositionally induced valence-band offset at the grain boundary of polycrystalline chalcopyrites creates a hole barrier.</a> Appl. Phys. Lett. 87, 211904-1-211904-3 (2005).</li><li>Zhang, S. B., Wei, S. -. H., Zunger, A., Katayama-Yoshida, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Defect+physics+of+the+CuInSe2+chalcopyrite+semiconductor.">Defect physics of the CuInSe2 chalcopyrite semiconductor.</a> Phys. Rev. B. 57, 9642-9656 (1998).</li><li>Cahn, J. W., Johnson, W. C., Blakely, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Interfacial Segregation. , 3-23 (1979).</li><li>Miller, M. K., Jayaram, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Some+factors+affecting+analysis+in+atom+probe.">Some factors affecting analysis in atom probe.</a> Surf. Sci. 266, 458-462 (1992).</li><li>Wuerz, R., Eicke, A., Kessler, F., Paetel, S., Efimenko, S., Schlegel, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CIGS+thin-film+solar+cells+and+modules+on+enamelled+steel+substrates.">CIGS thin-film solar cells and modules on enamelled steel substrates.</a> Sol. Energy. 100, 132-137 (2012).</li><li>De Geuser, F., Lefebvre, W., Danoix, F., Vurpillot, F., Forbord, B., Blavette, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+improved+reconstruction+procedure+for+the+correction+of+local+magnification+effects+in+three-dimensional+atom-probe.">An improved reconstruction procedure for the correction of local magnification effects in three-dimensional atom-probe.</a> Surf. Interf. Anal. 39, 268-272 (2007).</li><li>Kingham, D. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+post-ionization+of+field+evaporated+ions:+A+theoretical+explanation+of+multiple+charge+states.">The post-ionization of field evaporated ions: A theoretical explanation of multiple charge states.</a> Surf. Sci. 116, 273-301 (1982).</li><li>Letellier, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Etude des joints de grains et interphases dans les superalliages Astroloy par microscopie electronique et tomographie atomique [dissertation]. , (1994).</li><li>Hoummada, I., Mangelinck, K., Chow, D., Lee, J., Bernardini, <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Original+methods+for+diffusion+measurements+in+polycrystalline+thin-films.">Original methods for diffusion measurements in polycrystalline thin-films.</a> Defect and Diffusion Forum. 322, 129-150 (2012).</li></ol>

The authors have nothing to disclose.

In the current work, we have presented APT results on a random HAGB in CIGS, a compound semiconductor material used for photovoltaic application. Furthermore, we have also shown that APT in conjunction with complementary techniques, such as EBSD and TEM, is a powerful tool to elucidate the structure-composition properties relationship for the CIGS solar cells. Unfortunately, the correlation between APT and EDX/EELS in TEM was not possible because firstly, EDX/EELS has not sufficient resolution to detect low Na and O conc...

Thin-film solar cells based on the chalcopyrite-structured compound semiconductor Cu(In,Ga)Se2 (CIGS) as the absorber material have been under development for more than two decades because of their high efficiency, radiation hardness, long-term stable performance, and low production costs 1-3. These solar cells can be fabricated with only little material consumption due to the favorable optical properties of the CIGS absorber layer, namely, a direct bandgap and a high absorption coefficient 1,2. Absorber films of only a few micrometers in thickness are sufficient to generate a high photocurrent. Since the diffusion paths of photogenerated charge carriers to the electrodes are relatively short, CIGS absorbers can be produced in polycrystalline form. The maximum efficiency of a Cu(In,Ga)Se2 (CIGS) solar cell achieved so far is 20.4% 4, which is the highest value among all thin-film solar cells.
To further establish the CIGS thin-film photovoltaic technology, both the reduction of production costs and the enhancement of solar cell efficiency are essential. The latter is strongly dependent on the microstructure and chemical composition of the CIGS absorber layer. Internal interfaces, in particular grain boundaries (GBs) within the absorber, play a pivotal role, as they can affect the transport of photogenerated charge carriers.
One of the main unresolved issues with respect to CIGS solar cells is the benign nature of CIGS GBs, i.e. polycrystalline CIGS absorber films yield outstanding cell efficiencies despite a high density of GBs and lattice defects.
Several authors studied GBs in solar-grade CIGS films with respect to their electrical properties 5,6, character and misorientation 7-9 as well as impurity segregation 10-13. However, no clear link between these properties could be established so far. In particular, there is a substantial lack of information regarding the local chemical composition and impurity content of the GBs.
In the past two decades, Atom Probe Tomography (APT) has emerged as one of the promising nano-analytical techniques 14-17. Until recently APT studies of solar cells have been largely restricted by difficulties in the sample preparation process and the limited capability of analyzing semiconductor materials using conventional pulsed-voltage atom probes. These restrictions have been largely overcome by the development of the 'lift-out method' based on focused ion beam (FIB) milling 18 and the introduction of pulsed laser APT 16. Several papers about APT characterization of CIGS solar cells have been published 19-23, which are strongly encouraging for further investigations.
This paper gives a guideline of how to study internal interfaces in CIGS thin-film solar cells by the atom probe tomography technique.

atom probe tomography studies on the cu(in,ga)se2 grain boundaries

Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm).
Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography.
Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells.

Figure 3 shows a side view (x-z slice) elemental map of the random high-angle GB (HAGB) 28.5&deg;-&lt;511&gt;cub selected in Figure 2 by site-specific preparation method. Co-segregation of Na, K, and O at a CIGS HAGB is directly mapped using APT. These impurities most likely diffused out of the SLG substrate into the absorber layer during the deposition of the CIGS layer at ~ 600 &deg;C.
Figure 4a shows the Cu, In, Ga, and Se concen...

Watch this Scientific Journal Video about Atom Probe Tomography Studies on the CuIn,GaSe2 Grain Boundaries at JoVE.com

Atom Probe Tomography Studies on the CuIn,GaSe2 Grain Boundaries

In this work, we describe the use of the atom-probe tomography technique for studying the grain boundaries of the absorber layer in a CIGS solar cell. A novel approach to prepare the atom probe tips containing the desired grain boundary with a known structure is also presented here.

Atom Probe Tomography Studies on the Cu(In,Ga)Se2 Grain Boundaries

Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the ...

atom-probe-tomography-studies-on-the-cuingase2-grain-boundaries

Research

JoVE Journal

Engineering

12.6K Views.  Max-Planck-Institut für Eisenforschung GmbH. In this work, we describe the use of the atom-probe tomography technique for studying the grain boundaries of the absorber layer in a CIGS solar cell. A novel approach to prepare the atom probe tips containing the desired grain boundary with a known structure is also presented here.

Video: Atom Probe Tomography Studies on the CuIn,GaSe2 Grain Boundaries

Scanning-probe Single-electron Capacitance Spectroscopy

The integration of low-temperature scanning-probe techniques and single-electron capacitance spectroscopy represents a powerful tool to study the electronic quantum structure of small systems - including individual atomic dopants in semiconductors. Here we present a capacitance-based method, known as Subsurface Charge Accumulation (SCA) imaging, which is capable of resolving single-electron charging while achieving sufficient spatial resolution to image individual atomic dopants. The use of a capacitance technique enables observation of subsurface features, such as dopants buried many nanometers beneath the surface of a semiconductor material1,2,3. In principle, this technique can be applied to any system to resolve electron motion below an insulating surface.
As in other electric-field-sensitive scanned-probe techniques4, the lateral spatial resolution of the measurement depends in part on the radius of curvature of the probe tip. Using tips with a small radius of curvature can enable spatial resolution of a few tens of nanometers. This fine spatial resolution allows investigations of small numbers (down to one) of subsurface dopants1,2. The charge resolution depends greatly on the sensitivity of the charge detection circuitry; using high electron mobility transistors (HEMT) in such circuits at cryogenic temperatures enables a sensitivity of approximately 0.01 electrons/Hz&frac12; at 0.3 K 5.

Scanning-probe single-electron capacitance spectroscopy facilitates the study of single-electron motion in localized subsurface regions. A sensitive charge-detection circuit is incorporated into a cryogenic scanning probe microscope to investigate small systems of dopant atoms beneath the surface of semiconductor samples.

The integration of low-temperature scanning-probe techniques and single-electron capacitance spectroscopy represents a powerful tool to study the ...

The Measurement of Unsteady Surface Pressure Using a Remote Microphone Probe

Microphones are widely applied to measure pressure fluctuations at the walls of solid bodies immersed in turbulent flows. Turbulent motions with various characteristic length scales can result in pressure fluctuations over a wide frequency range. This property of turbulence requires sensing devices to have sufficient sensitivity over a wide range of frequencies. Furthermore, the small characteristic length scales of turbulent structures require small sensing areas and the ability to place the sensors in very close proximity to each other. The complex geometries of the solid bodies, often including large surface curvatures or discontinuities, require the probe to have the ability to be set up in very limited spaces. The development of a remote microphone probe, which is inexpensive, consistent, and repeatable, is described in the present communication. It allows for the measurement of pressure fluctuations with high spatial resolution and dynamic response over a wide range of frequencies. The probe is small enough to be placed within the interior of typical wind tunnel models. The remote microphone probe includes a small, rigid, and hollow tube that penetrates the model surface to form the sensing area. This tube is connected to a standard microphone, at some distance away from the surface, using a "T" junction. An experimental method is introduced to determine the dynamic response of the remote microphone probe. In addition, an analytical method for determining the dynamic response is described. The analytical method can be applied in the design stage to determine the dimensions and properties of the RMP components.

Here, we present a protocol to measure, with high spatial resolution, the unsteady surface pressure in turbulent flows. This method demonstrates the construction of a remote microphone probe (RMP) and the determination of its frequency-dependent, complex transfer function. An analytical determination of the dynamic response is presented and validated.

Microphones are widely applied to measure pressure fluctuations at the walls of solid bodies immersed in turbulent flows. Turbulent motions with various ...

Microfluidic Imaging Flow Cytometry by Asymmetric-detection Time-stretch Optical Microscopy (ATOM)

Scaling the number of measurable parameters, which allows for multidimensional data analysis and thus higher-confidence statistical results, has been the main trend in the advanced development of flow cytometry. Notably, adding high-resolution imaging capabilities allows for the complex morphological analysis of cellular/sub-cellular structures. This is not possible with standard flow cytometers. However, it is valuable for advancing our knowledge of cellular functions and can benefit life science research, clinical diagnostics, and environmental monitoring. Incorporating imaging capabilities into flow cytometry compromises the assay throughput, primarily due to the limitations on speed and sensitivity in the camera technologies. To overcome this speed or throughput challenge facing imaging flow cytometry while preserving the image quality, asymmetric-detection time-stretch optical microscopy (ATOM) has been demonstrated to enable high-contrast, single-cell imaging with sub-cellular resolution, at an imaging throughput as high as 100,000 cells/s. Based on the imaging concept of conventional time-stretch imaging, which relies on all-optical image encoding and retrieval through the use of ultrafast broadband laser pulses, ATOM further advances imaging performance by enhancing the image contrast of unlabeled/unstained cells. This is achieved by accessing the phase-gradient information of the cells, which is spectrally encoded into single-shot broadband pulses. Hence, ATOM is particularly advantageous in high-throughput measurements of single-cell morphology and texture &#8211; information indicative of cell types, states, and even functions. Ultimately, this could become a powerful imaging flow cytometry platform for the biophysical phenotyping of cells, complementing the current state-of-the-art biochemical-marker-based cellular assay. This work describes a protocol to establish the key modules of an ATOM system (from optical frontend to data processing and visualization backend), as well as the workflow of imaging flow cytometry based on ATOM, using human cells and micro-algae as the examples.

Microfluidic Imaging Flow Cytometry by Asymmetric-detection Time-stretch Optical Microscopy ATOM

This protocol describes the implementation of an asymmetric-detection time-stretch optical microscopy system for single-cell imaging in ultrafast microfluidic flow and its applications in imaging flow cytometry.

Scaling the number of measurable parameters, which allows for multidimensional data analysis and thus higher-confidence statistical results, has been the ...

In Situ Monitoring of the Accelerated Performance Degradation of Solar Cells and Modules: A Case Study for Cu(In,Ga)Se2 Solar Cells

The levelized cost of electricity (LCOE) of photovoltaic (PV) systems is determined by, among other factors, the PV module reliability. Better prediction of degradation mechanisms and prevention of module field failure can consequently decrease investment risks as well as increase the electricity yield. An improved knowledge level can for these reasons significantly decrease the total costs of PV electricity. 
In order to better understand and minimize the degradation of PV modules, the occurring degradation mechanisms and conditions should be identified. This should preferably happen under combined stresses, since modules in the field are also simultaneously exposed to multiple stress factors. Therefore, two 'Combined Stress test with in situ measurement' setups have been designed and constructed. These setups allow the simultaneous use of humidity, temperature, illumination, and electrical biases as independently controlled stress factors on solar cells and minimodules. The setups also allow real-time monitoring of the electrical properties of these samples. This protocol presents these setups and describes the experimental possibilities. Moreover, results obtained with these setups are also presented: various examples about the influence of both deposition and degradation conditions on the stability of thin film Cu(In,Ga)Se2 (CIGS) as well as Cu2ZnSnSe4 (CZTS) solar cells are described. Results on the temperature dependency of CIGS solar cells are also presented.

In Situ Monitoring of the Accelerated Performance Degradation of Solar Cells and Modules: A Case Study for CuIn,GaSe2 Solar Cells

Two &#39;Combined Stress test with in situ measurement&#39; setups, which allow real-time monitoring of accelerated degradation of solar cells and modules, were designed and constructed. These setups allow the simultaneous use of humidity, temperature, electrical biases, and illumination as independently controlled stress factors. The setups and various experiments executed are presented.

The levelized cost of electricity (LCOE) of photovoltaic (PV) systems is determined by, among other factors, the PV module reliability. Better prediction ...

Fabrication of Magnetic Nanostructures on Silicon Nitride Membranes for Magnetic Vortex Studies Using Transmission Microscopy Techniques

Electron and x-ray magnetic microscopies allow for high-resolution magnetic imaging down to tens of nanometers. However, the samples need to be prepared on transparent membranes which are very fragile and difficult to manipulate. We present processes for the fabrication of samples with magnetic micro- and nanostructures with spin configurations forming magnetic vortices suitable for Lorentz transmission electron microscopy and magnetic transmission x-ray microscopy studies. The samples are prepared on silicon nitride membranes and the fabrication consists of a spin coating, UV and electron-beam lithography, the chemical development of the resist, and the evaporation of the magnetic material followed by a lift-off process forming the final magnetic structures. The samples for the Lorentz transmission electron microscopy consist of magnetic nanodiscs prepared in a single lithography step. The samples for the magnetic x-ray transmission microscopy are used for time-resolved magnetization dynamic experiments, and magnetic nanodiscs are placed on a waveguide which is used for the generation of repeatable magnetic field pulses by passing an electric current through the waveguide. The waveguide is created in an extra lithography step.

A protocol for the fabrication of magnetic micro- and nanostructures with spin configurations forming magnetic vortices suitable for transmission electron microscopy (TEM) and magnetic transmission x-ray microscopy (MTXM) studies is presented.

Electron and x-ray magnetic microscopies allow for high-resolution magnetic imaging down to tens of nanometers. However, the samples need to be prepared ...

Fabrication of Robust Nanoscale Contact between a Silver Nanowire Electrode and CdS Buffer Layer in Cu(In,Ga)Se2 Thin-film Solar Cells

Silver nanowire transparent electrodes have been employed as window layers for Cu(In,Ga)Se2 thin-film solar cells. Bare silver nanowire electrodes normally result in very poor cell performance. Embedding or sandwiching silver nanowires using moderately conductive transparent materials, such as indium tin oxide or zinc oxide, can improve cell performance. However, the solution-processed matrix layers can cause a significant number of interfacial defects between transparent electrodes and the CdS buffer, which can eventually result in low cell performance. This manuscript describes how to fabricate robust electrical contact between a silver nanowire electrode and the underlying CdS buffer layer in a Cu(In,Ga)Se2 solar cell, enabling high cell performance using matrix-free silver nanowire transparent electrodes. The matrix-free silver nanowire electrode fabricated by our method proves that the charge-carrier collection capability of silver nanowire electrode-based cells is as good as that of standard cells with sputtered ZnO:Al/i-ZnO as long as the silver nanowires and CdS have high-quality electrical contact. The high-quality electrical contact was achieved by depositing an additional CdS layer as thin as 10 nm onto the silver nanowire surface.

Fabrication of Robust Nanoscale Contact between a Silver Nanowire Electrode and CdS Buffer Layer in CuIn,GaSe2 Thin-film Solar Cells

In this protocol, we describe the detailed experimental procedure for the fabrication of a robust nanoscale contact between a silver nanowire network and CdS buffer layer in a CIGS thin-film solar cell.

Silver nanowire transparent electrodes have been employed as window layers for Cu(In,Ga)Se2 thin-film solar cells. Bare silver nanowire electrodes ...

Visualization of Failure and the Associated Grain-Scale Mechanical Behavior of Granular Soils under Shear using Synchrotron X-Ray Micro-Tomography

The rapid development of X-ray imaging techniques with image processing and analysis skills has enabled the acquisition of CT images of granular soils with high-spatial resolutions. Based on such CT images, grain-scale mechanical behavior such as particle kinematics (i.e., particle translations and particle rotations), strain localization and inter-particle contact evolution of granular soils can be quantitatively investigated. However, this is inaccessible using conventional experimental methods. This study demonstrates the exploration of the grain-scale mechanical behavior of a granular soil sample under triaxial compression using synchrotron X-ray micro-tomography (&#956;CT). With this method, a specially fabricated miniature loading apparatus is used to apply confining and axial stresses to the sample during the triaxial test. The apparatus is fitted into a synchrotron X-ray tomography setup so that high-spatial resolution CT images of the sample can be collected at different loading stages of the test without any disturbance to the sample. With the capability of extracting information at the macro scale (e.g., sample boundary stresses and strains from the triaxial apparatus setup) and the grain scale (e.g., grain movements and contact interactions from the CT images), this procedure provides an effective methodology to investigate the multi-scale mechanics of granular soils.

The protocol describes procedures to acquire high-spatial resolution computed tomography (CT) images of a granular soil during triaxial compression, and to apply image processing techniques to these CT images to explore the grain-scale mechanical behavior of the soil under loading.

The rapid development of X-ray imaging techniques with image processing and analysis skills has enabled the acquisition of CT images of granular soils ...

Improving the Combustion Performance of a Hybrid Rocket Engine using a Novel Fuel Grain with a Nested Helical Structure

A technique to improve the combustion performance of a hybrid rocket engine using a novel fuel grain structure is presented. This technique utilizes the different regression rates of acrylonitrile butadiene styrene and paraffin-based fuels, which increase the exchanges of both matter and energy by swirl flow and recirculation zones formed at the grooves between the adjacent vanes. The centrifugal casting technique is used to cast the paraffin-based fuel into an acrylonitrile butadiene styrene substrate made by three-dimensional printing. Using oxygen as the oxidizer, a series of tests were conducted to investigate the combustion performance of the novel fuel grain. In comparison to paraffin-based fuel grains, the fuel grain with a nested helical structure, which can be maintained throughout the combustion process, showed significant improvement in the regression rate and great potential in improvement of combustion efficiency.

A technique utilizing a solid fuel grain with a novel nested helical structure to improve the combustion performance of a hybrid rocket engine is presented.

A technique to improve the combustion performance of a hybrid rocket engine using a novel fuel grain structure is presented. This technique utilizes the ...

Co-localizing Kelvin Probe Force Microscopy with Other Microscopies and Spectroscopies: Selected Applications in Corrosion Characterization of Alloys

Kelvin probe force microscopy (KPFM), sometimes referred to as surface potential microscopy, is the nanoscale version of the venerable scanning Kelvin probe, both of which measure the Volta potential difference (VPD) between an oscillating probe tip and a sample surface by applying a nulling voltage equal in magnitude but opposite in sign to the tip-sample potential difference. By scanning a conductive KPFM probe over a sample surface, nanoscale variations in surface topography and potential can be mapped, identifying likely anodic and cathodic regions, as well as quantifying the inherent material driving force for galvanic corrosion.
Subsequent co-localization of KPFM Volta potential maps with advanced scanning electron microscopy (SEM) techniques, including back scattered electron (BSE) images, energy dispersive spectroscopy (EDS) elemental composition maps, and electron backscattered diffraction (EBSD) inverse pole figures can provide further insight into structure-property-performance relationships. Here, the results of several studies co-localizing KPFM with SEM on a wide variety of alloys of technological interest are presented, demonstrating the utility of combining these techniques at the nanoscale to elucidate corrosion initiation and propagation.
Important points to consider and potential pitfalls to avoid in such investigations are also highlighted: in particular, probe calibration and the potential confounding effects on the measured VPDs of the testing environment and sample surface, including ambient humidity (i.e., adsorbed water), surface reactions/oxidation, and polishing debris or other contaminants. Additionally, an example is provided of co-localizing a third technique, scanning confocal Raman microscopy, to demonstrate the general applicability and utility of the co-localization method to provide further structural insight beyond that afforded by electron microscopy-based techniques.

Kelvin probe force microscopy (KPFM) measures surface topography and differences in surface potential, while scanning electron microscopy (SEM) and associated spectroscopies can elucidate surface morphology, composition, crystallinity, and crystallographic orientation. Accordingly, the co-localization of SEM with KPFM can provide insight into the effects of nanoscale composition and surface structure on corrosion.

Kelvin probe force microscopy (KPFM), sometimes referred to as surface potential microscopy, is the nanoscale version of the venerable scanning Kelvin ...

Application of Deep Learning-Based Medical Image Segmentation via Orbital Computed Tomography

Recently, deep learning-based segmentation models have been widely applied in the ophthalmic field. This study presents the complete process of constructing an orbital computed tomography (CT) segmentation model based on U-Net. For supervised learning, a labor-intensive and time-consuming process is required. The method of labeling with super-resolution to efficiently mask the ground truth on orbital CT images is introduced. Also, the volume of interest is cropped as part of the pre-processing of the dataset. Then, after extracting the volumes of interest of the orbital structures, the model for segmenting the key structures of the orbital CT is constructed using U-Net, with sequential 2D slices that are used as inputs and two bi-directional convolutional long-term short memories for conserving the inter-slice correlations. This study primarily focuses on the segmentation of the eyeball, optic nerve, and extraocular muscles. The evaluation of the segmentation reveals the potential application of segmentation to orbital CT images using deep learning methods.

Application of Deep Learning-Based Medical Image Segmentation via Orbital Computed Tomography

An object segmentation protocol for orbital computed tomography (CT) images is introduced. The methods of labeling the ground truth of orbital structures by using super-resolution, extracting the volume of interest from CT images, and modeling multi-label segmentation using 2D sequential U-Net for orbital CT images are explained for supervised learning.